Journal of Cleaner Production 54 (2013) 307e314

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Journal of Cleaner Production

journal homepage: www.elsevier.com/locate/jclepro

Cleaner production through using by-product palm stearin to

synthesis alkyd resin for coating applications
Alireza Azimi Nanvaee, Rosiyah Yahya, Seng-Neon Gan*
Faculty of Science, Chemistry Department, University of Malaya, 50603 Kuala Lumpur, Malaysia

a r t i c l e i n f o a b s t r a c t

Article history: This work describes the use of less valuable by-product palm stearin as a partial substituent for valuable
Received 10 June 2012 vegetable oils to polymerize alkyd resins. The fusion process was employed as it consumes lower energy
Received in revised form and has lower chemical pollution, the two main requirements for an environmental friendly process and
17 April 2013
cleaner production, as well as, being more economical production. Four types of alkyd resins based on
Accepted 18 April 2013
the mixture of oils were formulated and synthesized at lab, pilot and industrial scale. The extent and
Available online 10 May 2013
average degree of polymerization were monitored through measuring the acid number and viscosity of
the reaction mixture at various intervals of time. The performance of the synthesized resins for coating
Keywords:
Cleaner production
applications were determined using ASTM D 1640, 4366, 3559, 2794 and 1647. Results indicate that the
Palm stearin alkyd resin synthesized from the by-product palm stearin is a successful alternative to sustain and save
Alkyd resin natural resources, environment, and energy. It can result in a cleaner production compared to solvent
Environment friend process process, the other technique for synthesizing alkyds, which consumes fatty acids and more energy and
Green polymer enters aromatic solvent to the air.
Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction necessitates using alcoholysis technique along with fusion process

(Stoye and Freitag, 1998). This process can use waste or by-products
The current global production system is unsustainable due to of oil plant industries and consumes lower energy compared to
the huge increase in resources used and waste produced (Paredes, solvent process of synthesizing alkyds, which uses expensive oil
2002). Many of the world resources are finite, and wastes are un- fatty acids instead of oils and consumes more energy (Lambourne
avoidable by-products of most human activity. Nowadays, proper and Strivens, 1999). Moreover, solvent process has environment
management of resources usage and industrial wastes is one of the pollution due to aromatic solvent entering to the air (Oldring and
numerous environmental challenges faced by universities and in- Hayward, 1995).
dustries (Jegatheesan et al., 2009). Cleaner production can play a Palm oil, extracted from palm tree, is a versatile plant oil
critical role with respect to influencing changes in production and compared with other vegetable oils (Basiron, 2005). Over the past
consumption patterns. Material replacements and process changes decade palm and palm kernel oils have become important as raw
have the potential not only to bring the production into preventing materials in the world’s oil and fats scene (Kongsager and Reenberg,
or reducing wastes but also they are consistent with environment 2012). Palm oil now takes second place in the list of oils produced
(Huisingh and Gardner Lisa, 1987) and enhancing the efficiency and around the world and will probably overtake soybean oil in another
productivity (Huisingh et al., 1986). 10e15 years (Thai Office of Agriculture Economics, 2006). The
Vegetable oils, green renewable sources, are common raw ma- global demand for palm oil is currently increasing. Rapid devel-
terials in the organic coating industry, especially for alkyd resins opment in the palm oil industries over the recent decade should be
(Pramanik et al., 2012). It is estimated that about one million tones in tandem with the development of its environmental technical
of vegetable oils are used in surface coatings each year (Gunstone knowledge. The palm oil industry is aware of the environmental
et al., 2007). Using vegetable oil for synthesizing alkyd resin pollution and is striving toward quality and environmental con-
servation through ‘sustainable development and cleaner technol-
ogy’ approaches. Palm stearin (PS) is a by-product of palm oil
processing for producing olein and considered less valuable in the
* Corresponding author. Faculty of Science, Chemistry Department, University of
Malaya, 50603 Kuala Lumpur, Malaysia. Tel.: þ60 3 79674241; fax: þ60 3 79674193. palm oil industry. Developing palm oil industry is along with the
E-mail address: [email protected] (S.-N. Gan). huge quantities of PS by-product. Unfortunately, with the exception

0959-6526/$ e see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.jclepro.2013.04.027
308 A.A. Nanvaee et al. / Journal of Cleaner Production 54 (2013) 307e314

of few studies in the field (Gan and Teo, 1999), PS has not received Table 2
adequate attention. The main goal of current paper is to present the Constituents of synthesized alkyd resins.

results of using less valuable PS as partial replacement of linseed oil Alkyds code Raw materials (%)
(LO) and dehydrated castor oil (DCO) for preparing alkyd resin, a PA PE PS DCO LO
cleaner production with an environment friend polymer and wide
DCO100 24.93 13.71 e 61.36 e
applications. This replacement is expected to have desired effects
PSDCO2080 24.93 13.71 12.27 44.09 e
on the characteristics of virgin resins, thus this can lead to both PSDCO4060 24.93 13.71 24.54 36.82 e
environmental protection (environment gain) and cheaper pro- LO100 24.93 13.71 e e 61.36
duction (economic gain). Although a few components of alkyd PSLO2080 24.93 13.71 12.27 e 44.09
PSLO4060 24.93 13.71 24.54 e 36.82
resins are still petroleum based, it was recently shown that alkyd
resin could be made from completely renewable resources (Van
Haveren et al., 2005) and could be known as a green polymer. then cooled to 180 C. In esterification stage, phthalic anhydride
Cleaner production improves : environment by reducing pollution along with the second portion of polyol were added to the mono-
of water, air and land (Ross and Evans, 2003), economic by glyceride mixture. The temperature was raised to 240e245  C and
increasing efficiency and productivity (Narodoslawsky et al., 2008), maintained at this range. The reaction was monitored by periodic
and society by reducing health and safety risks (Tseng, 2013). determination of acid number (AN) of the mixture until to the
desired number of 8e10 mg KOH/g.
2. Experiments
2.3. Pilot plant and industrial scale synthesis
2.1. Materials
In order to fit the lab-bench synthesis data and results for a
Palm stearin was donated by local palm oil mill, Cogins Oleo- workable commercial manufacturing plant, a scale up of the syn-
chemicals Co. Other raw materials were commercial or analytical thesis was carried out first, in pilot plant scale (PSDCO2080 and
grades and were purchased and used without further treatment. PSLO2080 formulations), Fig. 1, and then by industrial scale (Marlyk
DCO and LO were obtained from the local market in the refined Inds. Co., PSDCO4060 and PSLO4060 formulations). All raw mate-
state. Table 1 shows the physicochemical properties of used oils. rials were prepared from local commercial sources where the same
Phthalic anhydride (PA, 99%) was from Laboratory UNILAB RE- raw material sources were used, such that comparison of results
AGENT, lithium hydroxide (monohydrate) from SIGMA, pentaery- will be more reliable.
thritol (PE, 98%) from Aldrich Chemical Company Inc., laboratory In pilot plant and industrial scale, first, the reactor was loaded
reagents from HOPKIN & WILLIAMS LTD, potassium hydroxide from with the oils. The reactor was purged with nitrogen gas for about
R & M Chemicals, and ethanol (95%) from John Kolin Chemicals. 5e15 min before heating was switched on. Nitrogen gas, as an inert
gas, removes the oxygen from within the reactor and prevents
2.2. Preparation of alkyd resins oxidation and colorizing action of atmospheric oxygen by blan-
keting the reacting mixture’s surface. Oxidation and colorizing may
Six alkyd resins were prepared. The recipes are shown in Table 2. result undesired characteristics and too darkening of the final
Each alkyd was designated as PSDCO or PSLO (abbreviation of palm product (resin). The oil was heated with adequate stirring. The
stearin, dehydrated castor oil and linseed oil) and numbers. reactor was well equipped with an anchor impeller to ensure
Numbers indicate the percentage of palm stearin and second oil, proper stirring and mixing. Inert gas bubbling is continued
respectively. For example, PSDCO2080 Alkyd symbol means the throughout the alcoholysis and polymerization.
correspond alkyd is based on the mixture of PS and DCO with 20
and 80 percentage, respectively. All resins were formulated as a 2.3.1. Alcoholysis process
long oil alkyd with 61.36% oil length, according to Patton’s constant A mixture composed of 25% of the pentaerythritol, and all
K (Jones, 2003). In the preparation of alkyd resins (fusion process), lithium hydroxide (as catalyst) was added to the reactor. LiOH is the
two stages are involved. The first stage is alcoholysis and the second alcoholysis catalyst which its amount, based on the dry weight of
stage is esterification. In alcoholysis, while heating the flask, the
blend of oils, first portion of PE and lithium hydroxide (as catalyst)
is charged into the flask and stirred for 10e15 min at room tem-
perature to attain desired reaction mixture (Ekpa and Issac, 2009).
By reacting the oil(s) with polyol at 230e240 C, monoglyceride is
formed. N2 gas is bubbled into the reaction mixture to prevent
oxidation of the oils. The reaction was stopped after one volume of a
sample withdrawn from the reaction mixture becomes soluble in
three volumes of anhydrous methanol. The reaction mixture was

Table 1
Physicochemical properties of used oils.

Property PS DCO LO

Specific gravity (g/cm3@ 30  C) 0.856 0.927 0.929

Free fatty acid (%, as oleic acid) 5.1a 3.0 11.3
Acid value (mgKOH/g) 0.43 6.00 24.50
Saponification value (mgKOH/g) 201.5 186.0 190.0
Iodine value (g I2/100 g) 36 145 155
Hydroxyl value (mgKOH/g) 7.5 12.7 e
a
As palmitic acid. Fig. 1. Schematic of the alkyd resin pilot plant.
 A.A. Nanvaee et al. / Journal of Cleaner Production 54 (2013) 307e314 309

polyol, ranges from 0.01 to 0.15%. Reactor heating was held at 240e mixture which is a good indication of the reaction completion and
245  C along with a good stirring. Adequate agitation is important viscosity measurements of the reaction mixture which is the sec-
to increase the rate of transesterification and maximum conversion ond criterion for monitoring the process evolution and molecular
(Chen et al., 1997). Sample of reaction mixture was withdrawn from weight-structure of the alkyd polymers were also investigated. The
the reactor at 10 min intervals for doing methanol solubility common procedure is to measure the flow time for a 50% solution
test(MST) to ensure the monoglycerides have been formed. At the of withdrawn sample in white spirit from a Ford cup at 20  C.
beginning of the synthesis, when PE, a highly polar compound, and
oil(s), nonpolar compound(s), are mixed, they are incompatible,
and very little reaction takes place. By increasing temperature, as 3. Characterization
soon as a small amount of monoester is produced, the combination
of all three constituents of the reaction mixture become compatible FTIR spectra of the synthesized alkyd resins were obtained using
and the reaction can go ahead faster. All alcoholysis processes took the Perkin Elmer spectrometer model Spectrum RXI. The samples
less than 1 h. In industrial batch alkyd polymerization, usually, it were spread as a thin layer on a KBr cell for recording the IR
takes about 1 h. Four hydroxyl groups of PE are primary alcoholic spectrum from 400 to 4000 cm1 at a resolution of 4 cm1 (Haken
function which are the most active hydroxyl group toward alco- and Iddamalgoda, 1991). Acid number was determined with titri-
holysis and result in very quick transesterification, one of the ad- metric method according to ASTM D 1639 (ASTM, 2003).
vantages of using PE in developed formulations. The oils/PE To determine drying time, hardness, gloss, and chemical resis-
mixture is converted into a mixture of mono., di., and. glyc- tance, except water resistance, the prepared alkyd resins were
erides, unreacted PE and unconverted oils, Scheme 1. The compo- applied by means of a four sided coating film applicator (BYK Co.)
sition of this mixture is highly determined by the oil type, the ratio with slot width of 90 microns onto cleaned glass plates of
of polyol to oil(s), purity of the reactants, catalyst, time, agitation 100  100  3 mm. For these tests, samples were prepared as 55%
and temperature (Lin, 2007). The characteristics of the reaction solution of each alkyd in white spirit with drying catalysts in the
mixture are of great importance in the next step in the synthesis, following amounts : 3 g of drier mixture [lead octoate (93%) and
the polyesterification reaction. In carried out syntheses, no lengthy cobalt octoate (7%)] per 100 g resin solution. For adhesion, me-
mass heterogenous liquid/liquid or liquid/solid system was seen chanical, and water chemical resistance measurements steel plates
during alcoholysis process due to oils mixture and solid PE pres- of 150  70  2 mm were used as substrate. All plates were kept
ence. These observations indicate good miscibility and compati- under standard conditions in a climatized laboratory (23  C and
bility of alcoholysate mixture which is a vital requirement for using relative air humidity of 50%) (ASTM, 2003).
oils mixture to synthesis an acceptable alkyd. The tendency for alkyd based coatings to discoloration is a
common concern all over the organic coatings industry. Natural
2.3.2. Polyesterification process and synthetic binders in exposure to sunlight absorb sun ultraviolet
For polyesterification process the reactor was cooled to 150e radiation and bear degradation reactions which leads to their
160  C and the balance of PE and PA were added and stirred. discoloration (yellowing) (Kockritz and Martin, 2008). To evaluate
Heating was continued up to 240e245  C and maintained at this yellowing resistance of the prepared resins, white air drying gloss
level until the desired acid value and viscosity were reached. The paint was prepared for all resins and their dried film plates were
extent of the reaction was monitored by acid number and viscosity exposed to outdoor environment. Exposure time was 3 months.
determination on samples that are removed from the reaction During exposure period averages of maximum and minimum
mixture at periodic intervals. When the acid number of the resin temperature was 33.4  C and 21.2  C, respectively. The average
reached below 10 mg KOH/g heating was stopped and the reactor relative humidity was 40%. After three months, the difference in
was cooled to temperature below 100  C along with addition of color between the paint films before and after exposures was
some white spirit to thin the resin in order to help the reduction of measured using a BYK-Gardner color guide (45/0 geometry).
the temperature as soon as possible and also facilitating the resin
evacuation into thinning tank. Sampling valve at the bottom of the
4. Results and discussion
reactor was opened to charge the alkyd resin solution in thinning
tank.
4.1. Laboratory synthesis
Polycondensation process carried out successfully with no sig-
nificant problem in the rate of water removed and attaining
4.1.1. FTIR spectroscopy analysis
adequate polymers. Passing the nitrogen gas through the reaction
The FTIR spectra data of the resins indicate the presence of
mixture accelerated the removing of water and reduced the ester-
important linkage such as olefinic double bonds, ester groups, and
ification reaction time to an outstanding extent comparable to that
other characteristic peaks, Table 3. All spectra have common peaks
attains in solvent process. The acidity determination of the reaction
because the structures of all resins are very similar and there is very
small difference between them (Ikhuoria and Okieimen, 2005).

Table 3
Distinguished FTIR peaks of synthesized resins and their corresponding
functional groups.

Peaks (cm1) Functional group

742 Aromatic CeH stretching

980 CeC stretching
1120e1157 Ester CeO stretching
1600e1648 C]C stretching
1755 C]O stretching
2850e2925 Aliphatic CeH stretching
Scheme 1. Transesterification of vegetable oils by PE for synthesizing alkyd resin.
310 A.A. Nanvaee et al. / Journal of Cleaner Production 54 (2013) 307e314

4.1.2. Acid number Table 5

The moderate acid numbers of the resins (Table 4) support their Chemical resistance of dried films of synthesized alkyd Resins.a

reactivity and suitability for coating applications. The alkyd resin Alkyds code Chemical medium
that has acid number of less than 15 is suitable for application of Distilled NaCl (10%) KOH (0.5 N) HCl (10%)
paint, according to literature and experiences (Tracton, 2006). water

DCO100 1 1 4 1
4.1.3. Drying time PSDCO2080 1 1 4 2
Table 4 summarizes the results for drying time of synthesized PSDCO4060 1 1 4 1
resins. All resins show acceptable drying time. Partial replacement LO100 1 1 4 2
PSLO2080 1 1 4 2
of DCO or LO by PS did not have the significant undesired effect on
PSLO4060 1 1 4 2
drying times of synthesized resins. In the drying process of air
a
drying organic coatings the physical drying first occurs, when sol- 1 ¼ completely unaffected, 2 ¼ unaffected, 3 ¼ partially affected, 4 ¼ completely
affected.
vent evaporates and a film is formed. The chemical drying, so-called
autoxidative drying, when unsaturated CeC bonds of oils or fatty
acids react with oxygen, takes place along with physical drying and 4.1.6. Chemical resistance
continues thereafter. The degree and nature of oils or fatty acids The results of chemical resistance test are shown in Table 5.
unsaturation indicate the susceptibility for drying by oxygen ab- Chemical resistance of all resins were good, except for the alkali
sorption and crosslinking to form a solid film (Soucek et al., 2012). resistance. Poor alkali resistance of alkyds is attributed to the
Palm stearin has a very low degree of unsaturation, so, it is expected presence of alkali hydrolysable ester linkages, and oil replacement
that partial replacement of DCO or LO by PS can increase drying does not have sensible effect on this property strongly. Poorest
time of synthesized resins. Results obtained show that partial alkali resistance was exhibited by resin which based on DCO only
replacement has caused small increase in drying time which could which is due to high acid value in DCO. Replacement DCO by PS
be ignored compared to environmental and economical advantages increased the alkali resistance.
attain through using a by-product. Although, only one research has
been reported regarding the partial replacement of oils for alkyd 4.1.7. Yellowing
synthesis (Muralidharan Nair et al., 1981), results of current Results are shown in Fig. 2. Replacement DCO and LO by PS has
research indicate it is applicable to replace high price and more enhanced yellowing resistance of paints. It is known that oils
useful oils, such as DCO and LO, by cheap by-product PS of up to 40% containing linolenic acid are subjected to discoloration because this
without any anxiety regarding drying time and other properties. acid is the main cause of discoloration. Yellowing take places when
conjugated unsaturated hydroperoxides, formed during auto-
4.1.4. Adhesion oxidation reaction, are converted into conjugated unsaturated ke-
Results reveal acceptable adhesion for all the synthesized resins, tones. These unsaturated ketones can produce colored materials
Table 4. However, they do not give significant evidence that could which leads to resin or paint discoloration (Mallegol et al., 2000).
be useful for interpretation regarding the effect of PS replacement LO contains a considerable amount of linolenic acid, thus, its resins
on adhesion characteristic of resins. This can be attributed to this are very sensitive against weathering. Discoloration from DCO
fact that most of the alkyd resins, particularly LO or DCO based based resins had advantages over LO based counterparts, because
counterparts, have good adhesion property, inherently. of absence of linolenic acid. PS does not contain linolenic acid, thus,
replacement of DCO and LO by PS does not have any adverse effects
4.1.5. Hardness test on yellowing resistance of the resin. Yellowing resistance
As shown in Table 4, both drying time and hardness results are enhancement is very significant for LO based resins compared to
parallel to each other and support the conclusion that partial DCO counterparts. Hence partial replacement LO by PS results in
replacement of used oils did not have undesired effects on resins environmentally, technically and economically alkyds.
characteristics (Ikhuoria et al., 2007). The physical properties of a
coating film depend strongly on the chemical type and molecular
structure of its binder. In organic coatings one molecular structural
quality of the binder that can drastically affect the properties of the
films is cross-linking. Binders with more cross-linked chains are
often harder than similar lower cross-linked binders (Dutta and
Karak, 2005). Results show that, although, PS has lower unsatura-
Colour change ( % )

tion than DCO or LO, partial replacement of DCO or LO by PS does

not decrease the cross-linking degree as much as the outstanding
decrease in hardness of the synthesized resins (Amarasinghe et al.,
2012).

Table 4
Physical characteristics of dried films of synthesized alkyd resins.

Alkyds code Acid number Set-to-touch Tack free Hardness (sec)

(mg KOH/g) time (min) time (min)

DCO100 8.5 55 180 18

PSDCO2080 8.5 55 190 17
PSDCO4060 8.3 60 210 17
LO100 8.3 55 175 17
PSLO2080 8.5 55 185 16
Fig. 2. Colour change trend of white gloss paints prepared with synthesized alkyd
PSLO4060 8.6 60 220 15
resins after 3 months natural weathering.
 A.A. Nanvaee et al. / Journal of Cleaner Production 54 (2013) 307e314 311

4.2. Pilot plant and industrial synthesis

4.2.1. Process characteristics

Figs. 3 and 4 show plots of the acid number and viscosity
changes versus polyesterification time for synthesized alkyds. The
time of adding the phthalic anhydride was taken as the beginning
of the polyesterification reaction. As can be seen, the decrease in
acid number and increase in viscosity, both with time, for all resins
follows the usual polyesterification reaction trend (Parsons, 1993).
The extent of polymerization at the end of synthesis process (Pe) for
all alkyds range between 96.5 and 97.3%. Since, the used polyol was
PE, which is a more active polyol than glycerol, the obtained values
for Pe are acceptable compared to values of 75e80% obtained for
esterification of PA and glycerol (Odian, 2004). Towards the end of
the polyesterification, there was an outstanding increase in the
viscosity of all of the resins. This increase occurs not only because of
the joining of long chain polymers but also as a result of CeC double
Fig. 4. (a): acid numberetime, (b): viscosity e time charts for scale-up pilot synthe-
bond networking reactions due to existence of unsaturated moi- sizing PSLO alkyds.
eties exists in the oils, particularly in linseed oil. The second and
more important factor is the possibility of formation of different
and inevitable chemical structures by the hydroxyl groups within ester linkage of the used oil(s). The band corresponding to polyol
PSDCO synthesis process, such as linear esterification, cyclic ester- OH group appears at 3500 cm1. Weak absorption band at this
ification, etherification and a combination of them. region confirms the complete participation of OH groups in the
The overall time for alkyd synthesis, including the alcoholysis formation of alkyd resins. High absorption of this band belongs to
and the polyesteification processes, is long and usually varies from PSDCO2080, due to the existence of some hydroxyl groups in DCO
6 to 10 h (Hernandez et al., 2010). In present study, lab pilot scale chain. By decreasing DCO from PSDCO2080 to PSDCO4060 this
and plant pilot scale synthesis lasted between 7 and 7.5 h, sepa- band becomes weak. Unsaturation of carbonecarbon appeared as a
rately, which is an acceptable time for an economical production for weak band near 1610 cm1. The high degree of similarity between
alkyds. This medium time for production can be contributed to the synthesized resins and commercial control resin indicates that the
formulations, including the highly reactive PE and good viscosity of scaling up of the PSDCO and PSLO resins proceeds in the same
the mixture of the oils. fashion, producing approximately the commercial control resin.
The prepared alkyd resins were tested for acid value, solid content,
4.2.2. Chemical and physical characteristics color, viscosity, solubility and compatibility. Resins were compared
Fig. 5 shows that the FTIR spectra of the synthesized resins to selected commercial conventional alkyd resins with comparable
nearly coincide with the spectra of the control sample, indicating composition, particularly oil length, to the synthesized alkyds.
the scale-up workability of the developed resins. Little difference Table 6 shows that the results obtained in laboratory scale correlate
was seen between the IR spectra of synthesized resins and control with those obtained in pilot plant and industrial scale. The acid
resin, even in the low frequency fingerprint region. Infrared anal- values and the viscosities of the prepared alkyds were comparable
ysis of the synthesized resins shows the expected functionality with those of the reference resin (SETAL 16 LV WS-70). All the resins
present with strong band with a maximum at 1745 cm1 for ester were clear and the color was between six to seven Gardner. The
carbonyl group stretching is the characteristic band for alkyds. A colors of the alkyds with higher percentage of PS, i.e. PSDCO4060
sharp and broad absorption band in 1350e1200 cm1 region and a initial light color of the PS. All the alkyd resins were soluble in white
twin band with medium intensity at 1150e1050 cm1 region are spirit, which is the most common solvent for resin and paint in-
characteristic of phthalate ester with some contribution from the dustries. Among the most common examples for the use of alkyds
in combination with other resins are the blends with amino,
phenolic and nitrocellulose resins. The blends of alkyds and the
mentioned resins were stored in cylindrical containers for three
months to track the and PSLO4060, were lighter in color than the
color of the reference, owing to the phase separation and changes
in physical properties. Neither any phase separation or any physical
change was observed. This indicates the good compatibility of the
synthesized alkyds with other common resins which results in the
ability to produce a wide variety of coatings based on blends of
resins.

4.2.3. Coating performance characteristics

The aims to scale up the synthesis were, firstly, to transfer the
developed laboratory knowledge to commercial production of
alkyd, and secondly, at the same time, providing identical samples
for end-users to characterize and evaluate by themselves. The
prepared alkyds and blank alkyds (5 samples) were separately
formulated into air drying gloss white paints and their character-
istics were compared to demonstrate the performance capability
Fig. 3. (a): acid numberetime, (b): viscosityetime charts for scale-up pilot synthe- and versatility of the resins. The paints were formulated to the
sizing PSDCO alkyds. same pigment to binder ratios and applied at equal dry film
312 A.A. Nanvaee et al. / Journal of Cleaner Production 54 (2013) 307e314

Fig. 5. Overlaid FTIR spectra of scale-up synthesized PSDCO and PSLO alkyd resins and control resin.

thickness for performance evaluation tests. Some properties of the progress and adequacy of drying process. Both drying time and
prepared paints and the commercial counterpart characteristics are hardness results correlate to each other and support the unsatu-
shown in Table 7. All the prepared alkyd paints had the desired ration effect of used oils. Since the amount of phthalic anhydride
drying behavior and after drying, they produced smooth and ho- used in alkyds synthesized from various vegetable oils blend were
mogenous films, implying the good leveling property of all the identical, difference between the hardness of the dried films is
paints. Hardness of the dried film of organic coatings is a mean- mainly due to the extent of unsaturation in each formulation.
ingful characteristic which can be considered in relation to the Hardness of DCO-based resins is higher than linseed oil-based

Table 6
Properties of pilot plant and industrial synthesized PSDCO and PSLO alkyd resins based on mixture of different oils.

Properties Resins

PSDCO PSLO Controla

2080 4060 2080 4060

Oil length (%) 63 63 63 63 60e65

Acid value (mgKOH/g)b 8.3 8.0 8.5 8.2 8.0e10.0
Viscosity (sec)c 19 18 17 18 18e21
Color (Gardner)d 7 6 7 6 6e7
Density (g/cm3@ 20  C)e 1.02 1.02 1.02 1.02 1.02
Solubility
White spirit Soluble Soluble Soluble Soluble Soluble
Xylene Soluble Soluble Soluble Soluble Soluble
Ethanol Limited Limited Limited Limited Limited
Butanol Limited Limited Limited Limited Limited
Butyl acetate Limited Limited Limited Limited Limited

Compatibility
Alkyd resins
Drying medium and short oil Complete Complete Complete Complete Complete
Drying long oil Complete Complete Complete Complete Complete
Amino resins
Melamine Formaldehyde resins Good Good Good Good Good
Urea Formaldehyde resins Good Good Good Good Good
Oil soluble hard resins
Phenolic resins Good Good Good Good Good
Other resins
Nitrocellulose Complete Complete Complete Complete Complete
a
Dugal S e 65, Dugal L e 65, SETAL 16 LV WS e 70, HAWALKYD SF.110 and 1117.
b
100% solid.
c
70% in WS, Flow time, Ford Cup No.4 @25  C.
d
70% in WS.
e
70% in WS.
 A.A. Nanvaee et al. / Journal of Cleaner Production 54 (2013) 307e314 313

Table 7 earth and its habitants. This is expected to open up new markets for
Coating performance of synthesized resins in air drying gloss paint. palm oil industry as well as resin and coating industries.
Paint properties Paint’s resin

PSDCO PSLO Controla

Acknowledgments
2080 4060 2080 4060

Drying It is authors pleasure to acknowledge financial support provided

Set-to-touch time (min) 50 55 50 55 50e55 by the University of Malaya through grant PS244/2009A. Many thanks
Tack free time (min) 180 195 180 205 180e190 are due to Marlyk Co. and all fellow-students and staff of UM Chem-
Physical
Hardness (sec) 18 17 17 17 17e18
istry department, particularly Mr. P. Azari, Mr. Zulkifli bin Abu Hasan,
Crosshatch adhesion (%) 100 100 100 98 100 Mr. Hashim bin Harun, Ms. Ho Wei Ling, Mrs. Nor Lela MD.Ali,
Gloss, 60 (%) 85 83 86 85 84e87 Mrs. S. Mazwan, Ms. Farhana Yusuf, and Ms. Murni Zawawi.
Mechanical
Direct/reverse impact resistance 60/60 60/60 60/60 60/60 60/60
1/8 inch mandrel bend Passed Passed Passed Passed Passed
References
Rheological
Brushability Good Good Good Good Good
Amarasinghe, A.D.U.S., De Silva, S.H.U.I., Premachandra, BB.A.J.K., Prashantha, M.A.BB.,
Leveling valueb 9 9 9 9 9
2012. Effect of karawila (Momordica charantia) seed oil on synthesizing the
Sagging resistance indexc 10 8 10 8 10 alkyd resins based on soya bean (Glycine max) oil. Prog. Org. Coat 74, 228e232.
a
Dugal S e 65, Dugal L e 65, SETAL 16 LV WS e 70, HAWALKYD SF.110 and 1117. ASTM, 2003. Annual Book Of ASTM Standards. Section 6, Paints, Related Coat-
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