G Model

JECE 101 1–9

Journal of Environmental Chemical Engineering xxx (2013) xxx–xxx

Contents lists available at SciVerse ScienceDirect

Journal of Environmental Chemical Engineering

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

2 Optimization of polyesterification process for production of palm oil modified

3 alkyd resin using response surface methodology
4 Q1 C.F. Uzoh a,*, O.D. Onukwuli a,b, R.S. Odera a, S. Ofochebe b
5 Q2 a Chemical Engineering Department, Faculty of Engineering, Nnamdi Azikiwe University, Awka, Nigeria
6 b
Mechanical Engineering Department, Faculty of Engineering, Nnamdi Azikiwe University, Awka, Nigeria

A R T I C L E I N F O A B S T R A C T

Article history: The optimization of polyesterification process of air drying alkyd resin from non-drying palm oil was
Received 28 April 2013 studied. Response surface methodology (RSM) based on central composite rotatable design (CCRD)
Received in revised form 12 July 2013 involving 30 experiments of four process variables at five levels was employed in view of its economical
Accepted 18 July 2013
way of obtaining optimal response with fewest number of experiments. Self cured resin was obtained by
modification of the saturated structure of palm oil with glycerol via alcoholysis, followed by unsaturated
Keywords: functional group of phthalic anhydride via polyesterification. The studied process parameters were
Alkyd resin
reaction temperature, reaction time, catalyst concentration and PA:MGO ratio. Predictive model
Central composite rotatable design
describing the fractional conversion in terms of process variables was derived from multiple regression
Optimization
Polyesterification analysis. Optimum fractional conversion of 97.28% was predicted at reaction temperature of 240.61 8C,
reaction time of 150 min, catalyst concentration of 0.03% and PA:MGO ratio of 0.38:1, for the process.
Extent of reaction at 120 min of polycondensation of the monomers was more than 85%. Model
validation experiment shows good correspondent between the actual (96.04%) and predicted (97.28%).
ß 2013 Published by Elsevier Ltd.

7
8 Introduction cost, controlled polymerization, low risk of batch failure and less 29
volatile organic components [1]. 30
9 Alkyd resin is a key ingredient of all surface-coating products The production of Alkyd resin used in manufacture of paints and 31
10 like paints, primer, adhesives and printing ink. Alkyd resins are other protective coating materials from non-drying palm oil 32
11 polyester polymer of fatty acids. They are responsible for the involves two-phase esterification process of the glyceride oil. The 33
12 mechanical properties, drying speed and durability of surface first phase known as alcoholysis involves the transesterification 34
13 coating materials. They consist mainly of polyhydroxyl alcohol and reaction of glycerol and the triglyceride of the oil in the presence of 35
14 polycarboxyl acid which chemically combine with various oil in catalyst to obtain monoglyceride oil while in the second phase 36
15 different proportion. The basic reaction involved in the preparation (esterification) the monoglyceride oil generated from the early 37
16 of alkyd resin is esterification. phase reacts with phthalic anhydride (PA) to form glyceride 38
17 phythalate (resin). It is noted that the application of vegetable oils 39
R-COOH þ ROH ! RCOOR þ H2 O for manufacture of resins are generally bedevilled by the presence 40
of some dissolved non-oil substances like carotene, chlorophyll, 41
20
19
18 Alkyd resin contains agro (50–70%) and petroleum (25%) base gossypol and other impurities like phosphatides, oxidation metals, 42
21 raw materials as compared to commercial resin containing 50–70% trace metals and traces of soaps in the crude samples [2]. In the 43
22 petroleum based products, which are imported. The alkyd resin same vein, other studies have also shown that the interactions of 44
23 produced is highly hydrophilic, hence it can be used in emulsion the some identified system parameters like reaction time, 45
24 polymer synthesis. Volatile organic compound (VOC) content on temperature, molar ratio of phthalic anhydride-to-glyceride oil 46
25 conventional alkyd resin is 40% while the new alkyd resin was 14%. and catalyst concentration on the polyesterification process may 47
26 The cost of novel alkyd resin is less than the commercial, as it uses equally affect the quality of the product. Hence, to ensure that high 48
27 more agro base products and less energy. Moreover, advantages of quality alkyd resin of good commercial value with acceptable 49
28 alkyd resins include agro based, energy efficient, eco friendly, low drying quality, appearance and other desired coating properties 50
are produced from this process, the unwanted dissolved sub- 51
stances must be separated from the actual oil sample, and the 52
reaction condition monitored to control the effects of these 53
Q3 * Corresponding author. Tel.: +234 8033762029.
Q4
E-mail address: epio4real@yahoo.com (C.F. Uzoh). influential process parameters. These objectives are achieved 54

2213-3437/$ – see front matter ß 2013 Published by Elsevier Ltd.

http://dx.doi.org/10.1016/j.jece.2013.07.021

Please cite this article in press as: C.F. Uzoh, et al., Optimization of polyesterification process for production of palm oil modified alkyd
resin using response surface methodology, J. Environ. Chem. Eng. (2013), http://dx.doi.org/10.1016/j.jece.2013.07.021
 G Model
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2 C.F. Uzoh et al. / Journal of Environmental Chemical Engineering xxx (2013) xxx–xxx

55 through characterization and optimization of the polyesterifica- oil and coconut oil can be attributed to kinetic, extent of reaction 118
56 tion process presented in this paper. The necessary and usual first and degree of polymerization [5,6]. Igwe and Ogbobe [7] carried 119
57 tasks involve applying a standard refining protocol to the raw out similar study using melon seed, rubber seed oils and linseed 120
58 sample such that oil product with appropriate physio-chemical and soybean oil. However, all these studies have neglected the 121
59 properties (like photometric colour, refractive index, specific interaction effect among process variables and their effect on 122
60 gravity, moisture content, FFA content, iodine value, etc.) as stated process or product characteristics. Earlier studies of alkyd resin 123
61 in the AOCS standard needed for production of alkyd resin may be synthesis from palm oil reported in the literature seem to rely on 124
62 processed. In view of the advantages related to the energy savings one factor at a time (OFAT) approach. Such method has been 125
63 and laboratory preference, the chemical (alkaline) refining method proven by research to be deficient, time consuming and 126
64 which essentially involves degumming, neutralization, washing, unsatisfactory. Hence the response surface methodology based 127
65 bleaching, dehydration, was chosen for this purpose instead of the on central composite rotatable design which is more robust in 128
66 distillation process that is gaining wider popularity in industrial handling multiple factors at a time, accounting for both the main, 129
67 refining due to some advantages associated with the reduced linear and quadratic interaction effects of the process parameters 130
68 operation steps and material cost. This is followed by the at a significantly reduce number of experimental runs has been 131
69 polyesterification process which must be carried out within a found to be a more sophisticated technology. 132
70 predetermined space of the controllable factors that are known to DOE facilitates systematic, efficient, cost effective planning and 133
71 have considerable effects on the system response. The characteri- analysis of experimental studies [8–11]. Numerous investigations 134
72 zation (or screening) of these major contributing variables to the in other fields have efficiently used such studies to get optimal 135
73 process response was achieved through design-of-experiment blend of product or process characteristics [12–14]. Thus 136
74 (DOE) and analysis of variance (ANOVA) while the control and experimental investigation based on simultaneous variation of 137
75 optimization tasks were accomplished using the well-known composition (process variables) rather than an OFAT approach is 138
76 response surface methodology (RSM). The experimental design needed to get more insight in the study of air drying of non-drying 139
77 was based on full-factorial central composite rotatable design that oil modified alkyd resins [15]. In this study an attempt is made to 140
78 guarantees a reduced number of experimental runs. The experi- develop a mathematical model for alkyd resin synthesis based on 141
79 mental analysis enhanced the characterization of the full effects of DOE technique. The reaction temperature, reaction time, weight 142
80 the four (4) factors at five (5) distinct settings. The global design ratio and weight % of catalyst were chosen as process parameter 143
81 matrix of Eq. (1) written in coded notations recommends sixteen and their effect on acid value was investigated. An optimization 144
82 (16) experimental runs at 24-full factorial distinct points, eight (8) problem was then formulated such that both this response should 145
83 runs at the 8-unique axial points and six (6) repeated runs at centre fall within a given range for a better product quality and 146
84 point which give rise to a total of thirty experimental runs. These productivity. 147
85 sequences of experiments were performed in the equivalent
86 natural units of the controllable factor space and the extents of Materials and methods 148
87 reaction (or fractional conversion) were recorded in terms of the
88 measured percentage drop in acid value of the solution over the Materials 149
89 reaction periods using the method of Eq. (1) [3,4]
AV i  AV j V i  V j Palm oil was obtained in crude form from an oil mill at Nise, 150
Yn ¼ ¼ (1) Anambra State. A rotary evaporator equipped with digital 151
AV i Vi
thermometer, rotatable round bottom flask, condenser and water 152
92
91
90 To study all standard effects of these process variables on the were also used. Other equipments include electronic weighing 153
93 responses analytically often requires fitting appropriate predictive balance, heating mantle, magnetic stirrer and general laboratory 154
94 model usually obtained from regression analysis to the resulting glassware. 155
95 data from which detailed statistical analysis and optimization Phthalic anhydride (C6H4(CO)2O) with minimum assay >97%, 156
96 exercise are based. Preliminary data analysis conducted using glycerol (C3H8O3) with assay >99%, sodium bisulphate (NaHSO4) 157
97 steepest ascent method shows that curvature effects exist. In view with assay 97.5% and lead(II) oxide (PbO) with assay >96.8% were 158
98 of curvature a reduced order quadratic model (ROQM) was fitted purchased from BDH chemicals ltd., Poole, England. Diethyl ether, 159
99 over the resulting data as suggested in Eq. (2) ethanol, xylene, anhydrous methanol, sodium hydroxide (NaOH) 160
with assay 96% was supplied by Wharefedale Laboratories, 161
X
k XX
k XX
k
Yorkshire, England. The chemicals purchased were of highest purity. 162
Y ¼ b0 þ bi X i þ bi j X i X j þ di j X i X j þ e (2)
i¼1 i< j¼2 i¼1 j¼1
Methods 163
100
102
101 Y is the measured system response (fractional conversion) of
103 the glyceride oil based esterification process. The first term by the The methods uses in the production of the alkyd resin are Q5 164
104 right side of the equation b0 is the model intercept; the second presented in Fig. 1. 165
105 terms characterizes the main linear effects of individual process
106 variables; the third term incorporates the interaction effects Neutralization of crude palm oil 166
107 between the variables; while the fourth term represents the main Neutralization of the crude palm oil was carried out according to 167
108 quadratic effects and e is the random error of experimentation. Xij AOCS standard [16]. 200 g of the crude sample (palm oil) was heated 168
109 represents the matrix of the uncoded process variables. in a flask to 60 8Cand then a strong 2N NaOH was added to neutralize 169
110 Eq. (2) serves as the global predictive equation from which the free fatty acid (FFA) content ensuring constant stirring. The 170
111 specific solution may be derived. The determination of the chemical reaction involved in this process is as follows: 171
112 unknown coefficients of b0,bi, bij and dij is accomplished via 172
113 regression analysis implemented on the statistical analysis R-COOH þ NaOH ! RCOONa þ H2 O
114 software Design-Expert Version 8.1.7.1 trial from the Stat-Ease
115 Inc. using the data recorded from the investigation. The neutralization progress was monitored using phenolphtha- 173
175
174
116 A critical review of existing literature on alkyd resin reveals that lein indicator. At the end of the neutralization process, sodium 176
117 there is scanty or no study on palm oil, a few studies on palm kernel chloride solution was added to the mixture to ensure adequate 177

Please cite this article in press as: C.F. Uzoh, et al., Optimization of polyesterification process for production of palm oil modified alkyd
resin using response surface methodology, J. Environ. Chem. Eng. (2013), http://dx.doi.org/10.1016/j.jece.2013.07.021
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C.F. Uzoh et al. / Journal of Environmental Chemical Engineering xxx (2013) xxx–xxx 3

Table 1
Production of crude oil from palm seed Quantity of reagents utilized for alkyd resin synthesis.
(mesocarp)
Raw material Weight (g) Weight (%)

Dehydrated palm oil 115 58.08

Neutralization with caustic soda (NaOH) at 600C Phthalic anhydride 48 24.24
and salting with NaCl Glycerol 35 17.68

Total 198 100

Dehydration with NaHSO4

Esterification: At this stage, phthalic anhydride was added to the 221
monoglyceride mixture. The temperature of mixture was main- 222
tained at the range of 230–240 8C. The reaction progress was 223
Alcoholysis and polyesterificaon of POMG at monitored by periodic determination of the acid value. The second 224
2600C stage reaction is continued at the elevated temperature and long 225
chain molecules are formed which contain excess hydroxyl group. 226
Addion of driers At this state water is released. Removal of water from the mixture 227
was facilitated by a solvent extraction method. The mixed vapor 228
generated was then condensed and collected. By choosing the 229
Fig. 1. Process flow diagram for alkyd resin synthesis raw palm oil. exact solvent (xylene) that does not mix with water in liquid phase 230
the mixture demarcated into two layers. Xylene is chosen for this 231
process since it has suitable boiling point and low water solubility. 232
178 salting or graining out the soap stock produced. Subsequently, the When the acid value dropped to a value somewhat below 8, the 233
179 mixture was poured into separating funnel. Three hours later, the reaction is stopped. The acid values of the alkyd resin were 234
180 mixture separated into two distinct layers. The lower layer which determined and chemical resistance was equally measured Q6235
181 contains the FFA rich soap stock was drained out while the upper (Table 1). 236
182 layer containing the neutralized oil was then washed with hot
183 water to remove any traces of soap. Washing was carried out until Physico-chemical test 237
184 colour of phenolphthalein indicator did not change to pink.
Spectral analysis. The chemical compositions of alkyd resin were 238
185 Bleaching/filtration/dehydration of neutralized oil confirmed by Buck M530 FT-IR. The FT-IR equipment was operated 239
186 The neutralized washed oil was introduced in a cylindrical with wavelength range 4000–500 cm1 240
187 vessel equipped with agitator called ‘ bleacher’ and then heated up
188 to 90 8C with steam under vacuum pressure. The moisture from oil Adhesion. The dried films were cut by cross hatch and the coatings 241
189 is thus evaporated and oil becomes dry. The dried oil was treated were cleaned using a brush. A scotch tape was adhered on to the 242
190 with 5% by mass of bleaching agent (mixture of fuller’s earth and film and peeled of quickly at 1808 angle. The peeled off grid areas 243
191 carbon at 1:1 ratio) to enhance the adsorption of the residual on the tape were observed by a magnifier. 244
192 colour. The process was allowed to continue for about 45 min
193 with constant agitation. After which the resulting mixture was Solubility. The solubility of the synthesized palm oil modified resin 245
194 filtered through a standard plate and frame press to enhance was tested in different solvents such as xylene, benzene, toluene, 246
195 separation to obtain clear oil very much lighter in colour than the DMF, acetone, ethanol and methanol. 247
196 neutralized oil. The oil charge was dehydrated under vacuum to
197 avoid any further deterioration due to oxygen. The bleached Chemical resistance. The chemical resistance of the alkyd was 248
198 dehydrated oil was weighed to calculate oil loss and the FFA determined in two media: distilled water and strong NaOH in 249
199 content was determined. The characteristic of the crude oil and solution. 250
200 neutralized oil were determined according to AOCS standard
201 [16]. Abrasion resistance test. The test is useful in determining the 251
resistance of organic coatings to a falling abrasive. 252
202 Synthesis of the alkyd resin
203 Palm oil modified alkyd resin was prepared with the Formulation of design matrix 253
204 dehydrated oil, glycerol and phthalic anhydride using PbO and The determination of unknown coefficient of Eq. (2) applies the 254
205 NaOH as catalyst. The preparation was done with a rotatable design matrix of Table 3 formulated by judicious transformation of 255
206 evaporator fitted with digital thermometer, a rotatable round the actual values of the four control variables at various levels over 256
207 bottom flask (agitation speed of 700 rpm), water bath and which the experiments were executed to their coded equivalents 257
208 condenser. In the synthesis of the alkyd resin, two stages were using 1 and +1 notations to designate low and high levels factor 258
209 involved. The first stage was alcoholysis and the second stage was setting and ‘a’ and ‘0’ for axial and centre points, respectively. It has 259
210 esterification. been shown that working with the coded variables enhances matrix 260
211 Alcoholysis: In this stage, monoglyceride was first synthesized transformation and helps in results analyses. A useful value of a is 261
212 by reacting oil with glycerol. Alcoholysis of oil was carried out with evaluated from the general expression a = f1/n(= 2), where f is the 262
213 0.1% (by wt) PbO catalyst and 0.2% (by wt) NaOH catalyst. In number of factorial points (=16) and n is the number of factors (=4) or 263
214 alcoholysis reaction, the oil was heated with agitation speed of for 2-level designs a = 2n/2. 264
215 700 rpm to 230 8C. Glycerol and selected catalyst were added and The coded values of the independent variables for the design of 265
216 alcoholysis reaction occurs at 230–240 8C. The reaction was the experiment for alkyd resin synthesis are given in Table 2. For 266
217 continued until a sample of the reaction mixture became soluble statistical analysis, the variables Xi (i = 1, 2, . . ., 4) were coded as A, 267
218 in 2–4 volume of anhydrous methanol. After the completion of B, C and D. 268
219 alcoholysis, the reaction mixture was cooled to 140 8C before The data given in Table 2 were used to formulate a global design 269
220 esterification commence. matrix of Table 3 from which further analyses were derived. 270

Please cite this article in press as: C.F. Uzoh, et al., Optimization of polyesterification process for production of palm oil modified alkyd
resin using response surface methodology, J. Environ. Chem. Eng. (2013), http://dx.doi.org/10.1016/j.jece.2013.07.021
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4 C.F. Uzoh et al. / Journal of Environmental Chemical Engineering xxx (2013) xxx–xxx

Table 2
Experimental range and levels of independent process variables for alkyd resin synthesis.

Independent variable Range and level

a 1 0 1 a
Temperature (8C) (A) 220 230 240 250 260
Time (min) (B) 3C 6C 9C 120 150
Molar ratio (C) 0.1:1 0.2:1 0.3:1 0.4:1 0.5:1
Catalyst concentration (wt%) (D) 0.02 0.04 0.06 0.08 0.10

271 Y is the measured fractional conversions (or extent of reaction From Table 4, it can be seen that the neutralization process 291
272 of PA) across the various experimental runs expressed as can reduce the FFA content of crude PO from 5.5 to 0.98, then a 292
273 percentage drop in acid value of reaction mixture during the refractive index of 1.484. The refined oil now possesses a specific 293
274 esterification process of PO modified alkyd resins. Eq. (2) was fitted gravity of 0.9716, while the viscosity and iodine value were 294
275 to the experimental data presented in Table 3 to obtain the final nearly the same with the crude samples. Although the 295
276 predictive equation for the reaction progress in terms of the coded neutralization technique reduces significantly FFA content in 296
277 variables the oil sample, it gave a slight effect on specific gravity, viscosity 297
and iodine value. The iodine and viscosity control of the extent 298
278 Process analysis. The transesterification process is analysed for the of reaction and set to touch time and drying time show the 299
279 different interaction effects of the process variables on the drying properties of the dehydrated sample. The drying time and 300
280 responses based on solutions derived from Eq. (2) at some set to touch time gave satisfactory results. Therefore, this 301
281 assumed experimental conditions so as to reveal possible routes to dehydrated oil sample was acceptable to prepare air drying oil 302
282 optimum fractional conversion. The popular surface response modified alkyd resin. 303
283 methodology was suitably utilized for this exercise. The design The alcoholysis reaction is usually completed within an hour or 304
284 expert analysis and optimization tool functions provided all the two hours after the batch had reached operating temperature [18]. 305
285 necessary computational assistance. The results were presented as Table 5 shows the solubility of the alcoholysis in anhydrous 306
286 response surface contours. methanol carried out for several hours using PbO and NaOH 307
catalysts. 308
287 Results and discussion In esterification reaction, it was observed that the longer the 309
reaction, the more viscous the mixture is. In this stage, adequate 310
288 Characteristics of crude, neutralized and dehydrated palm oil agitation was necessary for complete mixing of monoglyceride 311
mixture and phthalic anhydride. Unless adequate mixing was 312
289 The characteristics of crude, neutralized and dehydrated palm supplied in this stage, an unqualified alkyd resin would result. So 313
290 oil are shown in Table 4. the agitation speed of the rotatable flask was increase from 500 314
to 700 rpm. Xylene was also introduced to form azeotrope with 315
Table 3 water. Liberated water of esterification is carried off in the 316
Full factorial central composite rotatable design matrix for alkyd resin production in xylene under vacuum and generally heat and mass transfer of 317
coded notations from glyceride oil of palm oil. chemical reaction is greatly increased. Extent of reaction at 318
Std. Run Independent variables Response 120 min of polycondensation of monomers was more than 85% 319
[17]. 320
A B C D Y

21 l 0 0 2 0 58.3
10 2 l 1 1 1 76.2
26 3 0 0 0 0 69.5 Table 4
1 4 1 1 1 1 30.7 The characteristics of the crude, neutralized and dehydrated palm oil [17].
6 5 1 1 1 1 67.2
Characteristics Crude oil Neutralized oil Dehydrated oil
2S 6 0 0 0 0 78.5
11 7 1 1 1 1 66.7 Free fatty acid (%) 5.5 0.98 0.98
19 S 0 2 0 0 46.2 Colour, photometric Orange red Orange red –
4 9 1 1 1 1 75.0 Refractive index – 1.484 –
23 10 0 0 0 2 57.0 Viscosity (25 8C) (stroke) 4.5 4.8 1.69
14 11 1 1 1 1 79.0 Iodine value 45 45 127
S 12 1 1 1 1 88.5 Specific gravity 0.9633 0.9716 0.970
29 13 0 0 0 0 69.0 Set to touch time (h) – – 3.5
7 14 1 1 1 1 93.3 Drying time (h) – – 4.5
IS 15 2 0 0 0 90.4
25 16 0 0 0 0 77.4
24 17 0 0 0 2 72.2
13 13 1 1 1 1 47.5 Table 5
16 19 1 1 1 1 81.2 First stage alcoholysis reaction [17].
27 20 0 0 0 0 72.5
5 21 1 1 1 1 37.1 Alcoholysis Catalyst Reaction Completion of
30 22 0 0 0 0 72.4 catalyst (wt.%) time (h) alcoholysis reactiona
12 23 1 1 1 1 75.0
PbO 0.05 4 Not complete
17 24 2 0 0 0 66.5
0.1 4 Not complete
20 25 0 2 0 0 76.8
9 26 1 1 1 1 40.1 NaOH 0.1 4 Not complete
2 27 1 1 1 1 45.3 0.2 4 Not complete
15 2S 1 1 1 1 74.1 0.3 2 Complete
3 29 1 1 1 1 56.0 a
It was determined by testing the solubility of alcoholysis mixture in anhydrous
22 30 0 0 2 0 67.4
methanol.

Please cite this article in press as: C.F. Uzoh, et al., Optimization of polyesterification process for production of palm oil modified alkyd
resin using response surface methodology, J. Environ. Chem. Eng. (2013), http://dx.doi.org/10.1016/j.jece.2013.07.021
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C.F. Uzoh et al. / Journal of Environmental Chemical Engineering xxx (2013) xxx–xxx 5

Table 6 (6) homogenous factor settings given a total of thirty (30) 350
Chemical resistance of the alkyd resin film.
experimental runs following the procedure described earlier in 351
Media Immersion time (h) Appearance of filma Section 2.4, and the fractional conversion of the manufactured PO 352
Distilled water 18 No effect oil modified alkyd resins designated with Y was estimated in terms 353
of the measured reduction in acid value (AV) over the reaction 354
3NaOH 8 Whitening
periods. The responses recorded for the different runs were 355
16 Blistering
24 Removal substantially unique which shows that the factors have significant 356
a
effects. The deductions from the characterization, control and 357
It was examine after film was dry for 30 min.
optimization protocol implemented for the manufacturing pro- 358
cesses are discussed consequently in what follows. 359
321 Chemical resistance
Statistical analysis/factor screening 360
322 The resistance of the alkyd was determined in two media: The process characterization (or factor screening) was carried 361
323 distilled water and NaOH solution. It was observed that there was out to evaluate the system variables which provide the most 362
324 no effect on alkyd film after immersion in distilled water for 18 h. important effects in tune with the research objectives. The 363
325 When the alkyd film was immersed in strong alkali solution, 3N necessary computational tasks were aided with the ANOVA 364
326 NaOH, the film got whitening after immersion time of 8 h, function of the statistical software Design-Expert Version 8.1.7.1 365
327 blistering after immersion time of 16 h, and removal after In view of curvature a reduced order quadratic model of the 366
328 immersion time of 24 h. This result therefore, shows that PO oil general form given in Eq. (2) was appropriate for predicting the 367
329 Q7 modified alkyd resins have high chemical resistance (Table 6). overall process characteristics. The ANOVA results derived from 368
the predictive model show that the main linear effects due to 369
330 Spectral analysis of palm oil based resin and raw palm oil individual control factors temperature (x1), time (x2), molar ratio 370
(x3), and catalyst concentration (x4) coded as A, B, C, and D, 371
331 The IR spectra of raw palm oil and the corresponding resin are respectively, are all significant process variables indicated with the 372
332 shown in Fig. 2. In the IR spectrum of palm oil, the small shoulder observed P-values < 0.05 in the numerical analysis. This is equally 373
333 3600 cm1 corresponds to the hydroxyl (O–H) of the unsaturated true with the linear interaction effects between temperature and 374
334 fatty acid in palm oil. The carboxyl group (C5 5O) is indicated at time (AB), time and catalyst concentration (BD) and molar ratio and 375
335 1747 cm1.The straight chain of –CH– stretch in aliphatic catalyst concentration (CD). The quadratic effects of time, molar 376
336 compound is found at band 2854 cm1. Alkene group (CH5 5CH) ratio and catalyst concentration denoted by B2, C2 and D2, 377
337 is attributed to the band of 3000 cm1. The IR spectrum of the respectively, are significant while the quadratic effect of tempera- 378
338 prepared resin exhibits a characteristic straight chain ester band at ture A2 is insignificant. The data obtained for specific investigation 379
339 1738.64 cm1 and aromatic (C5 5C) ring ester at 1730.09 cm1. The were refitted with a modified model obtained by excluding the 380
340 presence of O5 5C–O–C also exhibits characteristic ester band non-significant variables from the general predictive equation and 381
341 1125.62 cm1. The absorption band at 3008.99 cm1 is character- the results of statistical analysis obtained for the sequence of 382
342 istic of Alkenes [19,20]. The appearance of ring ester band at experimentations are summarized in Table 7. The coefficients of 383
343 1730.09 cm1 confirms the esterification of palm oil monoglycer- determination R2 values of 0.90443 obtained for the PO based 384
344 ide with phthalic anhydride. esterification process show that more than 90% of the overall 385
system variability can be explained by the empirical models of 386
345 Optimization Eq. (3) which are specific case of the general predictive equation 387
derived for the investigations from the multivariate regression 388
346 The response obtained for the various experimental runs analyses implemented on design expert. 389
347 executed in the equivalent natural units of the process variables as
Y ¼ 74:28 þ 7:90A þ 10:33B þ 5:05C þ 3:21D  5:17AB
348 prescribed in the full factorial CCRD are presented in Table 3. The
349 experiments were carried out at twenty four (24) distinct and six  4:89BD  3:46CD  3:44B2  3:11C 2  2:67D2 (3)

Table 7
ANOVA for the response surface reduced order quadratic model (RSROQM) in terms
of only the significant process variables.

Source PO

F-value P-value

Model 17.96 <0.0001

A-temp. (8C) 41.01 <0.0001
B-time (min) 70.04 <0.0001
C-mole ratio 16.71 0.0006
D-catalyst conc. (w/w) 6.77 0.0175
AB 11.69 0.0029
BD 10.48 0.0043
CD 5.23 0.0339
A2 – –
B2 9.08 0.0071
C2 7.39 0.0136
D2 5.45 0.0306
PO Std. dev. 6.05 R-squared 0.9043
Mean 66.9 AdjR-square 0.8540
C.V. (%) 9.04 PredR-squared 0.7158
PRESS 2063.34 AdeqPrecision 17.764
Fig. 2. FT-IR of raw PO and PO based alkyd resin. DF: model = 9, residual = 20, total = 29.

Please cite this article in press as: C.F. Uzoh, et al., Optimization of polyesterification process for production of palm oil modified alkyd
resin using response surface methodology, J. Environ. Chem. Eng. (2013), http://dx.doi.org/10.1016/j.jece.2013.07.021
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392
391
390 where Y is the predicted value of the dependent variable (i.e.
393 fractional conversion). A, B, C and D are the main linear effects of
394 the independent process variables: temperature, time, molar ratio
395 and catalyst concentration, respectively, in coded units. AB, BD and
396 CD represent the linear interaction effects between temperature/
397 time, time/catalyst concentration and mole ratio/catalyst concen-
398 tration, respectively. A2, B2, C2 and D2 are the quadratic effects of
399 the respective process variables. The ‘‘Predicted R-Squared’’ of
400 0.7158 is in reasonable agreement with the ‘‘Adjusted R-Squared’’
401 of 0.8540; and the model F-value of 17.96 further indicates that the
402 model is significant. There is only a 0.01% probability that the
403 ‘‘model F-value’’ this large could occur due to noise. P value less
404 than 0.05 indicates model terms are significant. ‘‘Adequacy
405 Precision’’ measures the signal to noise ratio (SN). A ratio greater
406 than 4 is desirable. SN value 17.764 indicates adequate signal-to-
407 noise ratio.
408 The diagnostics analyses completed via normal probability Fig. 4. Response surface contour for interaction on PO modified alkyd resin
409 plots of residuals for the investigations are presented in Fig. 3. A production between temperature and time.
410 visual inspection of the graphs is sufficient to say that the residuals
411 follow a normal distribution. A picture of points which interlock a
412 straight line with some moderate scatter is expected with normal increase as the temperature setting shifts from 220 8C to 240 8C 437
413 data. and begins to show depreciating values at higher isotherms above 438
250 8C. This may be associated with the reversible nature of the 439
414 Process analysis esterification process and possible existence of a critical factor 440
415 The esterification process for the production of PO modified settings that guarantees optimum conversion of high-grade resin 441
416 alkyd resins is analysed based on the various solutions obtained at with desired polymerization properties under atmospheric condi- 442
417 possible reaction conditions from the model predictive equations tion and adequate economic value that may justify the efforts on 443
418 (3). The well-known RSM is considered appropriate owing to its experimental design and optimization study. 444
419 flexibility in navigating the design space. These equations were The observed interaction effects on the responses between 445
420 solved for the various interaction effects on alkyd resin conversion temperature (x1) and molar ratio (x3) are recorded in Fig. 5. The 446
421 considering at any instance the interactions between two factors quadratic effect of molar ratio is identified with smooth curves on 447
422 only, assuming the other variables are set at their mean coded the reference surface contour. The process responses are all 448
423 value of zero (0). The analyses and optimization exercises are maximized in a similar fashion as the phthalic anhydride-to-oil 449
424 completed accordingly using the Design expert 8.1.7.1 trial ratio is increased PO from a low value of 0.1:1 to mean values 450
425 application and the graphical solutions are presented as response between 0.3:1 and 0.45:1. Transition to the optimum fractional 451
426 surface contour diagrams. conversion of PO modified resins may be achieved with the molar 452
427 The interaction effects on the process response between ratios 0.32:1 as obtained from the optimization solution. An 453
428 temperature (x1) and time (x2) in their natural units associated important observation in the PO analysis is the persistent increase 454
429 with the resins produced are presented in Fig. 4. As expected for a in process response as temperature is adjusted upwards within the 455
430 typical batch process, the fractional conversion of the PO modified design space. This corresponds with the results of statistical 456
431 resins generally increases readily with reaction time, approaching analyses summarized in Table 7 which reveals that quadratic effect 457
432 70% at 100 min even at low level temperature setting of about of temperature (A squared) on response is insignificant within the 458
433 230 8C following first order reaction kinetics in sufficient factor range of the experiment with PO sample returning P-value 459
434 monoglyceride oil while towards the completion of the reactions, (>the threshold–0.05). Such observation is an indication that 460
435 the responses assume a second order. Such observations conform reaching a gel point by mere increasing the reaction temperature 461
436 to a large extent with the results of the literature [2]. The responses within the design space is not obvious. 462

Fig. 5. Response surface contour for interaction on PO modified alkyd resin

Fig. 3. Normal probability plots of residuals obtained from PO data analysis. production between temperature and molar ratio.

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resin using response surface methodology, J. Environ. Chem. Eng. (2013), http://dx.doi.org/10.1016/j.jece.2013.07.021
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Fig. 6. Response surface contour for interaction on PO modified alkyd resin Fig. 8. Response surface contour for interaction on PO modified alkyd resin
production between temperature and catalyst concentration. production between time and catalyst concentration.

463 Figs. 6–8 display the responses for the interactive factors; of the system to adjust in a way and manner as to allow unreacted 489
464 temperature (x1) vs catalyst concentration (x4), time (x2) vs molar or excess glycerol in the mixture to form an additional but 490
465 ratio (x3), and time (x2) vs catalyst (x4) concentration, respectively. undesirable product (glyceryl pthalate) which is insoluble in the 491
466 The 3D response surface plots show that the best results on alkyd wanted product (oil–acid glyceryl pthalate) and the unreacted 492
467 resin conversion are obtained at reaction time in the range of 95– glyceride oil [21]. It is further observed that the response on PO 493
468 120 min using catalyst concentration not less than 0.08% and based alkyd resin continues to show some discrepancies as the 494
469 reaction temperature between 240 and 250 8C. The response response increases uniformly with temperature all through and 495
470 surface contours report that allowing a short reaction time of follows a swift curvature as catalyst concentration is reviewed 496
471 30 min at low concentration of pthalic anhydride leads invariably upwards (see Fig. 6). This indicates that the optimum % conversion 497
472 to low fractional conversions and non-viscous products. The is associated with maximum esterification temperature of 260 8C 498
473 obvious reason for this has to do with non-completion of reaction; and mean catalyst concentration in the sample. A comparable 499
474 essentially abundant hydroxide (–OH) group of the monoglyceride result has been reported for the manufacture of alkyd resin from 500
475 oil is reacting with only scanty molecules of pthalic anhydride castor oil in Hlaing et al. [2] where 97.72% of the esterification 501
476 within some time substantially less that the optimum, giving rise reaction was completed at about 240 8C within the allowed 502
477 to poor yield of alkyd resin with relatively high acid value >15 [21]. 150 min of the reaction using pre-determined weights of phthalic 503
478 This type of product is not desirable for coating processes where anhydride and catalyst. The reaction was terminated after this 504
479 curing duration must be minimized. Alkyd resins with acid number duration to avert gelation. 505
480 <15 are preferable for improved polymerization properties at The response surface plot of Fig. 9 reveals that interactive 506
481 atmospheric conditions [22]. Evidently, the responses are maxi- effects between these two factors are important in the three 507
482 mized as the ratio of pthalic anhydride in the mixture is increased processes and need to be controlled. It is evident in the figure that 508
483 to some values above the mean, allowing the reaction to progress increasing catalyst concentration within the design space at fixed 509
484 uninterrupted for about 2 h (120 min). However, operating at setting of pthalic anhydride-to-oil molar ratio invariably leads to 510
485 extreme condition of time >130 min and molar ratio >0.45 an increased fractional conversion. Such response is desired 511
486 invokes decreasing responses. This explains the tendency that the but the best results under this condition are achievable at the 512
487 available –OH group from monoglyceride oil may be used up optimal molar ratio and moderate catalyst concentration. By and 513
488 towards the end of effective reaction time causing the equilibrium large, it is possible to achieve up to 87% fractional conversion in PO 514

Fig. 7. Response surface contour for interaction on PO modified alkyd resin Fig. 9. Response surface contour for interaction on PO modified alkyd resin
production between time and molar. production between molar ratio and catalyst concentration.

Please cite this article in press as: C.F. Uzoh, et al., Optimization of polyesterification process for production of palm oil modified alkyd
resin using response surface methodology, J. Environ. Chem. Eng. (2013), http://dx.doi.org/10.1016/j.jece.2013.07.021
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515 product even at lowest molar ratio setting and high catalyst on any formalized optimization paradigm yet it was able to show 568
516 concentration. However, such solution may not be of any economic that the results of Table 8 is realistic and reliable. On the other 569
517 or manufacturing importance as it would lead to relatively hand, the observations contained in this essay are apparently 570
518 high consumption of catalyst and poor yield of alkyd resin. The different from those reported in literatures; transesterification of 571
519 necessary detail on optimization analysis and results is given vegetable oils with ethanol by Giovannilton et al. [23] and 572
520 below. Freedman et al. [24] for biodiesel production, and transesterifica- 573
tion study of cynara oil by Encinar et al. [25]. This may be 574
521 Process optimization attributed to the inherent high activation energy associated with 575
522 As anticipated for a typical manufacturing process, the need for the equilibrium of reaction between phthalic anhydride and the 576
523 optimization arise where products which provide some obvious glyceride oils to form alkyd resin. 577
524 advantages like short drying time, reduced material cost, improved
525 colour (appearance) and weight are desired. Of particular interest Conclusion 578
526 is the drying time which is a critical issue highlighted in this paper.
527 We may recall that a major objective is to contrive a route to high Critical monitoring of the reaction progress in time indicates 579
528 quality resins with good polymerization properties for industrial rapid and linear transformation of the monomers to polymers in 580
529 coating processes from a non-drying oil. Other avenues for process the parameter space at the early stage of the reaction. This 581
530 optimization are through reduced reaction time and temperature observation however changed at the later stage where the 582
531 which in effect minimize the overall cost of manufacturing response shows certain degree of curvature with decreasing 583
532 simultaneously. Optimization problem may be compounded when conversion rate. The decrease in acid value of the alkyd was found 584
533 the process(es) pose a multiple desired targets which may be a to be rapid in the first 120 min of polyesterification reaction. Extent 585
534 combination of two or more of above stated conditions. This is of reaction at 120 min of the polycondensation of the monomer 586
535 actually the case with the esterification processes and many other was more than 85%. This shows that a linear type polymer was 587
536 real systems for that matter. A standard approach to this problem formed within this period. The response surface methodology 588
537 is to formulate global optimization criteria through which the based on central composite rotatable design employed for the 589
538 necessary trade-off may be affected so as to achieve what may be analysis and optimization of the polyesterification process of the 590
539 considered as the best combination to the desired result. palm oil predicts optimum fractional conversion of 97.28% at; 591
540 The optimization exercise for the manufacturing process for the reaction temperature 240.61, time 150 min, catalyst concentra- 592
541 production of PO modified resins was conducted separately tion 0.03% and PA: MGO ratio of 0.38:1. Fractional conversion of 593
542 utilizing the flexibility of the design expert optimization tool 97.28% predicted by statistical analysis shows close enough 594
543 function. Eq. (3) was solved for the best solutions such that the agreement with the 96.04% fractional conversion obtained with 595
544 responses (Yn) are maximized within the design space. No unique the validating experiment performed at the predicted optimum 596
545 solutions were possible. A usual approach, which involves conditions. 597
546 selecting the best solution based on economic consideration, is 599
547 adopted and the chosen optimal solutions were presented in Nomenclature 598
548 Table 8. Given that the various optimum reaction times and
549 temperatures were not considerably far separated from each other, ANOVA analysis of variance 602
601
550 the selection of desired optimum solution of Table 8 was mainly AOCS American Oil Chemists Society 604
603
551 influenced by the availability and cost of reagents. Experiment was CCRD central composite rotatable design 606
605
552 then performed using the optimal result of the numerical
DF degree of freedom 608
607
553 optimization executed by design expert. Fractional conversion of
F-value test statistics of F distribution 610
609
554 96.04% for PO obtained by experiment was in reasonable
555 agreement with that of statistical model of design expert. FFA free fatty acid 612
611
556 Effort to compare these solutions overtly with previous works MGO monoglyceride oil 614
613
557 found in the literature did not provide much desired result. This is P-value smallest level of significance that would lead to rejection of 616
615
558 because productions of alkyd resins via esterification process of null hypothesis in test statistics 617
559 non-drying palm oil have not received adequate research attention PA phthalic anhydride 619
618
560 deserved of them. However, it has been shown that a lot of RSM response surface methodology 621
620
561 similarities exist between the results of current research and that X coded independent system variables 623
622
562 reported by Hlaing et al. [2], where more than 97% of the Y dependent variables, predicted response 625
624
563 esterification process of monoglyceride of castor oil and pthalic
a axial point of factorial design 627
626
564 anhydride was completed within the first 150 min of reaction at
b constant coefficient of mathematical model 628
629
565 temperature maintained between 230 and 240 8C. Although Hlaing
566 et al. [2] observation was based on close monitoring of the reaction
e random error of mathematical model 631
630
632
567 progress via continual evaluation of the product acid number, not
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resin using response surface methodology, J. Environ. Chem. Eng. (2013), http://dx.doi.org/10.1016/j.jece.2013.07.021
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Please cite this article in press as: C.F. Uzoh, et al., Optimization of polyesterification process for production of palm oil modified alkyd
resin using response surface methodology, J. Environ. Chem. Eng. (2013), http://dx.doi.org/10.1016/j.jece.2013.07.021