Solubility of Terephthalic Acid in the Reaction

System Oligomeric Bishydroxybutyl

Terephthalates—1,4-Butanediol

Hainan Huang,1 Zuoxiang Zeng,1 Weilan Xue,1 Wanyu Zhu2

1
Institute of Chemical Engineering, East China University of Science and Technology, 200237 Shanghai, China

2
Shanghai Tianyang Hot-melt Adhesive Company Limited, 201802 Shanghai, China

The physical solubilities of terephthalic acid (TPA) in
the reaction system oligomeric bishydroxybutyl tereph-
thalates—1,4-butanediol (BD) are measured using an
analytic method from 449 to 507 K. The reaction sys-
tem is obtained by transesterification of dimethyl ter-
ephthalate and excess BD. These results are fitted with
the solubility model based on the Margules equation,
and the average deviation of the model is 1.20%; the
fusion enthalpies DHfus of TPA and infinite-dilution ac-
tivity coefficients c‘2 in the system are obtained by
regressing of the experimental data. In addition, syn-
thetic method is chosen to determine the total solubil-
ity which is complicated by chemical reaction, the
results indicate that the chemical reaction start at 452–
472 K. POLYM. ENG. SCI., 49:819–823, 2009. ª 2009 Society
of Plastics Engineers
INTRODUCTION
Terephthalic acid (TPA) is primarily used in the manu-
facture and production of various polyester [1], such as pol-
y(butylene terephthalate) (PBT) which is a widely used
industrial plastic. PBT has been synthesized from direct
esterification of TPA with excess 1,4-butanediol (BD) or
from transesterification of dimethyl terephthalate (DMT)
with BD [2, 3]. Heretofore, DMT has been more commonly
than TPA as a starting material. However, since TPA pro-
cess has an advantage over DMT process in the sense of
cost, a trend for synthesis of PBT by changing from DMT
process into TPA process became apparent [4]. Unfortu-
nately, the direct esterification reaction rate is very low, and
the reaction usually requires high temperature and long reac-
tion time, which will result in some side reactions [5]. A
particularly undesirable side reaction is the conversion of
BD and hydroxybutyl end groups into tetrahydrofuranate
(THF) [6]. Other things being equal, the economic advantage
obtained by the use of TPA as starting material will be nulli-
fied if BD loss is higher than 0.2 mol per mole of TPA [7].
Correspondence to: Weilan Xue; e-mail: wlxue@ecust.edu.cn
DOI 10.1002/pen.21321
Published online in Wiley InterScience (www.interscience.wiley.com).
V
C 2009 Society of Plastics Engineers
A faster reaction time is thus desired to reduce the
amount of THF generated during the direct esterification
reaction between TPA and BD.
Similar to the reaction between TPA and ethylene gly-
col, the reaction between TPA and BD is heterogeneous
[8], it can be assumed that the esterification occurs only
in the liquid phase [9, 10]. So the solubility of TPA in
the liquid phase has a significant effect on the esterifica-
tion rate. However, TPA is a crystalline solid that show
low solubility in BD [11]. To shorten the reaction time,
oligomeric bishydroxybutyl terephthalate (BHBT) pro-
duced by transesterification of DMT with BD is added
into the reaction system. Therefore, it is comparatively
meaningful to obtain the solubility data of TPA in the
reaction system containing oligomeric BHBT. Neverthe-
less, at present, the data are not available in literature.
In this study, the analytic method is used to determine
the physical solubility of TPA in the reaction system con-
taining oligomeric BHBT and BD. The system is obtained
by transesterification of excess BD and DMT with differ-
ent starting molar ratio. The experimental physical solu-
bility data are correlated by a three-parameter model
based on the Margules equation. In addition, the total sol-
ubilities in which chemical reaction is taken into account
are measured by the synthetic method.
EXPERIMENTAL SECTION
Materials
TPA (Sinopec Yangzi Petrochemical Co., Ltd.) and BD
(Shanxi Sanwei Group Co., Ltd.) used here are fiber forming
grade. Moisture is removed from BD by boiling and con-
densing it at 427 K under vacuum. Before use, TPA is dried
at 353 K under vacuum. DMT with a mass fraction purity
better than 99% is provided by Asahi Kasei Chemicals Cor-
poration and used as received. Tetrabutyl titanate and chloro-
form (purchased from Shanghai Chemistry Reagent Co.,
China) are an analytical reagent grade. Bidistilled water is
used here. Ethylene glycol is used as an internal standard.

POLYMER ENGINEERING AND SCIENCE—-2009

Experimental Method
The solubility of a solid in a liquid mixture is gener-
ally determined by two different methods: analytic
method [12, 13] and synthetic method [14, 15]. The ana-
lytic method has the advantage of measuring a large num-
ber of samples simultaneously. But it is time consuming
and tedious. For synthetic method, the accuracy of the
measurement depends on the ability to judge the disappear-
ance of the particles suspended in the solution and the sen-
sitivity of temperature control. According to the properties
of the solid studied in this work, we chose the last crystal
disappearance method [16, 17], one of the synthetic meth-
ods, to determine the total solubility. The physical solubil-
ity in the reaction system oligomeric BHBT-BD is deter-
mined by analytic method. The concentration of TPA in
the reaction system is analyzed by high performance liquid
chromatography (HPLC).
Transesterification
Transesterification between DMT and BD is carried out
in a four-necked round flask, which is fitted with a me-
chanical stirrer and a distillation system to remove the
released methanol. The flask is heated using a silicon oil
bath with a temperature controller. DMT and BD are
added into the flask and heated. When the reaction mixture
reached 433 K a few drops of titanium tetrabutoxide
(0.1% based on the mass of TPA) are added. Then the
temperature is raised to 503 K with stirring in a stream of
nitrogen throughout the esterification reaction, and the
temperature is maintained at this value until more than
95% of the theoretical amount of methanol is distilled off.
In this way, the reaction system oligomeric BHBT-BD is
obtained. The number average molecular weight of the oli-
gomeric BHBT is determined using gel permeation chro-
matography after repeated recrystallization from water.
Determination of BD in Reaction System
Excessive amounts of unreacted BD in the above men-
tioned system is quantitatively determined by gas chroma-
tography using ethylene glycol as an internal standard
[18]. After the reaction is completed, 0.2–0.4 cm3 liquid
is taken into the sampling vial and weighed using the
Mettler H542 balance with an accuracy of 0.01/0.1 mg.
About 15 mL of chloroform is added into the vial and
then the mixture was heated under reflux until the oligo-
meric BHBT has been completely dissolved (10–20 min),
appropriate amount of ethylene glycol and 15 mL water
are added and the mixture is shaken vigorously, then
standing still and demixing. The water layer is separated
on a Supelcowax-10 column and detection is achieved
using a thermal conductivity detector.
Solubility Determination Procedure
The total solubility is determined by the last crystal
disappearance method. This method is based on sequen-
820 POLYMER ENGINEERING AND SCIENCE—-2009
tially adding known masses of a solid compound to a
stirred solution kept at a fixed temperature. The initial
mass of solvent is known precisely (in this case, about
150 g). When a solid increment had completely dissolved,
the next portion of solid is introduced. This procedure
is repeated until the last increment remained partially
undissolved. The mass of the increment is gradually
decreased when the solution saturation is approached,
which is indicated by the lengthening time necessary for
each increment to dissolve completely. This process needs
more than 4 h, and the last increment added is approxi-
mately 0.01 g. The solution in which the last increment
remains undissolved is regarded as saturated. The pres-
ence of solid in the solution is indicated visually as a
cloud point which appears when light is passed through
the solution.
The physical solubility of TPA in the reaction system
refers to the portion of the total TPA that is not reacted.
The supernatant liquid without undissolved TPA of the
saturated solution in total solubility determination proce-
dure is used to determine the physical solubility of TPA
by HPLC.
The magnetically stirred measuring vessel is placed in
a silicon oil bath. The oil is thermostated and controlled
with a thermoelectric controller (type DKU-30, China) to
the desired temperature (60.2 K). A thermometer with an
uncertainty of 0.1 K is inserted through the hole in the
stopper to measure the temperature of the vessel. The
masses of the solute and oligomeric BHBT are measured
with an analytical balance (type Mettler H542). The total
amount of solute added is recorded, and the total solubil-
ity is calculated.
When the solution becomes saturated at the fixed tem-
perature, the stirrer is stopped. The supernatant liquid
(0.5–1.0 g) without undissolved TPA is withdrawn by
using a sampler after about 10 min of stirrer stop. By
repeating the above procedure at different temperatures, a
series of samples are obtained. The liquid samples are dis-
solved in chloroform and analyzed by HPLC at 254 nm.
The mobile phase used is a mixture of methanol þ water
(60/40 volume %). A flux of 1 mL/min and a temperature
of 313 K are adjusted. To interpret the HPLC chromato-
grams, calibration standards are prepared for TPA. Based
on the calibration curve and diluted multiple, the physical
solubility at different temperatures can be obtained. All
of the measurements are repeated twice, and the mole
fraction of TPA could be calculated based on the follow-
ing equation:
m2 =M2
x2 ¼ (1)
m2 =M2 þ m1 =M1 þ m3 =Mn
where m1, m2, and m3 stand for the masses of BD, TPA,
and oligomeric BHBT, respectively; M1 and M2, are the
molecular weights of BD and TPA, respectively; Mn is
the number average molecular weight of oligomeric
BHBT.
DOI 10.1002/pen
TABLE 1. Experimentally determined physical solubility data of TPA where A21 and A12 are the coupling parameters of Mar-
(2) in the reaction system from 449 to 507 K with r = initial molar ratio gules equation and A21 is related to the infinite-dilution
of BD to DMT.
activity coefficient (g‘2) of solute by the expression as
x2
x2cal x2
x2cal
T (K) x2 3100 T (K) x2 3100
A21 ¼ lnc1
x2 x2
2
r ¼ 1.2:1
453 0.1050 4.01 482 0.2284 0.24 By incorporating Eqs. 2 and 3, nonlinear equation can be
458 0.1165 21.20 485 0.2448 0.74 obtained:
463 0.1358 21.68 489 0.2657 1.03
469 0.1625 20.91 493 0.2833 0.55
472 0.1766 21.10 498 0.3061 20.08 1 R ln x2 RA21 ð1
x2 Þ2
¼


477 0.1978 22.46 505 0.3379 0.08 T DHfus DHfus
r ¼ 1.4:1
2RðA12
A21 Þ 1
453 0.0828 20.98 481 0.1618 20.56
ð1
x2 Þ2 x2 þ ð4Þ
458 0.0928 22.25 484 0.1753 1.09 DHfus Tm
463 0.1099 2.08 489 0.1911 20.26
468 0.1222 0.73 497 0.2235 0.41 The nonlinear least square method is used to regress the
473 0.1395 2.18 502 0.2401 21.07 experimental physical solubility data with the above equa-
477 0.1472 21.09 507 0.2617 20.69
tion to estimate the parameters A21, A12, and DHfus.
r ¼ 1.6:1
449 0.0531 1.12 481 0.1149 0.70
455 0.0594 23.07 487 0.1269 22.59 RESULTS AND DISCUSSION
460 0.0688 20.92 492 0.1437 20.76
465 0.0807 2.69 497 0.1617 0.87
470 0.0898 1.38 501 0.1746 0.61 Physical Solubility
475 0.1008 1.24 507 0.1931 20.60
r ¼ 1.9:1 The physical solubilities of TPA in the reaction system
449 0.0326 2.42 479 0.0634 21.25 are measured by the analytic method from 449 to 507 K
453 0.0343 21.85 484 0.0713 20.44
457 0.0394 2.12 489 0.0783 21.71
and the experimental data are shown in Table 1. The
462 0.0435 0.25 492 0.0841 20.94 reaction systems are obtained by transesterification of
467 0.0482 21.34 497 0.0942 0.02 excess BD and DMT with the initial molar ratio (r) 1.2:1,
471 0.0536 20.04 505 0.1137 2.72 1.4:1, 1.6:1, 1.9:1, and 2.1:1 of BD to DMT, respectively.
r ¼ 2.1:1 The experimental data in Table 1 are related by Eq. 4
449 0.0227 0.04 474 0.0395 21.71
452 0.0247 1.62 479 0.0446 20.31
and the parameters (DHfus, A21, A12) are obtained and
456 0.0264 21.08 485 0.0502 21.22 shown in Table 2. The values of the root-mean-square
460 0.0299 2.13 493 0.0590 21.71 deviations (RMSD) and the correlation coefficients (R2)
464 0.0321 0.05 499 0.0686 1.05 are also listed in Table 2. The RMSD of the mole fraction
469 0.0359 20.18 505 0.0776 1.31 is defined as
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
PN 2
i¼1 ðx2cali
x2i Þ
PHYSICAL SOLUBILITY MODEL r¼
N
According to thermodynamic description of solid-liquid
equilibrium, the solubility equation is based on the equal- where N is the number of experimental points, x2cali rep-
ity of chemical potentials between components in all the resents the physical solubility calculated by Eq. 4, x2i rep-
coexisting phases. For pure solid phase, the following sol- resents the experimental value. The comparison between
ubility equation can be used [19, 20]: experimental data and calculated ones are shown in Table

 1. The calculated solubilities show good agreement with
DHfus 1 1
ln g2 x2 ¼
(2) the experimental values. The average deviation between
R Tm T experimental values and calculated ones is 1.20%. The
physical solubilities of TPA in the reaction system oligo-
where g2 is the liquid-phase activity coefficient of solute,
DHfus is the molar enthalpy of fusion of solute at the nor- TABLE 2. Marjules equation fitting parameters of TPA in reaction
mal melting point temperature Tm, T is the absolute tem- system with r = initial molar ratio of BD to DMT.
perature, R is the universal gas constant, and x2 is the
mole fraction of solute. The value of Tm used here is 675 r DHfus (kJ/mol) A21 A12 103r R2
K [21]. In Eq. 2, the activity coefficient g2 is the function 1.2:1 42.878 21.1078 24.4864 2.382 0.9984
of mole fraction x2, which can be described by Margules 1.4:1 40.555 20.9430 22.8472 1.790 0.9988
equation: 1.6:1 42.242 20.7938 22.1397 1.555 0.9985
1.9:1 42.588 20.2914 20.7411 1.115 0.9983
ln g2 ¼ ð1
x2 Þ2 ½A21 þ 2ðA12
A21 Þx2  (3) 2.1:1 39.186 0.2997 0.0279 0.584 0.9990

DOI 10.1002/pen POLYMER ENGINEERING AND SCIENCE—-2009 821

 meric BHBT-BD determined in this work along with the
values calculated with Eq. 4 are given in Fig. 1 for com-
parison. As can be seen, the solubility of TPA increases
with an increase in temperature. At the same temperature,
the solubilities of TPA decrease significantly with the
increase of the initial molar ratios of BD to DMT. For

FIG. 1. Physical solubility of TPA (2) in the reaction system with r ¼

initial molar ratio of BD to DMT.

TABLE 3. Experimentally determined total solubility data of TPA (2)

in the reaction system and the values of Cr and Tr.

Stotal Cr T Stotal Cr
T (K) g/100 g (%) (K) g/100 g (%)

r ¼ 1.2:1; Tr ¼ 472 K
453 2.542 1.10 482 6.865 7.63
458 2.856 1.12 485 7.593 8.51
463 3.408 1.17 489 8.490 8.68
469 4.303 3.39 493 9.411 9.99
472 4.830 4.84 498 10.595 10.78
477 5.658 6.61 505 12.252 10.89
r ¼ 1.4:1; Tr ¼ 458 K
453 2.415 3.06 481 7.107 29.59
458 2.775 4.45 484 7.770 30.16
463 3.406 6.01 489 9.046 32.30
468 4.567 20.98 497 11.470 34.93
473 5.382 21.87 502 12.863 35.81
477 6.300 28.98 507 13.989 36.37
r ¼ 1.6:1; Tr ¼ 455 K
449 2.107 3.56 481 7.550 35.64
455 2.411 5.02 487 8.962 39.18
460 3.322 19.36 492 10.160 40.15
465 4.022 20.87 497 11.898 41.24
470 4.992 28.36 501 12.800 42.06
475 6.083 33.19 507 14.807 42.18
r ¼ 1.9:1; Tr ¼ 453 K
449 1.742 4.37 479 6.777 50.67
453 1.904 7.88 484 7.916 52.11
457 2.265 10.64 489 9.400 55.33
462 2.935 23.35 492 10.080 54.99
467 3.781 33.78 497 12.005 57.22
471 4.566 38.76 505 15.563 59.27
r ¼ 2.1:1; Tr ¼ 452 K
449 1.546 4.99 474 5.587 53.50
452 1.784 10.14 479 6.870 57.04
456 1.962 12.49 485 8.437 60.38
460 2.625 25.60 493 10.858 63.46
FIG. 2. Physical solubility and the total solubility of TPA (2) in the
464 3.327 36.91 499 13.488 65.47
reaction system with r ¼ initial molar ratio of BD to DMT: (a) r ¼
469 4.353 45.95 505 16.841 68.42
1.2:1; (b) r ¼ 1.4:1; (c) r ¼ 1.6:1; (d) r ¼ 1.9:1; (e) r ¼ 2.1:1.

822 POLYMER ENGINEERING AND SCIENCE—-2009 DOI 10.1002/pen

example, at 493 K, the solubilities (x2i) of TPA in the
reaction system at the initial molar ratio of 1.2:1 and
2.1:1 are 0.059 and 0.283, respectively.
From data listed in Table 2, it is clear that infinite-dilu-
tion activity coefficient of TPA increases with the
increase in initial molar ratio, i.e., c‘2 becomes largest at
the initial molar ratio of 2.1:1. Table 2 shows that the
enthalpies of fusion DHfus of TPA obtained by least-
squares regression method from different systems are con-
sistent. The average value is 41.490 kJ/mol. It is in agree-
ment with the generally accepted literature value 40.425
kJ/mol [22]. The correlation coefficients are greater than
0.998, which indicates that the model is reliable.
Total Solubility
The total solubilities of TPA in the reaction system are
determined by the synthetic method and the data are listed
in Table 3. Figure 2 presents the comparison between
physical solubilities (Sphy) and the total solubilities (Stotal)
with initial molar ratio 1.2:1 (a), 1.4:1 (b), 1.6:1(c),
1.9:1(d), and 2.1:1 (e) of BD to DMT. The values of the
chemical solubility fraction (Cr) of TPA are also given in
Table 3. The Cr is defined as
Stotal
Sphy
Cr ¼  100% (5)
Stotal
where Sphy and Stotal represent the experimental values g/
100 g of physical solubilities and total solubilities,
respectively. It can be seen in Table 3 that the Cr
increases with an increase in temperature for a given sys-
tem. Furthermore, the larger the initial molar ratio is, the
more remarkable is the influence of temperature. In gen-
eral, the error from chromatography analysis is approxi-
mately 5%, so it is reasonable to define a starting temper-
ature of the reaction (Tr) at which Cr value is greater than
5%. The Tr values of the five systems are also listed in
Table 3, from which it can be seen that the reactions of
TPA with BD begin at 452–472 K. This phenomenon also
can be observed from Fig. 2, concretely, the Tr of every
system is corresponding to the branch point of the tow
curves.
CONCLUSION
Physical and total solubilities are reported for TPA in
the reaction system oligomeric BHBT-BD from 449 to
507 K. The physical solubilities are correlated by a solu-
bility model based on the Margules equation and the aver-
age deviation of the model is 1.20%. The contribution
DOI 10.1002/pen
rate (Cr) of chemical reaction to the solubility and the
starting temperature of the reaction (Tr) are defined. The
experimental results indicate that the reaction of TPA
with BD begin at 452–472 K.
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