Polymer 52 (2011) 3443e3450

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Polymer
journal homepage: www.elsevier.com/locate/polymer

A quantum chemical study on the polycondensation reaction of polyesters:

The mechanism of catalysis in the polycondensation reaction
Isamu Shigemoto a, b, *, Tomonori Kawakami b, Hiroshi Taiko c, Mitsutaka Okumura a
a
Graduate School of Science, Osaka University, 1-1 Machikaneyama, Toyonaka, Osaka 560-0043, Japan
b
Advanced Materials Research Laboratories, Toray Industries, Inc., 2-1 Sonoyama 3-chome, Otsu, Shiga 520-0842, Japan
c
Composite Materials Research Laboratories, Toray Industries, Inc., 1515 Oaza-Tsutsui, Masaki-cho, Iyo-gun, Ehime 791-3193, Japan

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

Article history: We carried out a theoretical study on the mechanism of catalysis in the poly(ethylene terephthalate)
Received 30 November 2010 (PET) polycondensation reaction. Transesterification reaction of diethylterephthalate with ethanol is
Accepted 29 May 2011 investigated as a model system by using the B3LYP level of theory, and Sb(OEt)3, Ge(OEt)4 and Ti(OEt)4
Available online 6 June 2011
are adopted as model catalysts. We found that the metal center of metal alkoxides coordinates to the
carbonyl oxygen atom of the ester, and the alkoxy oxygen atom of alkoxy ligands attacks to the carbonyl
Keywords:
carbon atom of the ester to form the four-centered transition state. The activation energy for tetraethoxy
Poly(ethylene terephthalate)
titanium catalyzed reaction in vacuo is 15.47 kcal/mol; this is comparable to the experimental result of
Quantum chemistry
Polycondensation catalysis
11.2 kcal/mol for poly(butylene terephthalate)/Ti(OBu)4. Because the other mechanisms gave much
higher activation energies, this is the most convincing mechanism of PET polycondensation catalysis by
antimony, germanium and titanium alkoxides.
Ó 2011 Elsevier Ltd. All rights reserved.

1. Introduction catalyst [1,2,4,5]; although it demonstrates greater activity and

better color than antimony, high cost prevents its common use in
Poly(ethylene terephthalate) has become one of the most commercial production [1].
important thermoplastics because of its balance of excellent The most promising candidate as an alternative to antimony is
mechanical properties, good thermal properties and cost. It has titanium [1]. Although titanium-based catalysts are very active
assumed a role of primacy in the field of fibers, films and molding relative to antimony, the first generation of titanium-based cata-
materials. lysts, which were either alkoxides or simple chelates, were prone to
PET is made via a direct esterification route from terephthalic hydrolysis to reduce activity and yielded polymers of poor color.
acid (TPA) and ethylene glycol (EG) followed by polycondensation Now several companies are developing titanium-based catalysts
stage or by an ester interchange process involving dimethyl ester of and have patented in this area [1]. These latest catalysts are
TPA and EG followed by polycondensation [1e3]. Among a large designed to be stable and have been formulated to give a balance of
number of main group and transition metals that have been shown good activity and good color, however, more efficient and better
to have catalytic activity for the polycondensation of PET [2e5], color catalyst system is still demanded.
antimony trioxide is the most common polycondensation catalyst Despite the importance of catalysis to PET manufacture and
in commercial production. Although antimony has a good balance a number of patents on this subject, the mechanism of catalysis in
of catalytic activity, color and cost, more active catalyst is deman- the polycondensation reaction is poorly understood; yet an
ded to improve plant efficiencies. Furthermore, using antimony in increased understanding of how the metal center interacts with the
the preparation of PET has come under increasing scrutiny in polymerizing PET chain is important for facilitating further devel-
Europe and Asia [1]. This has led to PET manufacturers researching opments in catalyst design.
potential alternatives to antimony. Germanium oxide is a good Three different mechanisms have been proposed; (i) the metal
center acts as a Lewis acid, and activate carbonyl group to nucleo-
philic attack by the oxygen of an alcohol [5]. Other two mechanisms
assume exchange reactions between the metal ligands with OH
* Corresponding author. Toray Industries, Inc., Advanced Materials Research
Laboratories, 2-1 Sonoyama 3-chome, Otsu, Shiga 520-0842 Japan. Fax: þ81 77 533
end-groups of oligomers; then (ii) the alkoxy oxygen atom of the
8341. ester coordinates to the metal atom [6], or (iii) the carbonyl oxygen
E-mail address: [email protected] (I. Shigemoto). atom coordinates to the metal center, like the first mechanism, and

0032-3861/$ e see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymer.2011.05.055
3444 I. Shigemoto et al. / Polymer 52 (2011) 3443e3450

the carbonyl carbon atom have an attack by the alkoxy oxygen atom theory to determine the structures and energetics of the species
of a ligand oligomer [6]. These three mechanisms are illustrated in involved in the reaction. Furthermore, the polarizable continuum
Fig. 1. model was utilized to account for the effect of the solvent. Dieth-
In this work, we carried out a theoretical study of the mecha- ylterephthalate (DET) molecule was employed as a model of PET
nism of catalysis in the PET polycondensation reaction, using the oligomer, and antimony, germanium and titanium(IV) catalysts
hybrid density functional theory (DFT) method at the B3LYP level of were modeled as ethoxides, with the formulas being Sb(OEt)3,

H
R' O
L OR L OR
M O + R' OH M O
L R'' L R''

L OR'
M O + R OH
L R''
(i) Lewis acid mechanism (L)
R'
R' RO OR RO OR
O
O M M
R'' C
R'' RO OR O OR
O
O R
R RO OR
O + M
R'' R'O OR

O
(ii) Coordination of the ester alkoxy oxygen atom (E)
R
R'' RO OR R'' O OR
O M C M
R'O RO OR R'O O OR
OR
OR
RO OR RO O OR
OR
M C M
R'' C O OR R'' O OR
R'
OR'
RO RO OR
O + M
R'' R'O OR
(iii) Coordination of the carboxy oxygen atom (C)
Fig. 1. Proposed three mechanisms for polycondensation reaction of PET. (i) The metal center acts as a Lewis acid. (ii) The alkoxy oxygen atom of the ester coordinates to the metal
atom. (iii) The carbonyl oxygen atom coordinates to the metal center and the alkoxy oxygen atom of a ligand oligomer attacks to the carbonyl carbon.
 I. Shigemoto et al. / Polymer 52 (2011) 3443e3450 3445

Fig. 2. Optimized structure for the TS complex of transesterification reaction of DET

with ethanol without catalyst. Reaction path with four-centered TS was assumed.

Ge(OEt)4 and Ti(OEt)4, respectively. Three mechanisms illustrated

in Fig. 1 – Lewis acid (L), coordination of the ester alkoxy oxygen (E)
and the carbonyl oxygen (C) – were considered and reaction
pathways are investigated in detail. Methanol and ethanol were
used as solvents to mimic polar environments in the poly-
condensation reactor.

2. Computational procedure

All of the geometry optimizations were carried out in the gas

phase using hybrid DFT (B3LYP) [7e9]. LANL2DZ effective core
potentials and basis set [10e12] were used for titanium, antimony,
germanium atoms and 6-31G(d,p) basis set was adapted for oxygen,
carbon and hydrogen atoms in model molecules. The harmonic
vibrational frequencies of the reaction complexes were calculated
at the same level of theory, and used first to determine whether the
optimized structures are true minima or transition states (TSs). In
order to verify that the transition states connect the reactants with
the appropriate products, we calculated the intrinsic reaction
coordinates (IRC) using the algorithm developed by Gonzalez and
Schlegel [13,14]. The charge densities of each atom were obtained
using the standard Mulliken population analysis.
To account for the solvent effects, single point calculations were
performed using the polarizable continuum model (PCM) devel-
oped by Tomasi and co-workers [15,16] on the optimized struc-
tures.Methanol and ethanol were chosen as solvents to represent
polar environments, with the dielectric constants being 32.63 and
24.55, respectively. All calculations were performed with the
Gaussian03 program package [17].

3. Results and discussion

3.1. The polycondensation reaction without a catalyst

First of all, we had studied the transesterification reaction of DET

with ethanol as a model system of a polycondensation reaction of
PET without a catalyst. In this reaction, the oxygen atom of ethanol
acts as a nucleophile and attacks to the carbonyl carbon atom of
ester molecule, then four-center cyclic TS is formed. The geometry
of TS is illustrated in Fig. 2. The activation energy in vacuo was
calculated to be 45.35 kcal/mol; PCM corrected results were 46.14

Table 1
Activation energies (kcal/mol) of the transesterification reaction of DET with
ethanol. Fig. 3. Optimized structures of Sb(OEt)3, Ge(OEt)4 and Ti(OEt)4 model catalysts. Metal-
oxygen bond lengths are shown in angstroms.
Environment In vacuo Methanol Ethanol
Activation energies 45.35 46.14 46.08
3446 I. Shigemoto et al. / Polymer 52 (2011) 3443e3450

Table 2 and 46.08 kcal/mol for methanol and ethanol solvents, respectively.
Metal-oxygen bond distances and Mulliken charge distribution for model catalysts. These values are comparable to 40 kcal/mol reported by Yokoyama
MeO distance [Å] Mulliken charge et al. [18] for uncatalyzed polycondensation experiments, but
M O
higher than 23 and 21 kcal/mol according to Challa [19] and Hov-
enkamp [20] respectively. PCM correction has only a little effect on
Metal center Antimony 1.946e1.975 1.444 0.752 to 0.742
Germanium 1.752e1.755 1.810 0.752 to 0.743 activation energies (Table 1).
Titanium(IV) 1.800e1.810 1.289 0.629 to 0.625

Fig. 4. Optimized geometries of the reactants (left) and TSs (right) complexes in the Lewis-acid catalyzed transesterification reaction of DET with ethanol. Metal-carbonyl oxygen
bond lengths are shown in angstroms.
 I. Shigemoto et al. / Polymer 52 (2011) 3443e3450 3447

Table 3 Table 4
Activation energies (kcal/mol) of the transesterification reaction in the Lewis-acid The distance between the metal center and the carbonyl oxygen atom of DET
mechanism. (R(MeO)), the Mulliken charge densities of carbonyl carbon ( qcarbonyl C), and the
negative frequencies of TSs for the mechanism L.
Environment In vacuo Methanol Ethanol
Activation energies Antimony 46.84 47.12 47.07 R (MeO)/Å qcarbonyl C
Negative frequencies
Germanium 43.55 44.86 44.84 of TSs/cm1
Titanium(IV) 44.96 45.07 45.10 Uncatalyzed e 0.610 1131.59
Antimony 2.923 0.638 1193.00
Germanium 4.858 0.615 1178.31
Titanium(IV) 2.766 0.636 1165.03
3.2. The molecular structures of model catalysts

To investigate the molecular structures of model catalysts, have only a little effect on the reaction. PCM correction has only
geometry optimization was performed for Sb(OEt)3, Ge(OEt)4 and a little effect on activation energies.
Ti(OEt)4 metal ethoxides. Optimized structures are illustrated in The optimized geometries of the reactant and TS complexes
Fig. 3, and metal-oxygen bond distances and Mulliken charge shown in Fig. 4 exhibit the distance between the metal center and
distribution are shown in Table 2. Because the ion radius of anti- the carbonyl oxygen atom of DET (R(MeO)) in each model is too
mony(III) is larger than that of germanium(IV) or titanium(IV), the long to have strong interaction. The values of R(MeO) in the reac-
antimony-oxygen distances in Sb(OEt)3, 1.96 Å, is longer than 1.75 Å tant structures are written in Table 4. Table 4 also shows the Mul-
in Ge(OEt)4 or 1.80 Å in Ti(OEt)4. On the other hand, Sb(OEt)3 is liken charge densities of carbonyl carbon ( qcarbonyl C) in each model.
similar to Ge(OEt)4 with respect to Mulliken charge on oxygen Although Lewis acid withdraws electron density from the carbonyl
atoms and Ti(OEt)4 has different character from the other two
alkoxides. It is anticipated that the charge value on oxygen is
related to the activity as a polycondensation catalyst. Table 5
Activation energies (kcal/mol) and the negative frequencies of TSs (cm1) for the
mechanism E.
3.3. The polycondensations reaction with the Lewis acid mechanism
Activation energies Negative frequencies
of TSs (In vacuo)
The activation energies of the reaction with the Lewis acid In vacuo Methanol Ethanol
mechanism (mehcanism L) are reported in Table 3. Activation Antimony 31.87 32.43 32.46 167.37
energies shown in Table 3 are nearly identical to that for non Germanium TS not found
Titanium(IV) 26.91 26.58 26.61 142.91
catalyzed reaction; in this mechanism, metal ethoxides seem to

Fig. 5. Optimized geometries of the reactants (left) and TSs (right) complexes in the coordination of ester oxygen atom mechanism. Metal-ester oxygen bond lengths are shown in
angstroms. The TS for Ge(OEt)4 catalyst was not found in this mechanism.
3448 I. Shigemoto et al. / Polymer 52 (2011) 3443e3450

Fig. 6. Optimized geometries of the reactants (left) and TSs (right) complexes in the coordination of carbonyl oxygen atom mechanism. Metal-carbonyl oxygen bond lengths are
shown in angstroms. The quasi TS is illustrated for Sb(OEt)3 catalyst (see section 3.5 for detailed discussion).
 I. Shigemoto et al. / Polymer 52 (2011) 3443e3450 3449

Table 6
Activation energies (kcal/mol) and the negative frequencies of TSs (cm1) for the
mechanism C. Figures calculated for the quasi TS structure are written in parenthesis
(see text for detail).

Activation energies Negative frequencies

of TSs (In vacuo)
In vacuo Methanol Ethanol
Antimony (22.6) (22.1) (22.2) (e198.3)
Germanium 21.60 23.12 23.10 119.55
Titanium(IV) 15.47 15.73 15.63 225.21

group and activate the carbon atom to nucleophilic attack, qcarbonyl C

values in our models are almost identical to that of isolated DET
molecule. We did not found significant change in the negative
frequencies of TSs either.
These results suggest that the Lewis acid mechanism is not
applicable to antimony, germanium and titanium alkoxides.
However, Parshall and Ittel indicate that divalent metal ions, such
as calcium dication, are said to act as Lewis acids in the catalysis of
transesterification [5].

3.4. Coordination of the ester or carbonyl oxygen atom mechanisms Fig. 7. Contour plot of the potential energy surface of the Sb(OEt)3 catalyzed reaction
in the coordination of carbonyl oxygen atom mechanism. TS geometries for Ge(OEt)4
Fig. 5 shows the optimized geometries of the reactant and TS and Ti(OEt)4 catalysts are also indicated.

complexes in the coordination of ester oxygen atom mechanism

(mechanism E). In this mechanism, the alkoxy oxygen atom of
ethoxy ligands of antimony or titanium alkoxides attacks to the alkoxides. Our conclusion is consistent with the consideration by
carbonyl carbon atom of the ester to form four-centered TSs. Our Bradley and Mehrotra [6]
calculations failed to locate the TS for germanium alkoxide; it In addition, Tables 5 and 6 show that PCM correction have only
seems that the tetrahedral structure of Ge(OEt)4 is bulky and the a little effect in these two mechanisms, as same as Table 3.
interaction between germanium center and ester alkoxy oxygen
atom is too weak to activate this type of reaction. Activation ener-
gies and the negative frequencies of the TSs are reported in Table 5. 3.5. The potential energy surface for the antimony catalyzed
Activation barriers are much lower than that of uncatalyzed reac- reaction in the coordination of carbonyl oxygen atom mechanism
tion, but our result of 31.87 kcal/mol for antimony is higher than
18.5 kcal/mol for antimony catalyzed PET polycondensation Because the TS structure for the antimony catalyzed reaction in
according to Yokoyama [18]. For titanium, we obtained 26.91 kcal/ the coordination of carbonyl oxygen atom mechanism was not
mol but it is much higher than 11.2 kcal/mol for tetrabutoxy tita- obtained by standard procedure, we carried out a two dimensional
nium catalyzed poly(butylene terephthalate) reported by Pilati potential energy surface (PES) scan for the reaction. The first
et al. [21] coordinate was taken to be the distance between the carbonyl
Finally, another mechanism, coordination of the carbonyl carbon atom and the oxygen atom of ethoxy ligand (R(CeO)), and
oxygen atom (mechanism C), was investigated and activation the second coordinate was the distance between the antimony
energies are summarized in Table 6. Although this mechanism atom and the ethoxy oxygen (R(MeO)). These coordinates and the
includes multiple steps as illustrated in Fig. 1, we studied only the PES contour plot are illustrated in Fig. 7.
first half of the reaction because the TS of the second half is In the PES plot, the reactant structure is located at the lower
identical to the first one in our model system. Because we could right corner and the intermediate is at the upper left. While the
not find the exact structure of the TS for antimony, figures for TS should exist between these two points, any attempts to
antimony are calculated for the quasi TS structure and written in optimize the TS structure around R(CeO) ¼ 1.8 Å and
parenthesis to differentiate them from those for other catalysts, R(MeO) ¼ 2.2 Å failed to give false TS which corresponds to the
whose TSs are examined carefully. The case for antimony will be torsional motion of the ligand ethoxy group. This implies that any
discussed later in detail. Reactant and TS structures are illustrated potential energy well and the saddle point on the surface around
in Fig. 6, while shown TS for antimony is the quasi TS written the real TS must be shallow. We therefore picked up the point
above. (R(CeO), R(MeO)) ¼ (1.75 Å, 2.2 Å) as the quasi TS structure and
Table 6 shows the lowest activation barrier heights among all performed normal mode analysis to examine that the structure
three mechanisms. The activation energy for tetraethoxy tita- has only one negative sign frequency and the negative mode
nium in vacuo is 15.47 kcal/mol; this is slightly higher than oscillates in the right direction which connects the reactant and
11.2 kcal/mol for PBT/Ti(OBu)4 reported by Pilati et al. [21], but the intermediate.
approximately equivalent to the experimental result. Although The coordinates of the TSs for germanium and titanium are also
22.6 kcal/mol for antimony is a tentative value, it is also indicated in Fig. 7. In comparison with germanium and titanium,
comparable to the experimental result of 18.5 kcal/mol reported the TS for antimony has longer R(MeO). That reflects the ion
by Yokoyama [18]. radius of antimony(III) is larger than that of germanium(IV) or
These results suggest that the coordination of the carbonyl titanium(IV); the antimony-oxygen distances in an alkoxide,
oxygen atom is the most convincing mechanism of PET poly- Sb(OEt)3, is 1.96 Å, which is longer than 1.75 Å in Ge(OEt)4 or
condensation catalysis by antimony, germanium and titanium 1.80 Å in Ti(OEt)4.
3450 I. Shigemoto et al. / Polymer 52 (2011) 3443e3450

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the online version, at doi:10.1016/j.polymer.2011.05.055.