See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/255763013

Advanced chemical recycling of poly(ethylene terephthalate) through

organocatalytic aminolysis

Article  in  Polymer Chemistry · February 2013

DOI: 10.1039/C2PY20793A

CITATIONS READS

80 792

11 authors, including:

Kazuki Fukushima Di S. Wei

The University of Tokyo University of Denver
67 PUBLICATIONS   3,480 CITATIONS    1 PUBLICATION   80 CITATIONS   

SEE PROFILE SEE PROFILE

Hans W Horn Gavin O Jones

IBM IBM
60 PUBLICATIONS   19,293 CITATIONS    55 PUBLICATIONS   3,000 CITATIONS   

SEE PROFILE SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Natural fiber reinforcements and natural fillers for polymers View project

Quantum Chemistry with Quantum Computers View project

All content following this page was uploaded by Gavin O Jones on 05 November 2014.

The user has requested enhancement of the downloaded file.

 Polymer
Chemistry
View Article Online
PAPER View Journal | View Issue

Advanced chemical recycling of poly(ethylene

terephthalate) through organocatalytic aminolysis†
Cite this: Polym. Chem., 2013, 4, 1610

Kazuki Fukushima,*a Julien M. Lecuyer,ab Di S. Wei,c Hans W. Horn,a Gavin O. Jones,a

Published on 19 December 2012 on http://pubs.rsc.org | doi:10.1039/C2PY20793A

Hamid A. Al-Megren,d Abdullah M. Alabdulrahman,d Fares D. Alsewailem,d

Melanie A. McNeil,b Julia E. Ricea and James L. Hedrick*a
Downloaded by ST LAWRENCE UNIVERSITY on 12 February 2013

We report the effective organocatalysis of the aminolytic depolymerization of waste poly(ethylene

Received 25th September 2012
Accepted 20th November 2012
DOI: 10.1039/c2py20793a
www.rsc.org/polymers
terephthalate) (PET) using 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) producing a broad range of
crystalline terephthalamides. This diverse set of monomers possesses great potential as building blocks
for high performance materials with desirable thermal and mechanical properties deriving from the
terephthalic moiety and amide hydrogen bonding. Further, a computational study established
mechanistic insight into self-catalyzed and organocatalyzed aminolysis of terephthalic esters, suggesting
that the bifunctionality of TBD particularly concerning activation of the carbonyl group differentiates
TBD from other organic bases.

Introduction However, it is still uncertain whether these advances have

Recent advances in biomass transformation have enabled
poly(ethylene terephthalate) (PET), a widely used thermoplastic,
to be regarded as a bio-based polymer.1 The escalating
production of PET today is, however, still leading to a global
concern over the treatment of PET waste products and their
destructive impact to the environment.2 Commonly practiced
mechanical recycling has been considered as a temporary
solution because the recycled PET, which is oen used for
secondary materials other than beverage bottles, ends up in
landlls. Early issues of the mechanical recycling were that the
residual metal catalysts used in the production of PET deterio-
rate the physical properties of PET such as intrinsic viscosity
and clarity during the material post-production process,2–5 and
that the bottle material contains not only PET homopolymer but
also copolymers derived from cyclohexanedimethanol and iso-
phthalic acid3,5 and other polymers such as polyvinyl chloride
and polyethylene-vinylacetate.6 Several innovations such as
solid-state polymerization,7 the addition of additives such as
chain extenders,8 the formation of composites with virgin PET,9
and so-called super cleaning10 have enabled the establishment
of a bottle-to-bottle recycling process via mechanical recycling.
a
IBM Almaden Research Center, 650 Harry Road, San Jose, CA 95120, USA. E-mail:
fukushima@yz.yamagata-u.ac.jp; hedrick@us.ibm.com
b
Chemical and Materials Engineering Department, San Jose State University, San Jose,
CA 95192, USA
c
Physics and Astronomy Department, University of Denver, Denver, CO 80208, USA
d
King Abdul Aziz City for Science and Technology, Saudi Arabia
† Electronic supplementary information (ESI) available: Experimental details and
Cartesian coordinates for optimized structures. See DOI: 10.1039/c2py20793a
enabled the establishment of a sustainable recycling system.
Chemical recycling is an ideal way of recovering pure mate-
rial.5,11 However, in comparison with mechanical recycling,
chemical recycling will remain uncompetitive unless one
develops innovative techniques to reduce production costs and
energy consumption12 by reproducing the production of bottle-
grade polymers in a highly efficient way. Nonetheless chemical
recycling can be leveraged as a standby for mechanical recycling
when polymers that have been degraded through repeated
mechanical recycling are chemically broken down to the
monomers.
In addition, waste PET can be chemically processed to form
monomers as feedstock for a variety of valued materials.13 In
particular, the aminolysis of PET, which is more thermody-
namically favorable than alcoholysis, can potentially provide a
spectrum of terephthalamides that can be broadly applicable to
the formation of additives, modiers, and building blocks for
high performance materials.14–16 Aromatic amides used in these
applications oen have enhanced mechanical and thermal
properties due to hydrogen bonding and rigidity of struc-
ture.16,17 Most terephthalamides are currently prepared through
amidation of dimethylterephthalate (DMT)18 or terephthaloyl
chloride (TC)19 monomers of PET. Several groups have reported
aminolytic depolymerization16,20–22 and modication of PET23
illustrating that generating useful materials from waste can be
produced that could potentially alleviate existing environmental
concerns and positively impact the management of limited
petroleum sources.
Although aminolysis reactions may be thermodynamically
more favourable chemical transformations than alcoholysis,
the use of catalysts21 or microwave irradiation22 are still needed

1610 | Polym. Chem., 2013, 4, 1610–1616 This journal is ª The Royal Society of Chemistry 2013

Paper
for efficient depolymerization. We recently reported that a
potent organic catalyst, 1,5,7-triazabicyclo[4.4.0]dec-5-ene
(TBD), positively impacts the depolymerization of PET by
ethylene glycol (EG), comparable to conventional metal cata-
lysts.24 Moreover, a recent report has demonstrated that TBD is
effective in aminolysis of various esters carried out at room
temperature under solventless conditions, indicating the
potency and versatility of the catalyst.25 These studies motivated
us to extend our organocatalytic depolymerization technique to
the aminolysis of PET thereby exploring alternative approaches
to the synthesis of terephthalamide compounds other than
those derived from DMT, and TC. Thus we investigated the
Published on 19 December 2012 on http://pubs.rsc.org | doi:10.1039/C2PY20793A
usefulness of TBD in the aminolytic depolymerization of PET
and surveyed the transformation of diverse amine compounds
into a variety of terephthalamide compounds.
Downloaded by ST LAWRENCE UNIVERSITY on 12 February 2013
Experimental
Materials
Post-consumer PET beverage bottles were used as the PET
source. The bottles were washed with water, dried in air at room
temperature, and shredded by hand to a size of about 3 to 5
square mm. The PET akes were then further dried at 80
C
under the vacuum overnight prior to use. TBD, amine reagents,
and solvents were used as received (Sigma Aldrich).
Measurements
1 the reaction involving 1b in w/w). The temperatures at which the
H and 13C NMR spectra were obtained on a Bruker Avance 400
Instrument at 400 MHz. Differential scanning calorimetry (DSC)
was recorded on a TA Instruments DSC Q2000 with a ramp rate
of 5
C min1 under a nitrogen atmosphere. A melting point of
the product was determined as the onset temperature of the
melting endotherm. Thermal gravimetric analysis (TGA) was
recorded on a TA Instruments TGA Q500 with a ramp rate of
5
C min1 under a nitrogen purge.
General procedure for the TBD-catalyzed aminolysis of PET
PET akes (0.48 g) were added into a 25 ml Schlenk tube con-
taining a reagent in excess (greater than 3 eq.) and 0.05 eq. of
TBD (17.5 mg) relative to a molar amount of the repeating unit
of PET (192). The tube was heated at a predetermined temper-
ature under nitrogen atmosphere in the absence of solvents.
Aliquots were taken for NMR analysis to monitor the conversion
and determine the end of the reaction. Upon completion, the
product was isolated by trituration and washing with
organic solvents. Detailed procedures for the formation of each
terephthalamide is provided in the ESI.†
Results and discussion
We rst estimated the catalytic activity of TBD in the aminolysis
of PET by determining the conversion of PET into the products
as a function of reaction time using two aromatic amines with
or without catalyst (Fig. 1). Conversions were calculated as a
function of the molar ratio of the terephthalamide and amine
reagents as determined by integration of their NMR signals at
This journal is ª The Royal Society of Chemistry 2013
View Article Online
Polymer Chemistry
Fig. 1 General scheme of (a) the TBD-catalyzed aminolysis of PET and conver-
sions of PET into (b) 2a and (c) 2b as a function of reaction time. The aminolysis of
PET was conducted using 0.48 g of PET and 6 eq. of amine upon heating at 120
C
for 2a and 180
C for 2b.
specic time points. Since two amines are consumed to form a
terephthalamide, the end of the reaction (100% conversion)
was dened as when the ratio (terephthalamide : amine) is
2 : (x  2), where x is the eq. amount of the amine reagents
initially added. As a general rule, an excess of amine is used in
these reactions since PET akes are amorphous and bulkier
than powdered PET or PET pellets. Thus, about 6 eq. of amine
was used in reactions involving the depolymerization of PET
with benzyl amine (1a) and aniline (1b) (to be precise, 3.3 eq.
were used in the reaction involving 1a, and 3.0 eq. were used in
reactions were conducted were dependent on the reactivity and
boiling or melting point of the reagent. As previously repor-
ted,20,21 the reactivity of amines in amidation reactions with
esters are predominantly dictated by their basicity. The ami-
nolysis of PET with 1a (pKa ¼ 9.34 (ref. 26a)) at 120
C was
complete in an hour in the presence of 5% TBD. When the
reaction was run without catalyst, approximately 30% of PET
was converted into 2a aer an hour and was still not complete
even aer 2 hours under these conditions (Fig. 1b). The ami-
nolysis of PET using aniline (pKa ¼ 4.58 (ref. 26b)) proceeded
quite slowly even though the reaction was performed at 180
C.
The reaction reached complete conversion aer 24 hours in the
presence of 5% TBD, but was only 50% complete in the absence
of TBD over the same period of time, reecting the moderate
basicity of aniline (Fig. 1c). The discontinuous functional
prole shown in Fig. 1c indicates that the reaction proceeds via
a multistep pathway.
Depolymerization of PET is generally considered as a rst
order reaction27 in cases involving the use of excess reagent
(greater than 10 eq.) as solvent. We have performed kinetic
studies of reactions involving 1a and 1b under second order
conditions because changes in concentration of the reagents
are not negligible. The semilogarithmic plots of time against
the PET conversion showed a linear correlation only in
the reaction involving 1a in the presence of 5% TBD (ESI,
Fig. S1†), where the rate of reaction, k, was determined to be
2.02  104 mol1 s1.
Since the aminolysis of PET starts off as a nonhomogeneous
system, the apparent reaction rate is dominated by mass
Polym. Chem., 2013, 4, 1610–1616 | 1611

Polymer Chemistry
transfer and dissolution of PET into (melted) amine reagents,
rather than by the chemical reaction.23 In our studies, PET
akes were not completely consumed during the induction
period, during which time the reaction rate hardly increases as
seen in Fig. S1.† Consequently, the kinetics could not be simply
evaluated by measuring concentration proles. These results
suggest that TBD catalysis accelerates the mass transfer, leading
to reduction of the induction period. Comparison of rate
constants aer the initial induction period, suggests that TBD
promotes the reaction about ten times faster for the reaction to
form 2a. The semilogarithmic plots for the reaction to form 2b,
however, show exponential increase aer the induction period,
Published on 19 December 2012 on http://pubs.rsc.org | doi:10.1039/C2PY20793A
implying that another concentration factor is involved. As
previously reported,24 ethylene glycol (EG) also serves as a
catalyst. Thus, we speculate that the catalysis may be bolstered
Downloaded by ST LAWRENCE UNIVERSITY on 12 February 2013
by EG gradually formed from PET during the reaction, espe-
cially in reactions involving weakly basic amines such as 1b.
We then focused on producing functional terephthalamides
as a potential key building block of high performance mate-
rials using different amine compounds. A diverse library of
terephthalamides was successfully developed from post-
consumer PET via TBD-catalyzed aminolysis, as shown in
Fig. 2. Here, most of our interest was devoted to the formation
Fig. 2 Terephthalamides produced through organocatalytic aminolysis of PET. See Table 1 for reaction conditions.
1612 | Polym. Chem., 2013, 4, 1610–1616
View Article Online
Paper
of bis-amine functionalized terephthalamides (2c–2k), because
diamine compounds are in demand as monomers for highly
thermostable polymers such as polyamides, polyimides, poly-
urethanes, and polyureas, and also as a hardener/modier for
epoxy resins. To the best of our knowledge, only compounds 2c
and 2l have previously been synthesized through aminolysis of
PET.20–22 Unlike glycolysis,24 visual inspection was insufficient
to determine the end of the aminolysis reactions. The products
crystallize out as the reactions proceed, and some reactions
require further time for the completion aer the reaction
mixture becomes homogeneous. Thus, reaction completion
was monitored by 1H NMR spectroscopy. Table 1 summarizes
the results of the TBD-catalyzed aminolysis reactions of PET
using various amines. A small amount of oligomeric by-
product was formed when using diamine reagents, most likely
as a dimer or trimer; the lone exception was observed for the
reaction involving 4-aminobenzylamine (1k). Similar to
glycolysis,24 the oligomeric by-product was reduced to a
minimal level by increasing reagent loading to 16 eq. (5 to
11 eq. in w/w) relative to PET. As previously reported,24 the
catalyst and excess reagent can also be recycled in the ami-
nolysis to avoid wasting expensive reagents, although this
resulted in longer reaction times.
This journal is ª The Royal Society of Chemistry 2013
 View Article Online

Paper Polymer Chemistry

Table 1 Summary of TBD-catalyzed aminolysis of PET using various amine reagentsa

Amineb eq. in mol

(eq. in w/w) pKac mpd (bp) (
C) Rxn temp. (
C) Rxn time (h) Yield (%) mp (
C)

1c 16 (5.0) 9.98 (ref. 26a) (118) 110 1 89 191

1d 16 (7.4) 10.65 (ref. 26d) 25–28 110 1 82 217
1e 16 (9.7) 11.02 (ref. 26c) 42–45 110 1 63 171
1f 16 (11.4) 9.46 (ref. 26c) 60–63 150 1 79 223
1g 16 (11.4) 9.19 (ref. 26e) (265) 150 1 67 128
1h 16 (9.1) 6.08 (ref. 26b) 138–143 190 18 72 301
1i 16 (9.1) 4.88 (ref. 26b) 64–66 190 18 75 295
1j 16 (9.2) 6.48 (ref. 26f) 117–122 190 18 72 240
1k 3 (2.0) 9.70 (ref. 26g) 37 120 2 70 203
1l 6 (2.1) 9.50 (ref. 26a) (170) 120 2 93 233
Published on 19 December 2012 on http://pubs.rsc.org | doi:10.1039/C2PY20793A

1m 3 (1.7) 9.91 (ref. 26h) (133) 120 2 74 173

1n 6 (1.9) 9.49 (ref. 26a) (53) 45 4 81 220
1o 22 (6.4) 8.15 (ref. 26c) (83) 70 135 66 205
Downloaded by ST LAWRENCE UNIVERSITY on 12 February 2013

a
PET (0.48 g) and TBD (17.5 mg) was used. b Relative to PET. c Ref. 26; measured at 25
C in water. d Melting points of reagents (boiling points are
shown in parentheses, where applicable).

Reactions involving alkyl and benzylic diamines were
complete in 1 to 2 hours, while reactions involving aryl
diamines 1h–1j, with moderate pKa's, were only complete aer
leaving them overnight, even upon heating at 190
C. Compared
to reactions involving 1c–1e, those involving 1h–1j require
longer reaction times and higher temperatures for complete
conversion.
However, similar to the reaction involving 1b, when per-
formed in the absence of TBD the time required for completion
almost doubles. Reactions involving 1k and 1l provided
mixtures of products at temperatures higher than 150
C.
Nevertheless, 2k and 2l were selectively formed via aminolysis at
lower temperatures without undesired side products. The
formation of 2l by the aminolysis of PET has previously been
described.20–22 In terms of reaction time, reaction temperature,
and product yield, the TBD-catalyzed aminolysis for 2l reported
in this study was comparable to, or more favourable than,
previous reports. Terephthalamides derived from amines 1n
and 1o, could also be formed but at longer reaction times due to
their lower boiling points and reactivities. All products are
crystalline and most of the products were easily isolated by
trituration and solid–liquid rinse with ordinary organic solvents
providing highly pure products with yields over 70%. Most of
the products possessed melting points over 200
C. It appears
that the combination of the terephthalic moiety and hydrogen
bonding attributed to the amide fragments contribute to the
high melting points. The high yields obtained for these very
pure compounds were controlled by the use of excess amine
reagent as well as active promotion of the reaction by TBD.
Chemoselectivity was achieved at low temperatures when
asymmetric amines were used.
In addition to these reactions highlighting the TBD-catalyzed
aminolysis of PET with primary amines we have also performed
one example using a secondary amine. Piperidine (1p, pKa ¼
11.22)26a successfully depolymerized PET upon heating at 100
C
for 16 h, providing the corresponding terephthalamide (2p) in
high yield (72%, see ESI†). Despite the strong basicity of
piperidine, this reaction is presumably slower in comparison to
those involving primary amines because of steric congestion
around the nitrogen atom.
With regards to 1g and 1i in Table 1, it is obvious that the
reactions would take longer time to recover products in around
80% yield if the reactions were conducted at 110
C where both
1g and 1i have been completely liqueed. This indirectly
suggests that the basicity of amine reagents inuences the
efficiency of the aminolysis reaction.
The crude reaction mixture typically comprises the target
terephthalamide, oligomeric by-product, excess reagent, and
minimal catalyst and EG, which are easily separated. In the
aminolysis of PET to form 2c conducted at 110
C for 2 h using
16 eq. of ethylenediamine (1c, EDA), the weight ratios of iso-
lated 2c and the by-products were 50 : 6 (89% yield of tereph-
thalimide) for the reaction using TBD, 41 : 12 (77% yield of
terephthalimide) for the reaction using 1,8-diazabicyclo[5.4.0]
undec-7-ene (DBU), and 38 : 13 (74% yield of terephthalimide)
for the reaction using no catalyst, in accordance with the
observation that aminolytic depolymerizations of PET can be
completed in reasonable time without a catalyst in some cases
(e.g. EDA). The basicity of DBU (pKa ¼ 24.34 in acetonitrile)28 is
similar to that of TBD (pKa ¼ 26.03 in acetonitrile),28 but DBU is
not as effective a catalyst in the reaction involving 1c, we
surmised that bifunctional activation by TBD must play a
crucial role in the aminolysis.
To gain an understanding of the mechanism of aminolysis of
PET with EDA in the absence of a catalyst, we performed density
functional calculations with B3LYP/aug-cc-pVTZ//B3LYP/6-
31+G* 29 in a continuum dielectric using IEF-cPCM30 as imple-
mented in GAMESS-US.31 We chose an implicit solvent repre-
sentation of EDA with a dielectric of 8.9 to approximate
the experimental conditions of the PET aminolysis (in EDA at
115
C).32
The self-catalysis model of aminolysis of esters was moti-
vated by Schaefer's study on the ammonolysis of methylformate
(MF) in which two ammonia molecules form a reactant–catalyst
dimer complex (Fig. 3a)33 (see ESI†). Thus, we investigated the
aminolysis of dimethylterephthalate (DMT, model for the

This journal is ª The Royal Society of Chemistry 2013 Polym. Chem., 2013, 4, 1610–1616 | 1613

Polymer Chemistry
Fig. 3 Comparison of models of (a) two ammonia molecules during self-catalysis
(N–N distance ¼ 3.2 Å) and (b) an EDA molecule (N–N distance ¼ 3.0 Å).
repeat unit of PET) with EDA (Fig. 4a). The barrier heights for
Published on 19 December 2012 on http://pubs.rsc.org | doi:10.1039/C2PY20793A
reactions involving 1, 2 and 3 molecule(s) of EDA (1 EDA, 2 EDA
and 3 EDA) were 36.5 kcal mol1, 28.7 kcal mol1 and 27.3 kcal
mol1, respectively (Fig. 4b); as expected, the barrier decreases
Downloaded by ST LAWRENCE UNIVERSITY on 12 February 2013
when the number of EDA molecules increases. In comparison to
the reaction involving the self-catalyzed aminolysis of MF (see
ESI†), the reactivity trend is similar but, the barriers for
Fig. 4 Scheme of aminolysis of dimethylterephthalate (DMT) using (a) EDA and (b) comparison of the rate limiting step in 1 EDA, 2 EDA, and (2 + 1) EDA pathways for
the aminolysis of DMT with EDA.
1614 | Polym. Chem., 2013, 4, 1610–1616
View Article Online
Paper
reactions involving DMT are 6–8 kcal mol1 higher. This is in
accordance with the observation that aromatic ester bonds are
harder to break than aliphatic ester bonds.24 Thus, the self-
catalyzed aminolysis of PET with EDA is plausibly explained by
the use of a large excess of EDA even though the barriers are
high in comparison with those observed for the ammonolysis of
MF and the glycolysis of PET in the presence of TBD.24,32
A detailed computational investigation on the organo-
catalytic aminolysis of PET (repeat unit modeled by methyl-
benzoate) using TBD or DBU as catalyst is reported elsewhere.34
These results are discussed here for comparison and contrast
with the data presented herein for the self-catalysis of the
aminolysis with EDA. The barrier heights for reactions involving
TBD were 22.9/20.9 (1 EDA/2 EDA) kcal mol1 and 25.9 (2 EDA)
for reactions involving DBU. Despite the fact that DBU has only
one hydrogen bond acceptor, it is a stronger base, and thus a
better catalyst, than EDA itself. However, activation of the
carbonyl group by hydrogen bonding with TBD or EDA is an
This journal is ª The Royal Society of Chemistry 2013

Paper
important factor in the aminolysis of PET. The difference in the
computed barrier heights corresponds to the experimentally
observed product weight ratios.
In conclusion, we have demonstrated the effective organo-
catalysis to promote aminolytic depolymerization of waste PET
using TBD as well as the production of a broad range of ter-
ephthalamide compounds that are crystalline with desirable
thermal and mechanical properties. This diverse set of mono-
mers shows a large potential as a building block of high
performance materials due to their physical properties arising
from terephthalic moiety and amide hydrogen bonding. The
computational study ascertained the mechanistic insight of
Published on 19 December 2012 on http://pubs.rsc.org | doi:10.1039/C2PY20793A
self-catalyzed aminolysis and organocatalyzed aminolysis of
terephthalic esters, suggesting that the bifunctionality of TBD
in particular for activation of the carbonyl group differentiates
Downloaded by ST LAWRENCE UNIVERSITY on 12 February 2013
TBD from other organic bases.
Notes and references
1 (a) Y. Román-Leshkov, J. N. Chheda and J. A. Dumesic,
Science, 2006, 312, 1933–1937; (b) R. M. Kriegel, X. Huang
and M. W. Schultheis, US 20090246430, 2009.
2 (a) L. M. Rios, C. Moore and P. R. Jones, Mar. Pollut. Bull.,
2007, 54, 1230–1237; (b) J. Scheirs, Polymer Recycling: Science,
Technology and Applications, Wiley, New York, 1998, ch. 4.
3 D. D. Cornell, in Modern Polyesters: Chemistry and Technology
of Polyesters and Copolyesters, ed. J. Scheirs and T. E. Long,
Wiley, New York, 2003, ch. 16, pp. 565–587.
4 H. Zimmerman and N. T. Kim, Polym. Eng. Sci., 1980, 20,
680–683.
5 P. Klein, in Recycling and Recovery of Plastics, ed. J. Brandrup,
M. Bittner, G. Menges and W. Michaeli, Hanser Gardner
Publ., Cincinatti OH, 1996, ch. 5, pp. 494–502.
6 (a) N. Torres, J. J. Robin and B. Boutevin, Eur. Polym. J., 2000,
36, 2075–2080; (b) A. Pawlak, M. Pluta, J. Morawiec,
A. Galeski and M. Pracella, Eur. Polym. J., 2000, 36, 1875–
1884; (c) M. Paci and F. P. L. Manita, Polym. Degrad. Stab.,
1998, 61, 417–420.
7 (a) H. A. Ghatta, S. Cobor and T. Severini, Polym. Adv.
Technol., 1997, 8, 161–168; (b) I. Kenoka and Y. Kawakami,
JP 2000219728, 2000.
8 (a) S. Japon, L. Boogh, Y. Leterrier and J. E. Manson, Polymer,
2000, 41, 5809–5818; (b) N. Torres, J. J. Robin and
B. Boutevin, J. Appl. Polym. Sci., 2001, 79, 1816–1824; (c)
X. Xua, Y. Dinga, Z. Qiana, F. Wanga, B. Wena, H. Zhoua,
S. Zhanga and M. Yang, Polym. Degrad. Stab., 2009, 94,
113–123; (d) B. Jacques, J. Devaux, R. Legras and E. Nield,
Polymer, 1996, 37, 1189–1200; (e) D. M. Conor and
K. A. Keller, US 20060148914, 2006.
9 F. M. Schloss and D. C. Balduff, US 5965081, 1999.
10 (a) A. S. F. Santos, J. A. M. Agnelli and S. Manrich, Food Addit.
Contam., Part A, 2010, 27, 567–573; (b) G. W. Bohnert and
T. E. Hand and G. M. DeLaurentiis, US 7473758, 2009; (c)
M. Gupta, S. A. Bandi, S. Mehta and D. A. Schiraldi, J. Appl.
Polym. Sci., 2008, 107, 3212–3220.
11 D. Paszun and T. Spychaj, Ind. Eng. Chem. Res., 1997, 36,
1373–1383.
This journal is ª The Royal Society of Chemistry 2013
View Article Online
Polymer Chemistry
12 (a) D. Carta, G. Cao and C. D'Angeli, Environ. Sci. Pollut. Res.,
2003, 10, 390–394; (b) H. Kurokawa, M. Oshima, K. Sugiyama
and H. Miura, Polym. Degrad. Stab., 2003, 79, 529–533; (c)
V. A. Kosmidis, D. S. Achilias and G. P. Karayannidis,
Macromol. Mater. Eng., 2001, 286, 640–647; (d)
M. S. Farahat and D. E. Nikles, Macromol. Mater. Eng.,
2001, 286, 695–704; (e) N. D. Pingale, V. S. Palekar and
S. R. Shukla, J. Appl. Polym. Sci., 2010, 115, 249–254.
13 (a) S. R. Shulka, A. M. Harad and L. S. Jawale, Polym. Degrad.
Stab., 2009, 94, 604–609; (b) M. Lu and S. Kim, J. Appl. Polym.
Sci., 2001, 80, 1052–1057; (c) K. Ertas and G. Güçlü, Polym.-
Plast. Technol. Eng., 2005, 44, 783–794; (d) C. Kawamura,
K. Ito, R. Nishida, I. Yoshihara and N. Numa, Prog. Org.
Coat., 2002, 45, 185–191; (e) D. E. Nikles and M. S. Farahat,
Macromol. Mater. Eng., 2005, 290, 13–30; (f) P. Radenkov,
M. Radenkov, G. Grancharov and K. Troev, Eur. Polym. J.,
2003, 39, 1223–1228.
14 (a) M. Van der Schuur, B. Noordover and R. J. Gaymans,
Polymer, 2006, 47, 1091–1100; (b) W. Fischer and
C. Helbling, EP 19940810643, 1995.
15 (a) T. J. Stierman, US 5212261, 1993; (b) G. Raspanti and
M. Brena, EP 0575836, 1997; (c) R. V. Sparer and
S. A. Pogany, US 4549010, 1985.
16 T. Spychaj, E. Fabrycy, S. Spychaj and M. Kacperski, J. Mater.
Cycles Waste Manage., 2001, 3, 24–31.
17 (a) J. P. Sheth, D. B. Klinedinst, T. W. Pechar, G. L. Wilkes,
E. Yilgor and I. Yilgor, Macromolecules, 2005, 38, 10074–
10079; (b) E. J. Woo, G. Farber, R. J. Farris, C. P. Lillya and
J. C. W. Chien, Polym. Eng. Sci., 1985, 25, 834–840.
18 (a) J. Krijgsman, D. Husken and R. J. Gaymans, Polymer,
2003, 44, 7043–7053; (b) L. Nery, H. Lefebvre and A. Fradet,
Macromol. Chem. Phys., 2003, 204, 1755–1764.
19 (a) H. Li, C. Liu, G. Guo, X. Zhou, J. Zhang, D. Shen, Z. Zhang,
P. Xie, S. Yu and R. Zhang, J. Polym. Sci., Part A: Polym. Chem.,
2002, 40, 3161–3170; (b) I. Aoki and S. Shinkai, JP 06192224,
1994; (c) G. A. Sotzing, J. R. Reynolds, A. R. Katritzky,
J. Soloducho, S. Belyakov and R. Musgrave,
Macromolecules, 1996, 29, 1679–1684.
20 H. Zahn and H. Pfeifer, Polymer, 1963, 4, 429–452.
21 (a) S. R. Shukla and A. M. Harad, Polym. Degrad. Stab., 2006,
91, 1850–1854; (b) M. E. Tawk and S. B. Eskander, Polym.
Degrad. Stab., 2010, 95, 187–194.
22 N. D. Pingale and S. R. Shukla, Eur. Polym. J., 2009, 45, 2695–
2700.
23 (a) M. Avadanei, M. Drobota, I. Stoica, E. Rusu and
V. Barboiu, J. Polym. Sci., Part A: Polym. Chem., 2010, 48,
5456–5467; (b) S. Nakano, US 6107438, 2000.
24 K. Fukushima, O. Coulembier, J. M. Lecuyer, H. A. Almegren,
A. M. Alabdulrahman, F. D. Alsewailem, M. A. McNeil,
P. Dubois, R. M. Waymouth, H. W. Horn, J. E. Rice and
J. L. Hedrick, J. Polym. Sci., Part A: Polym. Chem., 2011, 49,
1273–1281.
25 C. Sabot, K. A. Kumar, S. Meunier and C. Mioskowski,
Tetrahedron Lett., 2007, 48, 3863–3866.
26 (a) H. K. Hall Jr, J. Am. Chem. Soc., 1957, 79, 5441–5443; (b)
K. C. Gross and P. G. Seybold, Int. J. Quantum Chem., 2000,
80, 1107–1115; (c) D. D. Perrin, Dissociation Constants of
Polym. Chem., 2013, 4, 1610–1616 | 1615

Polymer Chemistry
Organic Bases in Aqueous Solution, Butterworths, London,
1965; Supplement, 1972; (d) A. E. Martell and R. M. Smith,
Critical Stability Constants, Plenum Press, New York, 1974,
vol. 2; (e) B. Gawe1 and W. Lasocha, Z. Kristallogr. Suppl.,
2007, 26, 611–616; (f) X. Shi, I. Banyai, W. G. Lesniak,
M. T. Islam, I. Orszagh, P. Balogh, J. R. Baker, Jr and
L. P. Balogh, Electrophoresis, 2005, 26, 2949–2959; (g)
J. F. King, R. Rathore, J. Y. L. Lam, Z. R. Guo and
D. F. Klassen, J. Am. Chem. Soc., 1992, 114, 3028–3033; (h)
J. Hine, F. A. Via and J. H. Jensen, J. Org. Chem., 1971, 36,
2926–2929.
27 N. Halacheva and P. Novakov, Polymer, 1995, 36, 867–874.
Published on 19 December 2012 on http://pubs.rsc.org | doi:10.1039/C2PY20793A
28 I. Kaljurand, A. Kutt, L. Soovali, T. Rodima, V. Maemets,
I. Leito and I. A. Koppel, J. Org. Chem., 2005, 70, 1019–1028.
29 (a) A. D. Becke, J. Chem. Phys., 1993, 98, 5648–5652; (b)
Downloaded by ST LAWRENCE UNIVERSITY on 12 February 2013
C. Lee, W. Yang and R. G. Parr, Phys. Rev. B: Condens.
Matter Mater. Phys., 1988, 37, 785–789; (c) S. H. Vosko,
L. Wilk and M. Nusair, Can. J. Phys., 1980, 58, 1200–1211;
(d) P. J. Stephens, F. J. Devlin, C. F. Chabalowski and
M. J. Frisch, J. Phys. Chem., 1994, 98, 11623–11627; (e)
W. J. Hehre, R. J. Ditcheld and J. A. Pople, J. Chem. Phys.,
1972, 56, 2257–2261; (f) T. Clark, J. Chandrasekhar,
1616 | Polym. Chem., 2013, 4, 1610–1616
View publication stats
View Article Online
Paper
G. W. Spitznagel and P. v. R. Schleyer, J. Comput. Chem.,
1983, 4, 294–301; (g) D. E. Woon and T. H. Dunning,
J. Chem. Phys., 1995, 103, 4572–4585.
30 V. Barone and M. Cossi, J. Phys. Chem. A, 1998, 102, 1995–
2001.
31 M. W. Schmidt, K. K. Baldridge, J. A. Boatz, S. T. Elbert,
M. S. Gordon, J. H. Jensen, S. Koseki, N. Matsunaga,
K. A. Nguyen, S. Su, T. L. Windus, M. Dupuis and
J. A. Montgomery, J. Comput. Chem., 1993, 14, 1347–1363.
32 Equations of state for 3(T) were obtained from CRC
Handbook of Chemistry and Physics, 84th edn., CRC
Press, Boca Raton, Fl. 2003, vol. 1, pp. 6–158 and
extrapolated 3(1/T) to the temperature under which the
reactions are conducted experimentally.
33 S. IIieva, B. Galabov, D. G. Musaev, K. Morokuma and
H. F. Schaefer III, J. Org. Chem., 2003, 68, 1496–1502.
34 H. W. Horn, G. O. Jones, D. S. Wei, K. Fukushima,
J. M. Lecuyer, J. L. Hedrick and J. E. Rice, Computational
investigations on organocatalytic amidation and trans-
esterication of aromatic esters as a model for the
depolymerization of polyethylene terephthalate, J. Phys.
Chem. A, 2012, DOI: 10.1021/jp304212y.
This journal is ª The Royal Society of Chemistry 2013