Green Chemistry: E Ect of A Phase Transfer Catalyst Structure On The Alkaline Hydrolysis of Poly (Ethylene Terephthalate)

Green Chemistry
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Effect of a phase transfer catalyst structure on the

alkaline hydrolysis of poly(ethylene terephthalate)†
Open Access Article. Published on 11 October 2024. Downloaded on 10/21/2024 5:16:00 PM.
Cite this: DOI: 10.1039/d4gc05070c
Lee B. Anderson, Conall Molloy, Lorenzo Pedrini, Ian L. Martin and

Received 10th July 2024,
Accepted 10th October 2024 Stephen J. Connon *
DOI: 10.1039/d4gc05070c
rsc.li/greenchem
A systematic investigation into the factors which influence catalytic intensive superclean methodologies are utilised,3,6,7 while
activity in 50 simple (mostly) quaternary ammonium- and phos- chemical recycling via depolymerisation requires efficient
phonium halide catalysts for the hydrolysis of poly(ethylene tere- chemical processes on large scale (frequently at high tempera-
phthalate) has revealed the most efficacious constitutional isomer tures);7 however it can produce pure monomers which can be
class and the optimum properties these catalysts should possess. repolymerised to pristine PET for any application, thereby
General guidelines for catalyst design are provided. reducing reliance on fossil fuel-derived virgin PET.3,7 In
addition, in the case of PET, a recent analysis found that CO2
It has been estimated that from 1950 to 2015, 6.3 × 1012 kg of emission saving at end of life treatment is considerably lower
plastics have been synthesised – with a recycle rate of just ca. for chemical recycling than for mechanical recycling.3
9%. Without intervention, by 2050, 12 × 1013 kg of these poly- Chemical recycling methodologies include (inter alia) amino-
mers will either be in landfill or out polluting the natural lysis, alcoholysis, glycolysis and hydrolysis.8 A particularly
world;1 therefore (until replacement of traditional plastics with attractive potential PET recycling methodology is alkaline
sustainable materials is widespread) improvement in both the hydrolysis in the presence of a phase transfer catalyst (PTC).
rate and efficiency of recycling is needed to reduce both the This has the advantages of lower reaction temperatures (typi-
dependence on oil-derived virgin plastic and the contribution cally 80–100 °C) than those required by neutral hydrolysis and
its synthesis/disposal makes to the current climatological and less contamination by oligomers or decomposition of ethylene
ecological emergency. glycol using either neutral or acidic hydrolysis, respectively.8
Poly(ethylene terephthalate) (PET) polyester is a major con- While phase transfer catalysis9 of alkaline PET hydrolysis to
stituent in certain beverage bottles, textile fibres and food tray/ form (after acidic workup) terephthalic acid is known for over
pharmaceutical packaging, which in 2021 accounted for 12% two decades,8 the PTC characteristics required to bring about
of worldwide solid waste.2 Of the commonly bulk-manufac- efficient promotion of the process are poorly understood.
tured plastics, PET has the highest greenhouse gas (GHG) Attempts to elucidate a consensus model of the contributors to
emissions associated with its production (up to 4.5 kg GHG catalytic activity are confounded by studies using different cat-
per kg PET)3,4 yet it is one of the most amenable for various alysts, loadings (1–100 mol%), PET sources, particle sizes,
‘recycling’ methodologies – which can be broadly categorised temperatures, stirring speeds, NaOH stoichiometry, NaOH
as either incineration or mechanical or chemical recycling. concentrations,10–17 microwave-radiation18 and ultrasound.19,20
Incineration solves the landfill problem and can recover For instance, tetrabutylammonium iodide (TBAI) has been
energy from the materials but it has been determined after a reported as an active catalyst in one study19 at 1 mol% loading
recent study5 by the European Commission’s Joint Research (no control experiment without a catalyst reported), while its
Centre that it is less preferable from a climate change impact bromide analogue has been reported as completely inactive in
perspective. Mechanical recycling is operationally more facile, another study at 24 mol% loadings (conversion identical to
yet amplifies existing degradation and produces recycled PET that of the control).12 Both studies used similar PET sources
of lower value and quality unless complex, more resource and very small particle sizes (ca. 0.25 mm), but different reac-
tion temperatures and NaOH concentration/loadings. The
latter study identified the large, water-insoluble tributyl-
School of Chemistry, Trinity Biomedical Sciences Institute, Trinity College Dublin,
152-160 Pearse St., Dublin 2, Ireland. E-mail: connons@tcd.ie
hexadecylphosphonium bromide as the optimal catalyst.12
† Electronic supplementary information (ESI) available. See DOI: https://doi.org/ The non-PET hydrolysis literature offers clues regarding
10.1039/d4gc05070c ideal catalyst attributes but not conclusions – Herriot et al.21
This journal is © The Royal Society of Chemistry 2024 Green Chem.

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found that larger symmetrical cations outperformed catalysts Table 1 Alkaline hydrolysis of PET catalysed by symmetrical PTCsa
with one long chain in an SN2 reaction in benzene/water cata-
lysed by ammonium and phosphonium PTCs, while earlier
Starks9c had warned that ammonium PTCs were poor overall
promoters of alkaline ester hydrolysis if the ester incorporated

a long chain, including when using poly(methyl acrylate) as a
substrate.
Herein we report the results of investigations aimed at
shedding light on the contribution of the structural features of
simple quaternary phosphonium- and ammonium-based PTCs
to the catalytic activity in the alkaline hydrolysis of PET under

conditions that we considered might prove a useful starting
point from which a later real-world recycling process might be
developed by others: i.e. 500 mg of PET flakes of larger size
(ca. 5 mm square – consistent with the output from mechani-
cal PET recycling facilities) cut from colourless water bottles
purchased locally at a large supermarket chain, relatively low
NaOH loadings and water usage (500 mg NaOH dissolved in No. of Solubility under Yieldb
5 mL HPLC H2O – ca. 10 wt%, 4.8 eq.), 90 °C and 500 rpm stir- Entry Catalyst carbon atoms reaction conditions (%)
ring speed. Catalysts were utilised at 5 mol% loading. TPA was 1 None 0 — 4.2
isolated, with high purity by NMR spectroscopy, after protona- 2c None 0 — 3.9
3 1 4 Soluble 3.2
tion (see the ESI†) of disodium terephthalate with HCl (aq.); 4 2 4 Soluble 3.7
however to avoid any possibility of yield data being compro- 5 3 16 Soluble 49.4
mised by the presence of oligomers (which could confound 6 4 16 Soluble 32.2
7 5 16 Soluble 31.8
analysis), an internal standard (4-iodoanisole) was added after 8 6 16 Soluble 30.4
the reaction so that accurate yields could be determined by 1H 9 7 20 Finely dispersed 67.8
NMR spectroscopy. An ad hoc catalyst classification system to 10 8 24 Insoluble 47.1
11 9 32 Insoluble 37.6
allow facile comparison of data was decided upon at the outset 12 10 32 Insoluble 38.8
– catalysts were classified as being symmetrical, 3 chained (i.e.
a
one methyl group), 2 chained (i.e. 2 methyl groups), 1 chained, Reaction conditions as outlined in Scheme 1. b Determined by 1H
NMR spectroscopy using 4-iodoanisole as an internal standard.
benzylated, aromatic or ionophoric (generic structures not c
Repeat of the experiment outlined in entry 1.
shown). The catalyst classes and standardised conditions
under which they were evaluated are depicted in Scheme 1.
The investigation commenced with an examination of sym-
metrical catalysts (Table 1). To facilitate catalyst comparisons were utilised and the number of carbon atoms in each catalyst
from a lipophilicity standpoint, only hydrocarbon substituents is also provided. In the absence of any PTC, very low product
yields of 4% were reproducibly obtained (entries 1 and 2).
Tetramethylphosponium- and ammonium salts 1–2 (entries 3
and 4) appear to moderately inhibit hydrolysis; however the
commonplace water-soluble tetrabutylphosphonium-21,22 and
ammonium salts 3–6 exhibited appreciable activity (entries
5–8). The more lipophilic 3 considerably outperformed its
ammonium variants 4–6, while variation of the anionic com-
ponent had – as expected – little influence on the outcome
once the catalyst was soluble in the reaction medium. The tet-
rapentyl homologue 7 exhibited interesting behaviour: it was
partially soluble in the reaction medium and the undissolved
portion was very finely dispersed. This catalyst promoted the
reaction with considerably superior efficacy to the tetrabutyl
analogue 5 (entry 9). Further chain extension led to increasing
levels of insolubility (note: hereafter ‘insoluble’ is used as an
ad hoc term meaning that the catalyst forms a discrete aggre-
gated phase under the reaction conditions (5 mol% cat., 90 °C,
5 mL H2O, 500 mg NaOH) – this is not meant to imply that
Scheme 1 Standardised conditions utilised in the PTC-catalysed alka- that no fraction of that catalyst is soluble in the reaction
line PET hydrolysis and the catalyst classes employed. medium) and diminished yields (i.e. 9–10, entries 10–12).
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The evaluation of catalysts characterised by 3 longer chains Table 3 Alkaline hydrolysis of PET catalysed by 2-chain PTCsa
is outlined in Table 2. The tripentylmethylammonium species
11 facilitated the formation of 2 in appreciable yield (entry 1).
The partially soluble, finely dispersed homologue 12 is
capable of marginally greater activity (entry 2) – however as

observed earlier (vide supra), lipophilicity could not thereafter
be increased to advantage (i.e. 13–15, entries 3–5).
The two-chain catalyst class was the most useful and
instructive (Table 3). The soluble catalyst 16 possesses only 14
carbon atoms, yet could facilitate hydrolysis with >40% yield
(entry 1) – considerably greater than that associated with the

use of the 16-carbon symmetrical material 5 (compared to
Table 1, entry 7). Augmentation of each longer chain by one
methylene unit (i.e. 17, entry 2) resulted in a soluble catalyst
with 16-carbon atoms and strikingly improved efficacy superior
to that associated with any catalyst hitherto evaluated.
Most interestingly, further elongation of the 2 chains by a
methylene unit (i.e. catalyst 18, entry 3) resulted in a finely dis-
persed system and a reduction in performance. As mentioned
before, once a design change led to catalyst insolubility
without fine dispersion under the reaction conditions, efficacy
declined and all further chain elongations resulted in decreas-
ingly active catalysts (i.e. 19–23, entries 4–8).
Single long-chain quaternary ammonium salts (Table 4)
proved relatively ineffectual as catalysts, whether soluble or not
(i.e. 24–27, entries 1–4). Furthermore, these catalysts gave rise
No. of carbon Solubility under Yieldb
to emulsions which complicate the isolation of 2. The phos-
Entry Catalyst atoms reaction conditions (%)
phonium salts 28 and 29 are included here and mediate hydro-
lysis with moderate efficacy (superior to that associated with 1 16 14 Soluble 41.1
2 17 16 Soluble 81.9
24–27, entries 4–6). These catalysts possess one chain longer 3 18 18 Finely dispersed 70.6
than the others, yet their ‘small’ substituents are of 4–6 carbon 4 19 20 Insoluble 57.6
Table 2 Alkaline hydrolysis of PET catalysed by 3-chain PTCsa
a
Reaction conditions as outlined in Scheme 1. b Determined by 1H
atoms in length. Hence they can be seen as a hybrid of single-

chain (Table 4) and mid-sized symmetrical systems (e.g. 3,
Table 1) – which would correlate well with the levels of activity
observed. From this perspective, the longer chain does not
show greater contribution to efficacy than the shorter substitu-
ents – and it is noteworthy that adherence of the PET flakes to
each other was observed in both experiments.
Catalysts incorporating benzyl (or similar) units were next
examined (Table 5). These were hypothesised – a priori – to be
No. of carbon Solubility under Yieldb of promise due to the potential for attractive π-stacking inter-
actions with the polymer. Parikh et al.11 reported that benzalk-
1 11 16 Soluble 56.4 onium chloride outperformed aliphatic (albeit relatively hydro-
2 12 19 Finely dispersed 59.0
3 13 25 Insoluble 55.5 philic) tetraalkylammonium salts in the alkaline hydrolysis of
4 14 25 Insoluble 43.7 PET; however we are unaware of any systematic study regarding
5 15 25–31 Insoluble 27.6 the influence of this group on the catalytic activity.
a
Reaction conditions as outlined in Scheme 1. b Determined by 1H The small and soluble trimethylbenzyl ammonium salt 30
NMR spectroscopy using 4-iodoanisole as an internal standard. and its triethyl homologue 31 – the first PTC to be intensively

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Table 4 Alkaline hydrolysis of PET catalysed by 1-chain PTCsa Table 5 Alkaline hydrolysis of PET catalysed by benzylated PTCsa

1c 24 11 Soluble 17.1
2c 25 13 Soluble 26.9
3c 26 17 Soluble 32.8
4c 27 19 Soluble 29.7
5d 28 24 Insoluble 42.9
6d 29 32 Insoluble 53.4
a
c
Formation of an emulsion as the reaction progressed was observed.
d
Severe adherence of the PET flakes to each other was observed.
1 30 10 Soluble 5.6
studied 9b,23 – (entries 1 and 2) exhibited little activity under 2 31 13 Soluble 8.8
these conditions. The considerably more lipophilic 3 32 19 Soluble 43.6
4 33c 19 Soluble 19.7
ammonium salt 32 was shown to be a more suitable catalyst 5 34 23 Insoluble 75.9
(entry 3), while its phosphonium variant 33 decomposed 6 35 23 Insoluble 68.7
(entry 4). Extension of the π-system was generally advantageous 7 36c 23 Insoluble 14.6
(i.e. catalysts 34–38 entries 5 and 6) unless either a phos- 9 38 27 Insoluble 19.2
phonium salt (entry 7) or an anthracene unit (entry 9) was 10 39 25 Insoluble 40.5
involved. An interesting phenomenon was observed here: cata- 11 40 16 Soluble 18.9
12 41 20 Soluble 33.4
lysts of increasing size no longer immediately became less 13 42 22 Soluble 47.5
active when insoluble. For instance, both the insoluble 14 43c 26 Insoluble 81.4
naphthyl-substituted catalysts 34 and 35 show improvements 15 44c 24 Insoluble 53.3
16 45 28 Soluble 39.2
compared to the soluble, benzyl analogue 32 (entries 3, 5 and 17 46 30 Insoluble 60.5
6). It is clear that the introduction of aromatic substituents
a
changes the behaviour of these systems relative to aliphatic Reaction conditions as outlined in Scheme 1. b Determined by 1H
analogues. The dioctylisoquinolinium salt 39 (entry 10) was a c
Catalyst decomposition.
moderately effective catalyst which lacked the activity of
simpler systems mentioned above – so investigations along
these lines were halted and attention switched to novel diben-
zylated systems. from the impressive performance of the insoluble 43 (entry
As expected, the small, soluble salt 40 did not excel as a 14). Bis-naphthyl/bis-biphenyl analogues of 40 and 42 (i.e.
catalyst (entry 11); however its dipropyl- and dibutyl-analogues 44–46, entries 15–17) proved to be serviceable catalysts, yet all
(41 and 42, entries 12 and 13, respectively) showed significant were inferior to 43.
improvements. Once again, the immediate penalty paid from The evaluation of miscellaneous systems is outlined in
an efficiency standpoint when catalysts in previous classes Table 6. The simple trimethylanilinium species 47 showed
became wholly insoluble in the reaction medium is not of the little activity (entry 1) while both pyridinium salts 48 and 49
same magnitude in this class of promoters – as can be seen and the tetraphenylphosphonium salt 50 decomposed (entries

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Table 6 Aromatic- and ionophore-based catalystsa


1 47 9 soluble 7.0
2 48c 6 soluble 4.1
3 49c 13 insoluble 14.0
4 50c 24 insoluble 6.5
5 51 10 soluble 5.3
a
c
Catalyst decomposition.
2–4). The ionophore 51 – an efficient binder of Na cations –

was also inactive, which strongly indicates that effective deliv-
ery of the hydroxide anion to the PET surface is the most
important for catalyst competency and not effects stemming Fig. 1 Effect of increasing lipophilicity on the performance.
from the metal cation.
Analysis of these data allows conclusions to be drawn,
which may be useful to those interested in designing simple
ammonium- or phosphonium-based catalysts for alkaline PET ide from aqueous solution into the liquid phase comprising
hydrolysis. the insoluble catalyst itself and deliver it to the surface of the
1. In simple aliphatic systems, catalyst performance is maxi- also insoluble PET, or both.
mised when the catalyst is as lipophilic as possible while 3. In terms of simple aliphatic catalyst structures, a 2-chain
being either soluble or finely dispersed (cloudy solution) in structure is clearly a superior design template. 3-Chain
the reaction medium (Fig. 1). This avoids a triphasic catalysis systems are the next most generally favourable, followed by
scenario and explains why seemingly very small structural symmetrical systems; while one-chain systems are particularly
changes to the most lipophilic soluble/finely dispersed ill-suited to the task (e.g. compare the activities of the
systems can lead to dramatic losses of activity (e.g. compare 16-carbon atom, soluble ammonium catalysts 17, 11 and 5
the activities of 16 and 18 to that of 17, and the activities of 5 with both each other and the 17 carbon atom-containing cata-
and 8 to that of 7). It may also account for the discrepancies in lyst 26). We would suggest that the 2-chain systems evaluated
literature data – comparing studies using different loadings, represent an advantageous balance between being able to
reaction temperatures and NaOH concentrations is likely to deliver coordinated hydroxide to the ester carbonyl being
evaluate catalysts under very different conditions vis a vis cata- attacked (facilitated by a small hydrophilic ‘head’ unlikely to
lyst solubility. cause significant steric hindrance) and the ability to associate
2. Once an aliphatic catalyst is insoluble and aggregating with the PET surface through van der Waals attractive forces
under the reaction conditions, a further increase in catalyst between the hydrophobic polymer and the two long aliphatic
lipophilicity is deleterious to its activity (e.g. compare 18 to 21 catalyst chains.
and 8 to 10; also the more lipophilic phosphonium salt 3 is 4. Benzylated catalysts obey these rules when soluble;
superior to the less lipophilic ammonium salt 5 (both however the insoluble catalysts 34, 35, 43 and 46 aggregate
soluble), yet the phosphonium salt 9 is marginally inferior to under the reaction conditions, yet exhibit unexpectedly high
10 – as both are insoluble). This would imply that either the catalytic activity. It is also interesting to note that the 16
majority of the catalysis is carried out by that mole fraction of carbon debenzylated species 40 is less active than 17, 11 or 15.
the catalyst present in aqueous solution, or that bigger, in- These observations, coupled with the general improvement in
soluble catalysts are incrementally less able to extract hydrox- catalyst performance as the π-system is extended (Table 5),

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lead to the conclusion that these systems may behave differ-

ently from simple aliphatic analogues when aggregated and
thus warrant further investigation.
5. Benzylated phosphonium salts are unsuitable under
these reactions due to catalyst decomposition. Scheme 2 PET hydrolysis catalysed by 17 under concentrated
Conclusion 1 (vide supra) predicts that if the solubility of an conditions.
active, soluble catalyst is reduced to the point of heterogeneity,
that activity would be negatively impacted, while the opposite
would be expected if an active, finely dispersed catalyst is ren- soluble under the reaction conditions or being finely dis-
dered soluble. To test this, the insoluble iodide variant of the persed. Once a catalyst is insoluble and aggregating, a further
highly active, soluble catalyst 17 (i.e. 52) and the soluble chlor- increase in lipophilicity is deleterious – as are reductions in
ide analogue of the less active finely dispersed homologue 18 lipophilicity if the catalyst is soluble. Benzylated catalysts
(i.e. 53) were synthesised and evaluated (Table 7). The hetero- exhibited interesting behaviour which may indicate that
genous iodide 52 proved markedly inferior to 17 (entries 1 and π-stacking can allow largely insoluble ammonium salts to
2) while the soluble, more lipophilic cation containing (than possess considerable activity. After evaluation of over 50 cata-
17) catalyst 53 accelerated the PET depolymerisation more lytic systems, a picture emerged in which it is perhaps unwise
efficiently than all other catalysts evaluated in this study to search for a ‘universal’ optimum catalyst for the acceleration
(entries 3 and 4). of alkaline PET hydrolysis, but rather that the practitioner
Finally, since the reaction is heterogeneous and the flakes should design the catalyst and the reaction conditions together
relatively large (relative to powders), we reasoned that the – as the solutes in the aqueous medium and the reaction
simple adaptation of reducing the volume of water in the reac- temperature will alter the ability of the medium to solubilise
tion by 50% would bring about significant improvements in the catalyst – with dramatic consequences regarding catalyst
efficacy – as both hydroxide/catalyst concentration would be efficacy. While a given catalyst for one set of conditions may
doubled while the PET flakes would be in contact with a prove optimal, alteration of those conditions may shift the
greater proportion of the bulk solution – and the reaction solubility equilibrium such that a larger or smaller homologue
would generate less aqueous waste. Accordingly, we repeated of the original catalyst may be better suited. Other factors such
the standard PET hydrolysis with half the volume of aqueous as the PET source and particle size are no doubt also similarly
solvent and with only 1 mol% of the benchmark bromide cata- relevant. Further investigations along these lines are
lyst 17. The result was the isolation of TPA in near quantitative underway.
yield after 3 h (Scheme 2).
In summary, the first systematic investigation into the influ-
ence of the structure on activity in simple quaternary Data availability
ammonium- and phosphonium-based catalytic systems for
alkaline PET hydrolysis has revealed that catalysts incorporat- The data supporting this article have been included as part of
ing 2 longer aliphatic chains and a smaller hydrophilic cation the ESI.†
generally outperform other constitutional isomers. Optimum
catalysts were as lipophilic as possible while either remaining
Conflicts of interest
There are no conflicts to declare.
Table 7 Manipulation of catalyst solubility and activity via the halide
counteriona
Acknowledgements
This study emanated from research conducted with the
support of The Science Foundation Ireland Research Centre
for Pharmaceuticals (SSPC) under grant number 12/RC/
2275_P2 and Science Foundation Ireland under grant number
19/FFP/6527. For the purpose of Open Access, the author has
Entry Catalyst atoms reaction conditions (%) applied a CC BY public copyright licence to any Author
Accepted Manuscript version arising from this submission.
1 17c 16 Soluble 81.9
3 18c 18 Finely dispersed 70.6
4 53 18 Soluble 88.9 References
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Green Chemistry: E Ect of A Phase Transfer Catalyst Structure On The Alkaline Hydrolysis of Poly (Ethylene Terephthalate)

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Green Chemistry: E Ect of A Phase Transfer Catalyst Structure On The Alkaline Hydrolysis of Poly (Ethylene Terephthalate)

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Green Chemistry: E Ect of A Phase Transfer Catalyst Structure On The Alkaline Hydrolysis of Poly (Ethylene Terephthalate)

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Green Chemistry

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Eﬀect of a phase transfer catalyst structure on the

Cite this: DOI: 10.1039/d4gc05070c

Lee B. Anderson, Conall Molloy, Lorenzo Pedrini, Ian L. Martin and

This journal is © The Royal Society of Chemistry 2024 Green Chem.

Communication Green Chemistry

promoters of alkaline ester hydrolysis if the ester incorporated

to the catalytic activity in the alkaline hydrolysis of PET under

Green Chem. This journal is © The Royal Society of Chemistry 2024

Green Chemistry Communication

capable of marginally greater activity (entry 2) – however as

(entry 1) – considerably greater than that associated with the

atoms in length. Hence they can be seen as a hybrid of single-

This journal is © The Royal Society of Chemistry 2024 Green Chem.

Communication Green Chemistry

No. of carbon Solubility under Yieldb

Green Chem. This journal is © The Royal Society of Chemistry 2024

Green Chemistry Communication

Table 6 Aromatic- and ionophore-based catalystsa

No. of carbon Solubility under Yieldb

2–4). The ionophore 51 – an eﬃcient binder of Na cations –

This journal is © The Royal Society of Chemistry 2024 Green Chem.

Communication Green Chemistry

lead to the conclusion that these systems may behave diﬀer-

Green Chem. This journal is © The Royal Society of Chemistry 2024

Green Chemistry Communication

2 P. Benyathiar, P. Kumar, G. Carpenter, J. Brace and (l) C. Jehanno, M. M. Pérez-Madrigal, J. Demarteau,

M. M. Wright, J. Wu, V. M. Zavala, P. Zhou and 12 R. López-Fonseca, M. P. González-Marcos, J. R. González-

This journal is © The Royal Society of Chemistry 2024 Green Chem.

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