ChemSusChem
10.1002/cssc.202002124
RESEARCH ARTICLE
The crude mixture was suspended in 20 mL of distilled water,
unreacted plastics removed by filtration and the filtrate acidified.
The precipitated TPA was collected by filtration, washed and
dried at 70 °C overnight.
[1]
R. C Thompson, S. H. Swan, C. J. Moore, F. S. vom Saal, Phil. Trans.
R. Soc. B 2009, 364, 1973-1976.
[
2]
The New Plastics Economy: Rethinking the Future of Plastics, a report
by World Economic Forum, Ellen MacArthur Foundation and McKinsey
&
Company 2016, see: https://www.newplasticseconomy.org/about/
publications/report-2016.
Waste PET hydrolysis by vapour-assisted aging
[
3]
a) R. Geyer, J. R. Jambeck, K. Lewander Law, Sci. Adv. 2017, 3,
e1700782; b) I. Vollmer, M. J. F. Jenks, M. C. P. Roelands, R. J. White,
T. van Harmelen, P. de Wild, G. P. van der Laan, F. Meirer, J. T. F.
Keurentjes, B. M. Weckhuysen, Angew. Chem. Int. Ed. 2020, 59,
Manually mixed samples: Mixtures of waste PET (ca. 100–106
mg) and sodium hydroxide (ca. 41–45 mg, 1.0 eq) were briefly
manually homogenized with a spatula and distributed into five
vials. The vials were placed in aging chambers with the relative
1
5402-15423.
[
4]
S. Mandal, A. Dey, in Recycling of Polyethylene Terephthalate Bottles,
Plastics Design Library (Eds.: S. Thomas, A. Rane, K. Kanny, A. V. K.,
M. G. Thomas), Elsevier, Cambridge USA, 2019, pp. 1-22.
humidity levels set to 0% (P
2
O
5
), 8% (sat. ZnBr
2
), 43% (sat.
K
2
CO ), 75% (sat. NaCl) and 100% (dist. H
3
2
O). For aging in
[
[
5]
6]
N. George, T. Kurian, Ind. Eng. Chem. Res. 2014, 53, 14185-14198.
a) T. Yoshioka, N. Okayama, A. Okuwaki, Ind. Eng. Chem. Res. 1998,
37, 336-340; b) J.-W. Chen, L.-W. Chen, J. Appl. Polym. Sci. 1999, 73,
35-40; c) H. Kurokawa, M. Ohshima, K. Sugiyama, H. Miura, Polym.
Degrad. Stab. 2003, 79, 529-533; d) P. Gupta, S. Bhandari, in
Recycling of Polyethylene Terephthalate Bottles, Plastics Design
Library (Eds.: S. Thomas, A. Rane, K. Kanny, A. V. K., M. G. Thomas),
Elsevier, Cambridge USA, 2019, pp. 109-134. e) S. Ügdüler, K. M. Van
Geem, R. Denolf, M. Roosen, N. Mys, K. Ragaert, S. De Meester,
Green Chem. 2020, 22, 5376-5394.
organic vapours, dry acetonitrile, 1,4-dioxane, methanol or
ethanol were used. After aging at 25, 45 or 60 °C for the
respective reaction time, each reaction mixture was suspended
in 4 mL of distilled water and worked up as described above.
Pre-milled samples: A mixture of waste PET (600 mg) and
NaOH (250 mg) was milled with a 12 mm ball for 5 minutes.
Aliquots of the pre-milled mixture (140–145 mg) were then
distributed into five vials and left in aging chambers in a
controlled humid atmosphere at 25 °C for 3 days. Each reaction
mixture was worked up as described above.
[
[
7]
a) R. Esquer, J. J. García, J. Organomet. Chem. 2019, 902, 120972; b)
N. D. Pingale, V. S. Palekar, S. R. Shukla, J. Appl. Polym. Sci. 2010,
115, 249-254; c) S. R. Shukla, V. Palekar, N. Pingale, J. Appl. Polym.
Sci. 2008, 110, 501-506.
8]
9]
a) H. Wang, Z. Li, Y. Liu, X. Zhang, S. Zhang, Green Chem. 2009, 11,
Pre-heated samples: Mixtures of waste PET (ca. 100–106 mg)
and sodium hydroxide (ca. 41–45 mg, 1.0 eq) were briefly
manually homogenized with a spatula and left in an oven at
1
568-1575; b) T. Sako, I. Okajima, T. Sugeta, K. Otake, S. Yoda, Y.
Takebayashi, C. Kamizawa, Polym. J. 2000, 32, 178-181.
S. Chaudhary, P. Surekha, D. Kumar, C. Rajagopal, P. K. Roy, J. Appl.
Polym. Sci. 2013, 129, 2779-2788.
[
[
1
00 °C for 1 hour, followed by placing the reaction vials in aging
chambers at 25 °C for 3 days. Each reaction mixture was
worked up as described above.
10] a) M. Imran, D. H. Kim, W. A. Al-Masry, A. Mahmood, A. Hassan, S.
Haider, S. M. Ramay, Polym. Degrad. Stab. 2013, 98, 904-915; b) M.
Imran, B.-K. Kim, M. Han, B. G. Cho, D. H. Kim, Polym. Degrad. Stab.
2010, 95, 1686-1693; c) M. Genta, T. Iwaya, M. Sasaki, M. Goto, T.
Hirose, Ind. Eng. Chem. Res. 2005, 44, 3894-3900.
In the scale-up aging experiment, a mixture of transparent and
green waste PET (4.00 g) and NaOH (1.0 eq), which was pre-
milled for 5 minutes, was placed in a plastic air-tight container
made of polypropylene with saturated sodium chloride aqueous
solution (RH = 75%) and left at 45 °C for 3 days. The crude
mixture was suspended in 160 mL of distilled water and worked
up as described above.
[
11] a) S. Yoshida, K. Hiraga, T. Takehana, I. Taniguchi, H. Yamaji, Y.
Maeda, K. Toyohara, K. Miyamoto, Y. Kimura, K. Oda, Science 2016,
3
1
1
51, 1196-1199; b) R. Wen, W. Zimmermann, Microb. Biotechnol. 2017,
0, 1302-1307; c) R. Wei, W. Zimmermann, Microb. Biotechnol. 2017,
0, 1308-1322.
[12] F. Kawai, T. Kawabata, M. Oda, Appl. Microbiol. Biotechnol. 2019, 103,
253-4268.
4
1
Terephthalic acid (TPA): H NMR (600 MHz, [D
6
]DMSO, 25°C,
[13] F. Quartinello, S. Vajnhandl, J. Volmajer Valh, T. J. Farmer, B. Voncina,
A. Lobnik, E. Herrero Acero, A. Pellis, G. M. Guebitz, Microb.
Biotechnol. 2017, 10, 1376-1383.
TMS): δ=13.28 (brs, 2H; COOH), 8.04 ppm (s, 4H; Ar–H).
1
3
6
C NMR (150 MHz, [D ]DMSO, 25°C, TMS): δ=166.7 (COOH),
[
[
14] F. Gomollón-Bel, Chemistry International 2019, 41, 12-17.
15] a) T. Friščić, A. V. Trask, W. Jones, W. D. S. Motherwell, Angew. Chem.
Int. Ed. 2006, 45, 7546-7550; b) T. Friščić, S. L. Childs, S. A. A. Rizvi,
W. Jones, CrystEngComm 2009, 11, 418-426.
1
2
8
34.5 (C), 129.5 ppm (CH). IR (ATR): ν= 3104, 3064, 2816,
657, 2539, 1674, 1574, 1509, 1423, 1280, 1136, 1112, 927,
−
1
79, 780, 726, 525 cm .
[
[
16] T. Friščić, D. G. Reid, I. Halasz, R. S. Stein, R. E. Dinnebier, M. J. Duer,
Angew. Chem. Int. Ed. 2010, 49, 712-715.
17] a) D. Hasa, G. Schneider Rauber, D. Voinovich, W. Jones, Angew.
Chem. Int. Ed. 2015, 54, 7371-7375; b) D. Hasa, E. Carlino, W. Jones,
Cryst. Growth Des. 2016, 16, 1772-1779.
Acknowledgements
Dr. Davor Margetić, Dr. Zoran Glasovac and Dr. Nikola Basarić
[
18] A. Mukherjee, R. D. Rogers, A. S. Myerson, CrystEngComm 2018, 20,
3817-3821.
(
RBI) are greatfully acknowledged for valuable comments and
discussion, Dr. Tanja Jurkin (RBI) for the DSC analysis and the
Centre for NMR (RBI) for recording the NMR spectra. Financial
support was provided through the Ruđer Bošković Institute
internal funding programme.
[19] a) H. M. Titi, J.-L. Do, A. J. Howarth, K. Nagapudi, T. Friščić, Chem. Sci.
2020, 11, 7578-7584; b) A. A. L. Michalchuk, K. S. Hope, S. R.
Kennedy, M. V. Blanco, E. V. Boldyreva, C. R. Pulham, Chem.
Commun. 2018, 54, 4033-4036.
[
[
20] V. Štrukil, I. Sajko, Chem. Commun. 2017, 53, 9101-9104.
21] a) K. Užarević, N. Ferdelji, T. Mrla, P. A. Julien, B. Halasz, T. Friščić, I.
Halasz, Chem. Sci. 2018, 9, 2525-2532; b) J. M. Andersen, J. Mack,
Chem. Sci. 2017, 8, 5447-5453.
Keywords: Hydrolysis • Mechanochemistry • Polyethylene
terephthalate • Solid-state reactions • Vapour-assisted aging
[
22] a) T. Friščić, C. Mottillo, H. M. Titi, Angew. Chem. Int. Ed. 2020, 59,
1
018-1029; b) M. Pérez-Venegas, E. Juaristi, ACS Sustain. Chem. Eng.
7
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