RESEARCH HIGHLIGHT
Me al- ee ini ia o s pa e he way o chemically
ecyclable polyme s wi h indus ially ele an
p ope ies
To sol e he en i onmen al disas e ha is gene a ed by legacy plas ics accumula ion, esea che s a e looking o design plas ics
wi h enhanced end-o -li e op ions, bu many ci cula plas ics do no mee indus ial equi emen s. He e, we highligh a me al- ee
app oach o p oduce chemically ecyclable poly(1,3-dioxolane) wi h ul a-high molecula weigh and compa able p ope ies o one
o he mos p oduced plas ics, polye hylene.
One al e na i e o ansi ion om ou cu en linea plas ic
p oduc ion o a mo e sus ainable ci cula plas ic p oduc ion is o
design plas ics capable o chemical ecycling o monome s
(CRM)1–5. CRM mi iga es he need o con inuous eeds ock
sou cing and could po en ially minimize he accumula ion o
plas ic was e. While ini ial epo s on CRM plas ics did no
specifically ocus on he po en ial scalabili y o hese ma e ials, in
ecen yea s, special a en ion has been paid o he design o easily
scalable sys ems, accessing use ul ma e ial p ope ies, and
in oking simple p ocesses o depolyme iza ion o monome s.
Polyace als a e p omising candida es o CRM and, ecen ly, a
e e sible-deac i a ion ca ionic ing-opening polyme iza ion
(CROP) o cyclic ace als using a comme cial halome hyl e he
ini ia o and an indium(III) b omide ca alys was in oduced6,7.
Using his me hod, poly(1,3-dioxolane) (PDXL) o a ound
200 kDa was p oduced, ob aining ma e ials wi h ensile s eng hs
compa able o some commodi y polyolefins ha could be che-
mically ecycled in nea -quan i a i e yield in he p esence o
s ong acids. So a , sus ainable ca alys s/ini ia o s ha could
ans o m CRM plas ics in o ul a-high molecula weigh plas ics
wi h unique oughness hanks o hei supe io en anglemen
ha e been lacking.
Now, H. G ace Hes e , B ooks A. Abel, and Geo ey W.
Coa es om Co nell Uni e si y, USA, employ comme cially
a ailable Mee wein sal s as o ganic ini ia o s oge he wi h 2,6-di-
e -bu ylpy idine (DTBP) as a p o on ap o syn hesize ul a-
high molecula weigh PDXL o up o 2000 kDa om ecycled
DXL (h ps://doi.o g/10.1021/jacs.3c01901)8. The oxonium
(Mee wein) sal ini ia o s wi h non-nucleophilic coun e -anions
gene a e small concen a ions o p opaga ing ca ions. “We ea-
lized ha ansace aliza ion, a side- eac ion du ing CROP o
cyclic ace als, could be used as a mechanism o sha ing p opa-
ga ing ca ionic species among di e en polyme chains,”says
Abel. “This means ha e en i a p opaga ing polyme chain
e mina es, his ansace aliza ion ‘side- eac ion’ e i es he dead
chain by ans e ing he p opaga ing ca ion om a li ing chain
o he dead chain. This key insigh was c ucial o de eloping he
p esen cyclic ace al CROP sys em”. Because o he li ing na u e
o he polyme iza ion, ex emely low ini ia o concen a ions i.e.,
monome o ini ia o a ios o up o 40,000: 1 su fice o ini ia ing
he CROP o cyclic ace als. “We showed ha he use o DTBP as a
p o on ap du ing he CROP o cyclic ace als p e en s undesi ed
ini ia ion by acidic impu i ies and is c ucial o achie ing he
molecula -weigh con ol needed o each ul a-high molecula
weigh s,”says Abel. The eam ound ha he inc ease in mole-
cula weigh leads o a emendous imp o emen o he physical
pe o mance wi h maximum alues o ensile s ess a b eak o
105 MPa. The ma e ial is duc ile and ough and shows a highe
ul ima e s ess ole ance han ul a-high molecula weigh poly-
e hylene (UHMWPE) (mola mass ∼5000 kDa). “Ou me hod o
epolyme iza ion o ecycled DXL enables he syn hesis o p is-
ine PDXL wi h di e en molecula weigh s, mechanical p op-
e ies, and a chi ec u es wi hou a ec ing u u e ecycling o he
polyme ,”explains Abel.
Indus ially iable plas ics capable o CRM could b ing a
pa adigm shi o sol e issues a ising om he cu en unsus-
ainable plas ics p oduc ion sys em. P ope ca alys /ini ia o
selec ion may well acili a e he de elopmen o such unique
sus ainable polyme s. Fu he mo e, chemical di e sifica ion in
he field o CRM is c ucial o co e he many applica ions whe e
legacy plas ics a e p esen . O he physical aspec s such as mole-
cula weigh a e also c i ical o enhance he field o plas ic
ma e ials. “We a e now aking s eps o syn hesize polyace als o
a ying polyme a chi ec u es o enable u he uning o polyme
p ope ies o fi a pa icula applica ion,”says Abel.
Aina a Sang oniz1& Ha i z Sa don1✉
1POLYMAT, Uni e si y o he Basque Coun y UPV/EHU, Joxe
Ma i Ko a Cen e , A da. Tolosa 72, 20018 Donos ia-San
Sebas ian, Spain.
✉email: [email p o ec ed]
h ps://doi.o g/10.1038/s42004-023-00931-4 OPEN
COMMUNICATIONS CHEMISTRY | (2023) 6:127 | h ps://doi.o g/10.1038/s42004-023-00931-4 | www.na u e.com/commschem 1
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Re e ences
1. Coa es, G. W. & Ge zle , Y. D. Y. L. Chemical ecycling o monome o an
ideal, ci cula polyme economy. Na . Re . Ma e . 5, 501–516 (2020).
2. Jehanno, C. e al. C i ical ad ances and u u e oppo uni ies in upcycling
commodi y polyme s. Na u e 603, 803–814 (2022).
3. Jehanno, C., Pé ez-Mad igal, M. M., Dema eau, J., Sa don, H. & Do e, A. P.
O ganoca alysis o depolyme iza ion. Polym. Chem. 10, 172–186 (2019).
4. Hong, M. & Chen, E. Y. X. Chemically ecyclable polyme s: a ci cula
economy app oach o sus ainabili y. G een Chem. 19, 3692–3706 (2017).
5. Li, H. e al. Expanding plas ics ecycling echnologies: chemical aspec s,
echnology s a us and challenges. G een Chem. 24, 8899–9002 (2022).
6. Abel, B. A., Snyde , R. L. & Coa es, G. W. Chemically ecyclable
he moplas ics om e e sible-deac i a ion polyme iza ion o cyclic ace als.
Science 373, 783–789 (2021).
7. Hu endiek, A., Lingie , S. & Du P ez, F. E. The moplas ic polyace als: chemis y
om he pas o a sus ainable u u e? Polym. Chem. 10,9–33 (2019).
8. Hes e , H. G., Abel, B. A. & Coa es, G. W. Ul a-high-molecula -weigh
poly(dioxolane): enhancing he mechanical pe o mance o a chemically
ecyclable polyme . J. Am. Chem. Soc. 145, 8800–8804 (2023).
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