REVIEWS

Chemical recycling of waste plastics for

new materials production
AliReza Rahimi and Jeannette M. García
Abstract | Once referred to as ‘materials of 1,000 uses’, plastics meet demands in everything from
clothing and automotive sectors to the manufacturing of medical equipment and electronics.
Concomitant with usage, worldwide generation of plastic solid waste increases daily and is
currently around 150 million tonnes per annum. Although recycled materials may have physical
properties similar to those of virgin plastics, the resulting monetary savings are limited and the
properties of most plastics are significantly compromised after a number of processing cycles. An
alternative approach to processing plastic solid waste is chemical recycling, the success of which
relies on the affordability of processes and the efficiency of catalysts. In this Review, we describe
technologies available for sorting and recycling plastic solid waste into feedstocks, as well as
state‑of‑the-art techniques to chemically recycle commercial plastics. These evaluations are
followed by a survey of recent advances in the design of new high-performing recyclable polymers.

IBM Research-Almaden,
Chemistry and Materials,
650 Harry Road, San Jose,
California 95120, USA.
Correspondence to J.M.G.
jmgarcia@us.ibm.com
doi:10.1038/s41570-017-0046
Published online 7 Jun 2017
Plastics are polymers that are both ubiquitous and integral
in our society, being indispensable, for example, in food
packaging, disposable medical equipment and electronics.
Each year, plastics account for approximately 30 million
tonnes of municipal solid waste (MSW) in the United
States, of which less than 10% is recycled. Although
imperfect consumer compliance with best recycling
practices contributes to this low figure, technological lim-
itations are the overwhelming constraint on plastics recy-
cling. Four main techniques are implemented for plastics
recycling: primary (closed-loop), secondary (mechanical),
tertiary (chemical) and energy recovery (incineration)1.
Current recycling processes rely heavily on primary
recycling, which requires near-pristine input in the form
of uncontaminated, singly used plastics. Furthermore,
compared with virgin materials, poly­mers reprocessed
by melt-and-remoulding have lower molecular weights
and reduced thermal and mechanical robustness. Indeed,
materials recycled in this manner are typically inferior,
such that global plastic solid waste (PSW) production
has continued to increase to its present value of 150 mil-
lion tonnes per year. According to the US Environmental
Protection Agency (EPA), the vast majority (87%) of plas-
tic waste falls into the top six categories of plastics, which
are described by the Society of the Plastics Industry (SPI)
codes 1–6. Yet the recovery rate of plastic waste for recy-
cling in the United States was only 8.8% in 2012 (REF. 2).
Recycling practices are also not perfect across the Atlantic,
with the European Association of Plastics Recycling and
Recovery Organizations reporting that ~26 million tonnes
of post-consumer plastic were discarded in Europe in
2014, of which only ~30% and ~40% was recycled and
incinerated, respectively 3. These low figures indicate that
there is great room for improvement and highlight the
potential of the plastic recycling industry to contribute
significantly to the global economy. On average, each
tonne of plastic recycled saves ~130 million kilojoules
(123 million British thermal units (BTU)), a value equiv-
alent to the energy liberated on combusting ~22 barrels
of oil4. Advancing efficient and effective recycling tech-
nologies — such as chemical recycling — for global PSW
processing could save ~3.5 billion barrels of oil, an annual
monetary saving of US$176 billion. Based on estimates
of crude oil prices from Bloomberg Markets in January
2017, the recycling of PSW could add ~$38 billion to
the economy (in the United States alone) each year.
Discarded plastics primarily derived from petroleum
sources have accumulated in landfills (and oceans)5,6,
which we should now view as untapped resources for the
production of new materials7. Therefore, research efforts
towards the development of efficient recycling methods
for all PSW components will be critical in realizing
the substantial economic and environmental benefits
associated with recycling.
Present recycling methods
Recycled polymers are significantly cheaper than virgin
materials, with the monetary savings mostly arising from
the energy savings, which typically fall in the ~40–90%
range depending on the polymer type8. Monetary savings
associated with recycling plastics can be substantial and
depend on the grade and type of the recycled material

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(see PolymerTrack — The Global Polymer Price Index),
and on the cost of the virgin material, which itself is
dependent on oil prices that fluctuate and can often be
fairly low. These fluctuations are borne out in the prices
of virgin plastics in the United States, which varied
wildly from 2002 to 2017 (FIG. 1).
Recycling is enabled by the isolation of PSW from
MSW, with the fraction of the total PSW thus processed
being referred to as the recovery rate. Plastics that have
higher recovery rates are not necessarily cheaper than
those less frequently recycled. According to a 2015
report from the EPA (TABLE 1), the plastics with the
highest recovery rates are polyethylene terephthalate
(PET, SPI code 1, 19.5%), high-density polyethylene
(HDPE, SPI code 2, 10%) and low-density polyethyl-
ene (LDPE, SPI code 4, 5%). All other plastics, includ-
ing polypropylene (PP, SPI code 5) and polystyrene
(PS, SPI code 6), were recovered in less than 1%. The
recovery rate for polyvinyl chloride (PVC, SPI code 3)
was effectively zero2. These values are averaged over
the many products that end up in MSW, and the rela-
tive recovery rates for specific products may be higher;
PET bottles, for example, are recovered at ~31%. Once
PSW is collected and separated at materials recovery
facilities, the different plastics are subjected to various
end‑of‑life treatments, including incineration, recycling
or composting.
The different plastics recycling methods are referred
to as being ‘primary’, ‘secondary’, ‘tertiary’ or ‘energy
recovery’. Primary recycling refers to reprocessing a
plastic to give a product used for the same purpose as
the original plastic. This method — termed closed-loop
recycling — can only make use of near-pristine waste,
such as process scrap or post-consumer materials of
known origin. The production of plastic bottles from
blends of recycled PET (rPET) and virgin PET is a note-
worthy example of primary recycling.
Secondary (mechanical) recycling affords materi-
als for uses different from those for which the original
material was manufactured. Most reclaimed post-
consumer materials are recycled through this process, the
3 120
2.5 100
US oil prices ($ per barrel)
products of which are typically lower in value, such that
the process is often called ‘downgrading’ or ‘downcycling’.
Primary and secondary recycling both involve mechanical
processes in which polymers are sorted, ground, washed
and extruded. Such reprocessing causes varying degrees
of polymer degradation, with applications of mechanical
recycling being limited by the number of reprocessing
cycles that a given polymer can endure. Post-consumer
plastics are rarely recycled using currently available
mechanical methods.
Tertiary (chemical) recycling uses a chemical process
to recover the petrochemical components in plastics. An
example of this approach is pyrolysis, in which plastics are
subjected to high temperatures in the presence of a catalyst.
Chemical recycling is not commonly implemented on an
industrial scale because present methods require sizable
energy inputs. However, if the pure monomer could
be recovered through chemical recycling, the prices of
polymers would be decoupled from oil prices. This has
motivated the search for mild processes for the catalytic
conversion of polymers directly to monomers or to new
polymers. These approaches are discussed in more detail
in the following sections.
A further method of using waste plastics is incin-
eration, whereby a portion of the energy in plastics is
recovered in the form of heat. Of course, energy can be
derived from burning complicated mixtures, including
multilayer packaging, but not without releasing green-
house gases and toxins. Indeed, as long as there is no way
to recover incineration products for reuse, this method
can never represent a cradle-to‑cradle practice. On top
of the environ­mental effects of the pollutants generated,
the energy generated by mass burning of plastics is sub-
stantially less than the energy conserved by recycling9. For
example, the heating value for plastics is ~36,000 kJ kg–1,
whereas mechanical recycling conserves ~60,000–
90,000 kJ kg–1. Therefore, recycling plastic waste ultimately
conserves more energy than the process of incinerating
plastic waste can generate.
Plastics sorting technologies
The sorting of PSW is important both to remove con-
taminants, such as metals, wood and rubber, and to sep-
arate the individual polymer materials, each of which
may respond very differently to reprocessing. As manual

separation of plastics is ineffective, challenging and time-

Plastic prices ($ per kg)

PET (SPI code 1)

2 80 consuming, automated separation techniques have been
HDPE (SPI code 2) developed to expedite the process. Such sorting tech-
1.5 60 PVC (SPI code 3) niques rely on measurable differences in material proper-
LDPE (SPI code 4) ties, such as density, electrostatics, wettability or spectral
1 40
PP (SPI code 5) signatures10. For example, the densities of commercial
PS (SPI code 6)
polymers can differ greatly, with PVC (~1.10–1.45 g cm–3)
0.5 20
and PET (~1.38–1.40 g cm–3) being denser than polyamide
Price of crude oil
0 0 (~1.07–1.18 g cm–3), polystyrene (~1.04–1.11 g cm–3) and
2000 2005 2010 2015 2020 polyethylene (~0.91–0.97 g cm–3)11.
Year The complex demands of polymer recycling have
Figure 1 | The prices of virgin SPI code 1–6 plastics in theNature
UnitedReviews
States between necessitated advancements in mechanical and optical
| Chemistry
2002 and 2017. Plastic prices (see MacroTrends) reflect an annual average of weekly technologies for materials identification and separation.
data and correlate with oil prices. PET, polyethylene terephthalate; HDPE, high-density State‑of‑the-art mechanical and optical separation tech-
polyethylene; PVC, polyvinyl chloride; LDPE, low-density polyethylene; nologies have shown promise as a means to sort plastic
PP, polypropylene; PS, polystyrene. components from mixed waste with particles as small as

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2 mm. These methods thus maximize the usefulness of
processing PSW sources such as household rubbish12,13.
Mechanical separation systems target the physical prop-
erties of materials, which can be further distinguished by
using optical techniques in parallel. Some of the most
commonly used technologies for plastics separation are
summarized in BOX 1.
Sorting processes in recycling plants will require
effective, efficient, affordable and accurate separation
technologies for heterogeneous plastic waste to be
converted to high-purity feedstocks. There is a need
to develop plastics separation technologies that are
unconstrained by the type of waste input, its original
application or the presence of non-plastic contaminants.
Once a high-purity feedstock is available, new recycling
methods for plastics, such as chemical depolymerization
processes, will be easier to implement.
Recycling of commercial polymers
Having introduced some commonly recycled plastics
and their uses (TABLE 1), we lament that only two types,
PET and HPDE, are regularly recycled. Expanding the
scope of plastics that can be recycled by non-mechani-
cal methods requires state‑of‑the-art depolymerization
techniques. These strategies, introduced in the context of
each plastic (SPI codes 1–7), are discussed below.
SPI code 1: polyethylene terephthalate. PET is a tough
and mouldable plastic used in the production of bev-
erage bottles, fibres and filaments1. The ductility of
PET during mechanical recycling drops from ~310 to
~218% after one cycle and is 2.9% by the third cycle11.
As a result, only a small portion of PET is recycled for
its original application, with most (50–77%) being con-
verted into fibres used for the production of mixed mate-
rials such as carpeting. Plastic bottles are typically made
from PET with relatively high molecular weights, and
the recycling process, even though it reduces the chain
lengths, still affords a material with average molecular
weight high enough for fibre production.
Thermal degradation of PET is observed at temper-
atures above ~300 °C. PET can be decomposed both
with and without the action of an acid precatalyst, such
as ammonium polyphosphate. On comparing the two

Table 1 | The SPI codes for different types of plastics and the recovery rates from total plastic solid waste2
SPI Full name Chemical structure Uses Currently Density Recovery
number recyclable? (g cm−3) Rate (%)
1 Polyethylene Disposable bottles for Yes 1.38–1.40 19.5
terephthalate drinks, medicines and
O O
many other consumer
products
O O
n

PETE/PET

2 High-density More durable Yes 0.93–0.97 10

polyethylene n
containers, such as
HDPE
those for detergent,
bleach, shampoo or
motor oil
3 Polyvinyl chloride Cl Piping, cables, garden No 1.10–1.45 0
furniture, fencing and
n carpet backing
PVC

4 Low-density Plastic bags, Mostly no 0.91–0.94 5

polyethylene n
wrapping films,
trays and computer
LDPE
components
5 Polypropylene Bottle caps, reusable Sometimes 0.90–0.92 1
food containers and
n
car parts
PP

6 Polystyrene Ph Plastic utensils, Sometimes 1.04–1.11; 1

packaging peanuts 0.016–0.64
n and styrofoam (EPS) (EPS)
PS

7 Other: for example, Me Me Multilayer barrier No varies varies

polycarbonate films, toothbrushes,
and polymethyl CO 2Me O some food containers,
methacrylate CDs and DVDs
n
O O n

PMMA PC
EPS, expanded polystyrene; SPI, Society of Plastics Industry.

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processes, it was noted that the primary process for bond
cleavage during pyrolysis involves cyclic oligomer forma-
tion and hydrogen abstraction, these reactions giving rise
to a vinyl group14 (FIG. 2a). Surprisingly, the products of
the acid-catalysed reaction indicate an ionic mechanism
as the primary decomposition pathway, although a rad-
ical pathway is also possible, including in cases in which
PET waste is irradiated with an electron beam15.
Chemolysis of PET, which can proceed with or with-
out catalysts, can be used to aid depolymerization of
PET even when it is present in a mixture16. The result-
ing small-molecule products include bis(hydroxyethyl)
terephthalate, dimethyl terephthalate and terephthalic
acid17–19. Depolymerization of PET occurs through trans-
esterification at the polymer backbone by nucleophiles
such as ethylene glycol, methanol, water or hydroxide.
This process, which affords monomers or terephthalic
oligoesters, often requires inorganic catalysts and high
temperatures or pressures. The chemical recycling of PET
is challenging in that it is less efficient when the input is
dyed (for example, green flake) and can also afford mon-
omer products that are discoloured. In each case, decol-
orization and the removal of dyes require an additional
Box 1 | Technologies for plastics separation
Magnetic density separation
Separates waste according to the density differences between plastics, despite an
overlapping or narrow range of densities for different plastics114. Magnetic density
separation (MDS) uses a magnetic mixture (nanometre‑sized FeO particles suspended
in water), the effective density of which varies vertically in a magnetic field, to sort
plastic particles of varying density. MDS enables single-step, accurate and rapid
material sorting for high-density polyethylene, low-density polyethylene and
polypropylene from each other and from other materials such as rubber and metals10,115.
Triboelectric separation
Uses friction to charge polymer particle surfaces and separate them based on their
anionic or cationic nature116,117.
Froth flotation methods
Target the critical surface tension (wettability) of plastics and separate them based on
their hydrophobic or hydrophilic character118.
Speed accelerators
Work to delaminate polymers from other materials at high speed for further separation10.
Solvent-based recovery
Effective for polyvinyl chloride, which is soluble in organic solvents and can thus be
separated from insoluble materials51.
Hyperspectral imaging
Uses an in‑line sensor technology that combines spatial and spectral analysis of defined
solids119. Cameras perform 3D imaging of the materials by interrogating them with light
in the 400–1,700 nm spectral range (in the visible and infrared). Hyperspectral imaging
technology is exploited as a quality control technique to continuously monitor
processes in which polyolefins are separated by mechanical methods such as MDS.
Laser-induced breakdown spectroscopy
Used to evaluate compositional elements of materials by comparing real-time atomic
emission spectral data of plastics to referenced sources120.
X‑ray fluorescence and infrared spectroscopy
These are examples of other methods that are used for spectroscopic separation
purposes10,11.
Ultrasound technology
Currently used for commercial medical imaging and has also shown promising results for
monitoring the separation of plastic waste and assessing process quality information121.
step in the process20,21. Ideally, depolymerization catalysed
by bases such as the guanidine 1,5,7‑triazabicyclo[4.4.0]
dec‑5‑ene affords high-purity monomers22,23 (FIG. 2b). In
addition to oxygen‑centred nucleophiles, the catalysed
chemolysis is also amenable to many nitrogen‑containing
nucleophiles such as amines and anilines. Such reactions
afford amide-containing monomers that are valuable
co‑­monomers used, for example, in polycondensations
to give poly(aryl ether sulfone amide) hybrid materials24
(FIG. 2c).
SPI codes 2, 4 and 5: high-density polyethylene,
low-density polyethylene and polypropylene. We now
consider recycling of the polyolefins HDPE, LDPE and
polypropylene, the approaches for which are similar to
each other. HDPE finds use in electrical insulators, toys,
bottles, pipes and films, with LDPE being a main con-
stituent of device and food packaging, and plastic wrap.
The recycling of polyethylene is not adversely affected
by the presence of other materials — indeed, additive or
blend formulations can undergo recycling more cleanly
than the parent material25,26. The comparatively high
thermal stability of polyethylene allows it to undergo
multiple melt-and-remould cycles in mechanical recy-
cling processes. For example, LDPE can be extruded up
to 100 times at 240 °C, although long-term performance
suffers after 40 extrusions, with significant changes in
processability and mechanical properties observed. The
latter are attributed to chain scission and crosslinking —
processes that lead to structural rearrangement during
thermal treatment 27. HDPE and linear-LDPE are much
more linear polymers than LDPE, and their decom-
position is thought to occur primarily through chain
scission, with only minimal crosslinking observed.
However, in each case, subjecting the material to ele-
vated temperatures (>280 °C) in air leads to faster
degradation on account of surface oxidation, which
affords aldehydes and organic acids as smoke during
extrusion28. Polypropylene sees extensive use in indus-
trial settings owing to its toughness and high chemical
resistance. As a result, it is commonly encountered in
fibre manufacturing, injection moulding, wheel covers,
instrument panels and pipe coatings29. Polypropylene
is vulnerable to oxidation during reprocessing, because
activation of C–H groups at tertiary carbon centres
would afford radical sites sufficiently long-lived to react
with oxygen. It is perhaps no surprise that mechanical
recycling compromises the mechanical properties of
polypropylene much faster than those of polyethylene.
The molecular weight of polypropylene drops after sev-
eral cycles of processing, leading to diminished values
for elongation-at‑break and fracture toughness, and a
higher melt flow index 30.
HDPE undergoes thermal depolymerization at tem-
peratures above 400 °C, but only small quantities of
low-molecular-weight products are produced; instead,
a mixture of products is typically recovered, including
a solid wax. The mechanism of thermal degradation
involves random scission and chain scrambling through
C–C bond homolysis and recombination of the resulting
radical fragments31. Thermolysis to produce gasoline

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(liquid C4–C9 products)32 can be achieved with hetero­
geneous high-surface-area catalysts33–35. The introduction
of various transition metals to the catalyst can influence
the molecular weight distribution of hydro­carbons
formed. For example, HDPE can be depoly­merized
to give Arge wax — a commercially available material
with an average chain length of C48 — through the use
of a dinuclear zirconium catalyst immobilized on Al2O3
particles. The Zr active sites act to sequester radicals
during bond cleavage of poly­ethylene at 370 °C (REF. 36),
a sequestration that apparently occurs to a lesser extent
when Ni‑impregnated zeolites are used as catalysts, these
affording short chains (C4–C8) with >98% selectivity 37.
The difficulties associated with chemical recycling of
polyethylene — namely, random scission and recombi-
nation — also hamper the recycling of polypropylene.
Therefore, most attempts at depolymerization of poly­
propylene and polyethylene involve pyrolysis, which
affords waxes38 and light hydrocarbon mixtures that can
be used for fuel39. The pyrolysis (500–900 °C) of poly-
propylene usually produces a mixture of products and
is energy intensive owing to the insulating properties of
polypropylene as well as the energy input requirements
for thermal C–C bond cleavage (‘cracking’). This has led
to the development of heterogeneous catalysts, such as
high-surface-area zeolites40 and co‑pyrolysis conditions41,
specifically designed to crack polypropylene at temper-
atures below 500 °C. Catalyst development involved
tuning surface area and composition to afford a material
that could, under the right conditions, influence depoly­
merization in a selective manner to access non-wax,
low-molecular-weight products42. Nevertheless, the high
temperatures necessary for thermolysis still give a mix-
ture of products, with varying degrees of saturation in the
isolated materials.
The depolymerization of polypropylene to propylene
is best achieved through non-pyrolytic approaches, such
as ionization. For example, when polypropylene is sub-
jected to an inductively coupled plasma, it converts to
a gas containing 94% propylene43. Chemical approaches
to polyethylene depolymerization rely on modifica-
tion before controlled breakdown, with the saturated
hydrocarbon backbone first being functionalized, then
depolymerized. A tandem catalytic system for poly­
ethylene depolymerization has been developed that
adapts a small molecule dehydrogenation–metathesis
sequence to long-chain substrates 44 (FIG. 3). When in a
sealed vessel at relatively low temperatures (150 °C) in
the presence of a short alkane, the supported dehydro-
genation catalyst generates alkene groups in the chains.
Following this, a mixed Rh2O7–Al2O3 catalyst cleaves
the polymer into smaller segments through cross olefin
metathesis to give liquid products in ~56% yield. Such
studies with precious metal catalysts represent useful
proofs-of‑concept, but processes for polyolefin depolym-
erization must not only be efficient but also economically

a O OH

O
H O
O
O
O O +
O Δ

O
O

b O
O
O N
(5 mol%)
N N HO NH O
H
O n
+ 200 °C
O HN OH

HO NH 2

c O O Me Me O O
HO NH O S S

O HN OH O O O
F F n
m
+ O O
O
Me Me
N
H
Me Me NH
HO OH
O

Figure 2 | Depolymerization of waste PET can afford a range of useful monomers. a | Thermolysis of polyethylene terephthalate affords carboxylic
Nature Reviews | Chemistry
acid- and vinyl-terminated fragments14. The reaction can be conducted in the absence or presence of an acid catalyst. b | A guanidine base catalyses
depolymerization to ethylene glycol and N,Nʹ-bis(4‑hydroxyphenyl)terephthalamide 23. c | The N,Nʹ-bis(4‑hydroxyphenyl)terephthalamide product can
be copolymerized with bisphenol A and bis(4‑fluorophenyl) sulfone to afford poly(aryl ether sulfone amide)s24.

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a degradation, can contaminate entire batches of polymers

(excess)
+ +
[Ir I ]
1. Dehydrogenation 3. Hydrogenation
[Ir III H 2]
2. Olefin
+
metathesis
+
b Dehydrogenation and hydrogenation catalysts
PtBu2 O PtBu2 O PiPr2
H Re2O7–Al2O3
tBu (O)P Ir MeO Ir
Ir
H
2 undiminished relative to virgin materials51. There remains
PtBu2 O PtBu2 O PiPr2
Figure 3 | Depolymerization of polyethylene. In the presence of short-chain alkanes,
Nature Reviews | Chemistry
such as n‑hexane, depolymerization of polyethylene occurs through dehydrogenation,
alkene metathesis and hydrogenation. The overall result of these three reactions is cross
alkane metathesis. a | Dehydrogenation of polyethylene and n‑hexane affords a
long-chain olefin and hexene. Cross olefin metathesis results in the scission of the
polyethylene chain into shorter chains, which are hydrogenated to give back saturated
products. Multiple cycles of the reaction sequence result in the conversion of
polyethylene to short alkanes appropriate for use as transportation oil44. b | The iridium
pincer complexes catalyse both the dehydrogenation and hydrogenation steps. Olefin
metathesis is carried out by the mixed oxide catalyst Rh2O7–Al2O3.
viable if the recycling of post-consumer waste materials to
their corresponding monomers is to be made attractive.
SPI code 3: polyvinyl chloride. PVC is an inexpensive,
high-performance, durable polymer that is used in
many products, including construction and architec-
tural materials45. Certain commercial products require
rigidity and environmental resistance, and therefore
PVC is often blended with additives such as fillers and
dyes. When PVC is plasticized with phthalates (such as
di‑(2‑ethylhexyl) phthalate), its use can be extended to
medical equipment and common household items that
require high levels of flexibility, such as shower curtains.
PVC contributes to ~12% of the total demand of plas-
tics; 55 million tonnes of PVC was globally produced in
2013 (REF. 46). However, the additives used in PVC-based
materials contaminate products of the recycling process,
making PVC one of the most problematic plastics for
the environment because it releases phthalate plasticizers
and chlorine-containing organics (for example, dioxins)
upon degradation. Thermal degradation of PVC begins
upon heating to ~200 °C, at which dechlorination
occurs. A second onset — affording HCl, tar and a liq-
uid fraction containing benzene as main side products
— proceeds at temperatures above 360 °C (REF. 47). When
exposed to HCl, PVC degrades spontaneously through a
process dominated by radical reactions48.
The main problem with PVC recycling is the release
of HCl, which leads to equipment corrosion, a pro-
cess that has prompted the improvement of seques-
tration methods. Even small quantities of PVC, upon
in recycling plants and corrode reactors. This problem is
Liquid fuels
circumvented by subjecting mixtures to a pretreatment
and waxes (typically performed at 300 °C for 60 min) that reduces
the chlorine content by ~75 wt%49. Dechlorination is
then followed by catalytic pyrolysis of these materials.
The high energy cost associated with thermal dechlo-
rination of PVC has motivated the search for alternative
methods. One such method is a mechanochemical
approach in which a planetary ball mill grinds PVC with
the HCl scavenger CaO in a process that does not require
heat and affords a calcium salt by-product that can be
washed away 50. In addition, PVC has some solubility
Olefin metathesis
in organics, leading to solvent-based PVC recovery —
catalyst
commercially developed in Europe — to economically
recover PVC with properties (such as density) that are
a need for better methods, catalysts and HCl inhibitors
to recycle PVC waste effectively. Inhibitors should hinder
HCl formation, and catalysts should have the efficacy to
facilitate PVC breakdown primarily to monomers in the
presence of chlorine, HCl or other plastics.
SPI code 6: polystyrene. Polystyrene is inexpensive,
durable and chemically inert, such that it sees use in
many products including appliances, automotive parts,
electronics, food services, medicines and packaging 52.
In 2012, the United States generated ~2 million tonnes
of polystyrene waste, of which only 0.9% was recov-
ered2. The low recovery rate was partially a result of
the difficulties associated with the separation of the
waste. Approximately 10% of polystyrene is in the form
of expanded polystyrene (EPS) foam, and only 50%
of polystyrene produced is used in its pure form, with
the remainder being blended with other materials or
used as segments in copolymers53. The diversity of pol-
ystyrene materials complicates their sorting, and, for
example, the density of polystyrene products can vary
from 1.04 g cm–3 to much lower values in the range of
~0.016–0.64 g cm–3 for EPS in particular 54.
Thermolysis of polystyrene over magnesium-impreg-
nated solid catalysts produces liquid products that are typ-
ically a mixture of hydrocarbons such as benzene, toluene,
ethylbenzene, styrene and α-methylstyrene55. Adjusting
the pH of the reaction at which thermolysis is conducted
allows selective access to dimers, oligomers or monomer,
and in the case of basic catalysts, such as Al2O3 catalysts
containing NaOH (REF. 56) or metal oxides (for example,
MgO, BaO, CaO or K2O), the product mixture can con-
tain >70% styrene57. The sensitivity of depolymerization
to the reactive environment may allow for the design of
catalysts to affect styrene recovery selectively.
Limitations in polystyrene recycling have motivated
the pursuit of alternatives to traditional recycling meth-
ods. For example, a 2015 study showed that mealworms
could be used to digest polystyrene to enable the com-
posting of EPS58. The solubility of polystyrene can also be
exploited: when solubilized in limonene and precipitated
into supercritical CO2, it is converted into pure micro-
cellular foams with desirable pore size (8–200 μm) and
distribution (3–20 μm)59. In addition, waste poly­styrene

6 | ARTICLE NUMBER 0046 | VOLUME 1 www.nature.com/natrevchem

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can be sulfonated to afford polyanions that are useful
flocculating agents60, the performance and properties of
which rival commercial products such as Praestol 2515.
SPI code 7: other. SPI code 7 is the catchall ‘other’
category that includes polyurethane, polyurea, poly­
carbonate, biopolymers, nylon, polymethyl meth-
acrylate (PMMA), high-performance thermoplastics
such as polyethersulfone (PES) and thermosets such as
epoxies. Their high value and utility in speciality appli-
cations have motivated the study of new catalysts for
end‑of‑life treatment, a process essential for the future
of plastics remanufacturing. Some polymers in this
category feature degradable linkers in their backbones
such that they are amenable to chemical breakdown.
For example, bases such as NaOH and Cs2CO3 affect
hydrolysis of poly­carbonate to give bisphenol A (BPA),
although in modest yield and purity 61 (FIG. 4). Here, high
temperatures cause the reactive carbonate linkers in
the backbone to decompose to BPA with concomitant
evolution of CO2 and unwanted by-products. Other depo-
lymerization approaches involve in situ deconstruction
of poly­carbonate to BPA without isolation of mono­mer.
Compact discs (polycarbonate composites with metal
foil) were recently shown to be a useful latent mono­
mer source for the single-operation conversion of poly-
carbonate to PES62. PMMA63,64 and polyamides such as
nylon65–68 can be efficiently depolymerized to monomer
using thermal and photochemical approaches.
Thermoplastics and thermosets used in high-
performance engineering are characterized as SPI code
7 materials. A notable example is PES, which is used
for high-temperature medical equipment, in plumbing
materials, and as a substrate for reverse osmosis mem-
branes. PES can be reprocessed mechanically, but the
molecular weight drops by approximately ~10 kDa per
Me Me Me Me
O
K2CO3
K code 7 also include biopolymers — materials produced
O O O O
K
− CO2
Me Me Me Me
K
O O
K
O
O enable it to be used as a replacement for PET in applica-
O O O O O O
K K
Me Me Me Me
K K
O − CO2 O thermo­plastic starch cast some doubts over the long-term
O
O O O O
O
O O
K
K long-term stability, variability of micro­organisms in land-
Figure 4 | Depolymerization of poly(bisphenol A carbonate). Potassium
Nature Reviewscarbonate
| Chemistry
undergoes decarboxylation to serve as a source of oxide nucleophile in the
depolymerization of poly(bisphenol A carbonate). Further decarboxylation of the
backbone carbonate affords the potassium salt of the bis(phenoxide)62.
remoulding cycle11. Although minimal efforts have been
made towards the chemical recycling of PES, the repro-
cessing of epoxy has been investigated to some degree.
Epoxy is a thermoset typically formed on reaction of a
bis(epoxide) monomer, such as bisphenol A diglycidyl
ether (DGEBA), with an amine hardener, such as tri-
ethylenetetramine. Having applications in electronics,
automotive, aerospace, adhesives, insulators and metal
coatings, epoxy also has desirable chemical resistance
and mechanical properties that see it commonly used as
a matrix resin for composites with fibreglass or carbon-
fibre fillers. Composites represent an attractive light-
weight engineering alternative to metals, but owing to
the irreversible nature of thermoset production, they
cannot be melted and remoulded as part of a conven-
tional recycling process. Recycling is made even less
economically feasible given the need for separating
resin from the filler. Despite these difficulties, ther-
mal, mechanical and chemical separation methods are
available for epoxy composites69. Thermal (pyrolysis)
approaches use heat to separate the resin from the
filler, whereas mechanical processes can take the form
of simple milling. Chemical separation of epoxy com-
posites has involved the use of supercritical n‑propanol
for separation of resin from the filler 70. Acid-cleavable
crosslinks between the linear chains in epoxies have
been engineered for a built‑in end-of-life treatment 71,72.
One recently developed recyclable composite exhib-
ited comparable properties to unrecyclable analogues:
tensile strengths of ~10–15 MPa, flexural strengths of
~91–98 MPa and a Young’s modulus of ~23 GPa were
reported71. For comparison, commercial epoxy com-
posites report tensile strengths of ~85 MPa and flex-
ural strengths of ~112 MPa. In another study, cleavable
epoxies were synthesized through radical alternating
copolymerization of 2,4‑dimethyl‑1,3‑pentadiene with
maleic anhydride and DGEBA73. The strained trisubsti-
tuted olefin in the backbone repeat unit introduced an
ozone-degradable linkage.
The thermosets74 and thermoplastics classified as SPI
from naturally derived monomers. Because they exhibit
good thermomechanical properties, biopolymers may
represent attractive alternatives to commercial polymers
in certain applications. For example, the density, elastic
modulus, glass transition temperature (Tg), strength-
to‑weight ratio and ultimate tensile strength of polylactide
tions such as food packaging. Despite the potential sus-
tainability of biopolymers relative to petroleum-derived
plastics, lifecycle analyses of bio-based materials such
as bio-based poly(ethylene terephthalate) (bio-PET),
bio-based 1,3‑propanediol, polyhydroxyalkanoate and
environmental benefits of bio­polymers. Factors such as
increased agricultural demands for monomer isolation,
fills and energy requirements for industrial composting
must be factored in when considering the economical
viability of replacing petroleum-based polymers with
biopolymers75.

NATURE REVIEWS | CHEMISTRY VOLUME 1 | ARTICLE NUMBER 0046 | 7

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New design regimes for recyclable polymers consider them as a recyclable alternative to thermosets
Polymer networks held together by covalent bonds in current use98–100 (FIG. 5).
that form and break reversibly are known as dynamic Self-immolative polymers represent a class of de­
covalent materials76,77. Chemistries for dynamic cova- gradable thermoplastics with reversibly triggerable
lent networks have so far capitalized on the reversible properties attractive for sensing, tissue engineering,
formation of disulfides78, imines79,80, olefins81, Diels– lithography and drug delivery applications. Some
Alder adducts82,83, thiol–ene adducts84, alkoxyamines85, examples include polyacetals (poly(phthalaldehyde)s101
hydrazines86, triazoles87, boronic esters88, and, recently, and poly(glyoxylate)s)102, polyurethanes103 and poly-
hemiaminals89 and thioaminals90. Constituents of such carbonates104. Depolymerizations typically involve a
networks are linked through dynamic covalent bonds cascade event in which an end group is activated so as
and may include supramolecular interactions involv- to break down the polymer successively and linearly, a
ing secondary, dative and/or ionic bonding. Examples process that relies on the presence of functional repeat-
of such weak forces include metal–polymer interac- ing units. The kinetics of depolymerization can often
tions91–93, hydrogen bonding 94,95 and π–π stacking 96,97. be controlled through electronic modification of mon-
Vitrimers are reversibly formed materials that mimic omers and changes in ceiling temperature (Tc) of the
properties of thermosetting networks but can respond polymer. Revertible thermoplastics, such as polyesters,
chemically to a stimulus without undergoing depolym- have been synthesized with photodegradable linkages
erization. These desirable properties have led many to in their repeating units105, and examples with base-
depolymerizable polybutyrolactones106 and polybenzyl
a ethers107 are also known. Motifs from these dynamic
assemblies can potentially be applied to the develop-
ment of new recyclable materials, because the products
and their processing are economically competitive with
plastics available on the market.
Thermosets offer high performance but cannot undergo
thermal treatments such as those required for mechanical
recycling. As a consequence, it is particularly important
to develop methods aimed at their chemical reversion.
b We now describe some recent examples of high-perfor-
OH mance degradable thermosets; for a detailed discussion,
O O OH the reader is referred to a more specialized review 108.
OH A degradable crosslinked rubber can be prepared on
O O a scaffold of linear poly(butadiene) chains by incorporat-
Me Me O ing reversible Diels–Alder crosslink junctions that revert
thermally at temperatures greater than 150 °C (REF. 109).
O
In this study, the solubility of the polymer before and after
OH O crosslinking of the linear chains indicated reprocessabil-
O O O O O ity. Tuning the degradation kinetics can be achieved by
altering the crosslink structure. In 2014, a thermosetting
O O
polymer was prepared that, when exposed to acidic (pH
Me Me ~0) solutions, underwent selective and reversible hydro-
lytic depolymerization. Monomer recovery in ~86%
yield involved dissolving the polymer slowly in a 0.5 M
H2SO4 solution, followed by neutralizing and filtering
OH OH
pure mono­mer without further purification. Because
O O O O O
typical operating environments are not highly acidic,
O O the crosslinked polyhexahydrotriazine otherwise proved
Me Me remark­ably robust 110. In another example, composites
woven from healable polyimine resins allowed for selec-
tive hydrolysis of the resin structure leaving a carbon filler
OH OH
material intact 111,112. The polyimines could be healed by
O O O O O
mechanically pressing pieces together under a load and
O O applying heat or moisture. The incorporation of steric
Me Me
strain in a polymer backbone is another strategy to allow
for reversible interconversion between polymer and mon-
Figure 5 | Dynamic covalent materials can undergo topological rearrangements
omer units, as exemplified by the reversibility of polyurea
Nature
while still maintaining their network integrity. a | Exchange Reviews
processes Chemistry
in a|network hydrolysis113. Urea linkers bearing sterically bulky alkyl
occur to preserve the total number of links and average functionality of crosslinks. The groups (tBu or iPr) around the nitrogen atoms undergo
middle image illustrates that the exchange does not require depolymerization in the controlled hydrolysis, which affects the chemical equilib-
intermediate step. b | A common reversible process is transesterification, which is rium for the depolymerization reaction (k1/k−1), as well as
observed in hydroxyl ester networks98. the kinetics of the irreversible hydrolysis step (k2) (FIG. 6).

8 | ARTICLE NUMBER 0046 | VOLUME 1 www.nature.com/natrevchem

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O R2 R1 R2 R1 k2 R2 R1 materials can only undergo a finite number of processing

O
k1
+ C
H2O
N N k−1 NH N H2N
H
− CO2
R3 R3
R1 = Me, H Keq = k1/k−1
R2 = Me, H
R3 = tBu, iPr
Nature Reviews
Figure 6 | Steric strain at urea linkers enables hydrolysis of tunable polyurea | Chemistry
networks.  The presence of a large substituent R3 at the tertiary amide centre introduces
steric strain into the polymer backbone by distorting it from planarity. This results in an
increase in k1, the rate constant associated with depolymerization to the corresponding
isocyanate. In turn, the increased rate of isocyanate formation accelerates its hydrolysis113.
The design of next-generation recyclable polymers is
motivated by the production of materials for specific
applications, and the market demands both high perfor-
mance and conveniently triggered network breakdown
under the right conditions at the end of life.
Conclusions
The recover-and-recycle rates for plastics are extremely
low at present owing to the inefficiency of mechanical
recycling. State‑of‑the-art sorting technologies based
on the physical properties of polymers (for example,
magnetic density separation and triboelectric separa-
tion) or on their optical characteristics (for example,
hyper­spectral imaging and laser-induced breakdown
spectroscopy) are limited in their ability to differentiate
between polymers. This is especially the case for com-
plex materials, such as composites, or materials that have
been partially degraded, such as those subjected to envi-
ronmental stresses. Primary and secondary recycling of
commercial polymers have largely involved thermal
treatments such as ‘melt-and-remould’, with a popular
tertiary method being the thermal catalytic cracking
of polymers into chemical fuels. Polymer thermolysis
over solid catalysts often requires high temperatures
and affords multiple products with varying degrees of
saturation. Recycling approaches have limitations in that
cycles before their properties are substantially compro-
mised. Melt-and-remould approaches cannot be applied
to thermosets or composites. The most extreme method
of deriving some value from waste polymers is incinera-
tion, which is used to extract energy when the materials
can no longer be separated effectively. However, it repre-
sents a net energy loss, as the amount of energy that can
be obtained through incineration is less than the energy
saved through recycling, in which functional monomer
and/or polymer materials can be recovered.
Many opportunities exist for the design of reusable
polymeric materials, and studies on dynamic covalent
materials, self-immolative polymers and vitrimer net-
works will inform the design of new recyclable constructs.
Because the recycling of plastics is largely motivated by
economic factors, new inexpensive materials designed
with end‑of‑life recycling in mind have proved attractive,
so long as the depolymerization conditions includes cat-
alysts that are easily separated after use. These products
and processes must be further developed to make renew-
able technologies more competitive, given the fluctuating
nature of oil prices.
The discovery of catalytic methods for the chemical
recycling of polymers, operative under mild temperatures
and with high selectivities, could aid in monomer recov-
ery on an industrial scale. Processing methods should
be simple and not energy-intensive, with monomers
easily isolable and reversions highly efficient. Crucially,
the materials must also possess mechanical and thermal
properties necessary for the target applications while
maintaining their environmental robustness to serve
as drop‑in alternatives to the plastics currently used.
Ultimately, the development of new methods and mate-
rials that meet economic requirements could result in
global savings of billions of dollars. Perhaps most impor-
tantly, such research would minimize both environmen-
tal pollution and our dependence on non-renewable
petrochemicals for plastics production.

1. Singh, N. et al. Recycling of plastic solid waste: a
state of art review and future application. Composites
B 115, 409–422 (2016).
2. Environmental Protection Agency. Plastics. EPA
https://www3.epa.gov/epawaste/conserve/tools/
warm/pdfs/Plastics.pdf (2015).
3. PlasticsEurope. Plastics — the facts 2016. An
analysis of European plastics production, demand
and waste data. PlasticsEurope http://www.
plasticseurope.org/documents/
document/20161014113313-plastics_the_
facts_2016_final_version.pdf (2016).
4. Environmental Protection Agency. Energy impacts.
EPA https://www3.epa.gov/warm/pdfs/Energy_
Impacts.pdf (2015).
This number reflects cumulative values for mixed
plastic waste, HDPE and PET combined. One barrel
of crude oil is 5,535,600 BTU.
5. Barnes, K. A., Galgani, F., Thompson, R. C. &
Barlaz, M. Accumulation and fragmentation of plastic
debris in global environments. Phil. Trans. R. Soc. B
364, 1985–1998 (2009).
6. Jambeck, J. R. et al. Plastic waste inputs from land
into the ocean. Science 347, 768–771 (2015).
7. García, J. Catalyst: design challenges for the future of
plastics recycling. Chem 1, 813–815 (2016).
8. Huchinson, A. Recycling by the numbers: the truth
about recycling. Popular Mechanics http://www.
popularmechanics.com/science/environment/
a3757/4291576/ (2008).
9. Morris, J. Recycling versus incineration: an energy
conservation analysis. J. Hazard. Mater. 47, 277–293
(1996).
10. Di Maio, F., Rem, P., Serranti, S. & Bonifazi, G. The
W2Plastics project: exploring the limits of polymer
separation. Open Waste Manage. J. 3, 90–98 (2010).
11. Mantia, F. Handbook of Plastics Recycling (Rapra,
2002).
12. Carey, J. On the brink of a recycling revolution? Proc.
Natl Acad. Sci. USA 114, 612–616 (2017).
13. Gitschel, G. Mechanized and recovery system for solid
waste. US Patent 9061289 (2015).
14. Montaudo, G., Puglisi, C. & Samperi, F. Primary
thermal degradation mechanisms of PET and PBT.
Polym. Degrad. Stab. 42, 13–28 (1993).
15. Jamdar, V., Kathalewar, M., Dubey, K. A. & Sabnis, A.
Recycling of PET wastes using electron beam
radiations and preparation of polyurethane coatings
using recycled material. Prog. Org. Coat. 107, 54–63
(2017).
16. Nakao, T. et al. Method for recycling PET bottle. US
Patent 7462649 (2008).
17. Guclu, G., Yalcinyuva, T., Ozgunu, S. & Orbay, M.
Hydrolysis of waste polyethylene terephthalate and
characterization of products by differential scanning
calorimetry. Thermochim. Acta 404, 193–205 (2003).
18. Goto, M. et al. Depolymerization of polyethylene
terephthalate in supercritical methanol. J. Phys.
Condens. Matter 14, 11427–11430 (2002).
19. Kurokawa, H., Ohshima, M., Sugiyama, K. &
Miura, H. Methanolysis of polyethylene terephthalate
(PET) in the presence of aluminium triisopropoxide
catalyst to form dimethyl terephthalate and ethylene
glycol. Polym. Degrad. Stab. 79, 529–533
(2003).
20. West, S. Improved polyethylene terephthalate
decontamination. WO Patent 1995027753A1
(1995).
21. Grzybowski, P. The method for de‑colorization of
polyethylene terephthalate pet waste. WO Patent
2016159800A1 (2016).
22. Fukushima, K. et al. Organocatalytic depolymerization
of poly(ethylene terephthalate). J. Polym. Sci. A 49,
1273–1281 (2011).
23. Fukushima, K. et al. Advanced chemical recycling of
poly(ethylene terephthalate) through organocatalytic
aminolysis. Polym. Chem. 4, 1610–1616 (2013).
24. Gardea, F. et al. Hybrid poly(aryl ether sulfone amide)s
for advanced thermoplastic composites. Macromol.
Chem. Phys. 215, 2260–2267 (2014).
25. Kartalis, C. N., Papaspyrides, C. D. & Pfaendner, R.
Recycling of post-used PE packaging film using the
restabilization technique. Polym. Degrad. Stab. 70,
189–197 (2000).

NATURE REVIEWS | CHEMISTRY VOLUME 1 | ARTICLE NUMBER 0046 | 9

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i
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i
g
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s
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e
s
e
r
v
e
d
.
REVIEWS

26. Vallim, M., Araujo, J., Spinacé, M. & Paoli, M.
Polyamide‑6/high-density polyethylene blend using
recycled high-density polyethylene as compatibilizer:
morphology, mechanical properties, and thermal
stability. Polym. Eng. Sci. 49, 2005–2014 (2009).
27. Jin, H., Gonzalez-Gutierrez, J., Oblak, P., Zupančič, B.
& Emri, I. The effect of extensive mechanical recycling
on the properties of low density polyethylene. Polym.
Degrad. Stab. 97, 2262–2272 (2012).
28. Andersson, T., Stålbom, B. & Wesslén, B. Degradation
of polyethylene during extrusion. II. Degradation of low-
density polyethylene, linear low-density polyethylene,
and high-density polyethylene in film extrusion.
J. Appl. Polym. Sci. 91, 1525–1537 (2004).
29. Karian, H. Handbook of Polypropylene and
Polypropylene Composites (Marcel Dekker, 2003).
30. Phuong, N. & Gilbert, V. Preparation of recycled
polypropylene/organophilic modified layered silicates
nanocomposites part I: the recycling process of
polypropylene and the mechanical properties of
recycled polypropylene/organoclay nanocomposites.
J. Reinf. Plast. Compos. 27, 1983–2000 (2008).
31. Wall, L. A., Madorsky, S. L., Brown, D. W., Straus, S. &
Simha, R. The depolymerization of polymethylene and
polyethylene. J. Am. Chem. Soc. 76, 3430–3437
(1954).
32. Sharma, B. K., Moser, B. R., Vermillion, K. E.,
Doll, K. M. & Rajagopalan, N. Production,
characterization and fuel properties of alternative
diesel fuel from pyrolysis of waste plastic grocery bags.
Fuel Process. Technol. 122, 79–90 (2014).
33. Miskolczi, N., Angyal, A., Bartha, L. & Valkai, I. Fuels
by pyrolysis of waste plastics from agricultural and
packaging sectors in a pilot scale reactor. Fuel
Process. Technol. 90, 1032–1040 (2009).
34. Abbas-Abadi, M. S., Haghighi, M. N., McDonald, A. G.
& Yeganeh, H. Estimation of pyrolysis product of LDPE
degradation using different process parameters in a
stirred reactor. Polyolefins J. 2, 39–47 (2015).
35. Achilias, D. S., Roupakias, C., Megalokonomos, P.,
Lappas, A. A. & Antonakou, E. V. Chemical recycling of
plastic wastes made from polyethylene (LDPE and
HDPE) and polypropylene (PP). J. Hazard. Mater.
149, 536–542 (2007).
36. Lal, S., Anisia, K. S. & Kumar, A. Depolymerization of
HDPE to wax in presence of catalyst formed by
homonuclear macrocyclic zirconium complex
chemically bonded to alumina support. Appl. Catal. A
303, 9–17 (2006).
37. Wong, S., Ngadi, N., Abdullah, T. A. T. & Inuwa, I. M.
Catalytic cracking of LDPE dissolved in benzene using
nickel-impregnated zeolites. Ind. Eng. Chem. Res. 55,
2543–2555 (2016).
38. Aguado, R., Olazar, M., San José, M. J. & Bilbao, J.
Wax formation in the pyrolysis of polyolefins in a
conical spouted bed reactor. Energy Fuels 16,
1429–1437 (2002).
39. Sakata, Y., Uddin, M. A. & Muto, A. Degradation of
polyethylene and polypropylene into fuel oil by using
solid acid and non-acid catalysts. J. Anal. Appl.
Pyrolysis 51, 135–155 (1999).
40. Lin, Y.‑H. & Yang, M.‑H. Chemical catalysed recycling
of waste polymers: catalytic conversion of
polypropylene into fuels and chemicals over spent FCC
catalyst in a fluidised-bed reactor. Polym. Degrad.
Stab. 92, 813–821 (2007).
41. Ballice, L. & Reimert, R. Temperature-programmed
co‑pyrolysis of Turkish lignite with polypropylene.
J. Anal. Appl. Pyrolysis 65, 207–219 (2002).
42. Achilias, D. S. et al. in Material Recycling — Trends
and Perspectives Ch. 1 (ed. Achilias, D.) 6–7 (InTech,
2012).
43. Guddeti, R. R., Knight, R. & Grossmann, E. D.
Depolymerization of polypropylene in an induction-
coupled plasma (ICP) reactor. Ind. Eng. Chem. Res. 39,
1171–1176 (2000).
44. Jia, X., Qin, C., Friedberger, T., Guan, Z. & Huang, Z.
Efficient and selective degradation of polyethylenes
into liquid fuels and waxes under mild conditions. Sci.
Adv. 2, e1501591 (2016).
45. Sadat-Shojai, M. & Bakhshandeh, G.‑R. Recycling of
PVC wastes. Polym. Degrad. Stab. 96, 404–415
(2011).
46. Yu, J., Sun, L., Ma, C., Qiao, Y. & Yao, H. Thermal
degradation of PVC: a review. Waste Manage. 48,
300–314 (2016).
47. McNeill, I. C., Memetea, L. & Cole, W. J. A study of the
products of PVC thermal degradation. Polym. Degrad.
Stab. 49, 181–191 (1995).
48. Troitskii, B., Troitskaya, L. S., Myakov, N. &
Lepaev, A. F. Mechanism of the thermal degradation of
poly(vinyl chloride). J. Polym. Sci. Polym. Symp. 42,
1347–1361 (1973).
49. Lopez-Urionabarrenechea, A., de Marco, I.,
Caballero, B. M., Laresgoiti, M. F. & Adrados, A.
Catalytic stepwise pyrolysis of packaging plastic waste.
J. Anal. Appl. Pyrolysis 96, 54–62 (2012).
50. Mio, H., Saeki, S., Kano, J. & Saito, F. Estimation of
mechanochemical dechlorination rate of poly(vinyl
chloride). Environ. Sci. Technol. 36, 1344–1348
(2002).
51. Vandenhende, B. & Fassiau, E. Process for the solvent
treatment of a plastic. WO Patent 2005100461A1
(2005).
52. Chemical Safety Facts. Polystyrene. Chemical Safety
Facts https://www.chemicalsafetyfacts.org/wp-content/
uploads/2014/05/082514_ChemSafety_Print-
Polystyrene.pdf (2014).
53. Wünsch, J. R. Polystyrene: Synthesis, Production and
Applications 5 (Rapra, 2000).
54. Goodier, K. Making and using an expanded plastic.
New Sci. 240, 706–707 (1961).
55. Shah, J., Jan, M. R. & Adnan, A. Tertiary recycling of
waste polystyrene using magnesium impregnated
catalysts into valuable products. J. Anal. Appl.
Pyrolysis 114, 163–171 (2015).
56. Marczewski, M. et al. Catalytic decomposition of
polystyrene. The role of acid and basic active centers.
Appl. Catal. B 129, 236–246 (2013).
57. Zhang, Z. et al. Chemical recycling of waste
polystyrene into styrene over solid acids and bases.
Ind. Eng. Chem. Res. 34, 4514–4519 (1995).
58. Yang, Y. et al. Biodegradation and mineralization of
polystyrene by plastic-eating mealworms: part 1.
Chemical and physical characterization and isotopic
tests. Environ. Sci. Technol. 49, 12080–12086
(2015).
59. Gutiérrez, C., Rodriguez, J. F., Gracia, I., de Lucas, A.
& García, M. T. Reduction of the carbon footprint
through polystyrene recycling: economical evaluation.
Process Saf. Environ. Prot. 101, 144–151 (2016).
60. Bajdur, W., Pajączkowski, J., Makarucha, B.,
Sułkowska, A. & Sułkowski, W. W. Effective
polyelectrolytes synthesized from expanded
polystyrene wastes. Eur. Polym. J. 38, 299–304
(2002).
61. Sato, Y., Kondo, T., Tsujita, K. & Kawai, N.
Degradation behaviour and recovery of bisphenol‑A
from epoxy resin and polycarbonate resin by liquid-
phase chemical recycling. Polym. Degrad. Stab. 89,
317–326 (2005).
62. Jones, G. O., Yuen, A., Wojtecki, R. J., Hedrick, J. L. &
García, J. M. Computational and experimental
investigations of one-step conversion of
poly(carbonate)s into value-added poly(aryl ether
sulfone)s. Proc. Natl Acad. Sci. USA 113, 7722–7726
(2016).
63. Cowley, P. R. E. J. & Melville, H. W. The photo-
degradation of polymethylmethacrylate. I. The
mechanism of degradation. Proc. R. Soc. Lond. A 210,
461–481 (1952).
64. Chen, Y.‑C. Thermal Degradation of Poly(methyl
methacrylate) in Solution in Various Solvents. Thesis,
Univ. Missouri (1965).
65. Zheng, Y.‑F., Chen, T.‑Y., Sun, Y.‑L. & Deng, R. L.
Method for preparing pure nylon 6 from nylon 6 waste
as raw material. CN Patent 105367818 (2016).
66. Braun, M., Levy, A. B. & Sifniades, S. Recycling nylon 6
carpet to caprolactam. Polym. Plast. Technol. Eng. 38,
471–484 (1999).
67. Chaupart, N., Serpe, G. & Verdu, J. Molecular weight
distribution and mass changes during polyamide
hydrolysis. Polymer 39, 1375–1380 (1998).
68. Bryson, L. G. Monomer Recovery from Nylon via
Reactive Extrusion. Thesis, Georgia Inst. Technol.
(2008).
69. Howarth, J., Mareddy, S. S. R. & Mativenga, P. T.
Energy intensity and environmental analysis of
mechanical recycling of carbon fibre composite.
J. Cleaner Prod. 81, 46–50 (2014).
70. Jiang, G. et al. Characterisation of carbon fibres
recycled from carbon fibre/epoxy resin composites
using supercritical n‑propanol. Compos. Sci. Technol.
69, 192–198 (2009).
71. La Rosa, A. D., Banatao, D. R., Pastine, S. J., Latteri, A.
& Cicala, G. Recycling treatment of carbon fibre/epoxy
composites: materials recovery and characterization
and environmental impacts through life cycle
assessment. Composites Part B 104, 17–25 (2016).
72. Liang, B., Qin, B., Pastine, S. & Li, X. Reinforced
composite and method for recycling the same. WO
Patent 2013007128A1 (2013).
73. Tsujii, A., Namba, M., Okamura, H. & Matsumoto, A.
Radical alternating copolymerization of twisted
1,3‑butadienes with maleic anhydride as a new
approach for degradable thermosetting resin.
Macromolecules 47, 6619–6626 (2014).
74. Kristufek, S. L. et al. Synthesis, characterization, and
cross-linking strategy of a quercetin-based epoxidized
monomer as a naturally-derived replacement for BPA
in epoxy resins. ChemSusChem 9, 2135–2142 (2016).
75. Hottle, T. A., Bilec, M. M. & Landis, A. E. Sustainability
assessments of bio-based polymers. Polym. Degrad.
Stab. 98, 1898–1907 (2013).
76. Rowan, S. J., Cantrill, S. J., Cousins, G. R. L.,
Sanders, J. K. M. & Stoddart, J. F. Dynamic covalent
chemistry. Angew. Chem. Int. Ed. 41, 898–952
(2002).
77. Maeda, T., Otsuka, H. & Takahara, A. Dynamic
covalent polymers: reorganizable polymers with
dynamic covalent bonds. Prog. Polym. Sci. 34,
581–604 (2009).
78. Takahashi, A., Ohishi, T., Goseki, R. & Otsuka, H.
Degradable epoxy resins prepared from diepoxide
monomer with dynamic covalent disulfide linkage.
Polymer 82, 319–326 (2016).
79. Wu, X. et al. Self-assembly of a ‘double dynamic
covalent’ amphiphile featuring a glucose-responsive
imine bond. Chem. Commun. (Camb.) 52, 6981–6984
(2016).
80. Pettignano, A. et al. Self-healing alginate–gelatin
biohydrogels based on dynamic covalent chemistry:
elucidation of key parameters. Mater. Chem. Front. 1,
73–80 (2017).
81. Lu, Y.‑X., Tournilhac, F., Leibler, L. & Guan, Z. Making
insoluble polymer networks malleable via olefin
metathesis. J. Am. Chem. Soc. 134, 8424–8427
(2012).
82. Chen, X. et al. A thermally re‑mendable cross-linked
polymeric material. Science 295, 1698–1702
(2002).
83. Bergman, S. D. & Wudl, F. Mendable polymers.
J. Mater. Chem. 18, 41–62 (2008).
84. Scott, T. F., Schneider, A. D., Cook, W. D. &
Bowman, C. D. Photoinduced plasticity in cross-linked
polymers. Science 308, 1615–1617 (2005).
85. Higaki, Y., Otsuka, H. & Takahara, A. A
thermodynamic polymer cross-linking system based
on radically exchangeable covalent bonds.
Macromolecules 39, 2121–2125 (2006).
86. Wang, T.‑N., Yang, G., Wu, L.‑B. & Chen, G.‑S. Self-
assembly of supra-amphiphile of azobenzene-
galactopyranoside based on dynamic covalent bond
and its dual responses. Chin. Chem. Lett. 27,
1740–1744 (2016).
87. Wei, Q. et al. Self-healing hyperbranched
poly(aroyltriazole)s. Sci. Rep. 3, 1093–1098 (2013).
88. Chang, X. et al. Dynamic covalent chemistry-based
sensing: pyrenyl derivatives of phenylboronic acid for
saccharide and formaldehyde. Sci. Rep. 6,
31187–31195 (2016).
89. Fox, C. H. et al. Supramolecular motifs in dynamic
covalent PEG-hemiaminal organogels. Nat. Commun.
6, 7417 (2015).
90. Wojtecki, R. J. et al. Developments in dynamic
covalent chemistries from the reaction of thiols with
hexahydrotriazines. J. Am. Chem. Soc. 137,
14248–14251 (2015).
91. Whittell, G. R., Hager, M. D., Schubert, U. S. &
Manners, I. Functional soft materials from
metallopolymers and metallosupramolecular
polymers. Nat. Mater. 10, 176–188 (2011).
92. Rossow, T., Hackelbusch, S., van Assenbergh, P. &
Seiffer, S. A modular construction kit for
supramolecular polymer gels. Polym. Chem. 4,
2515–2527 (2013).
93. Krogsgaard, M., Behrens, M. A., Pedersen, J. S. &
Birkedal, H. Self-healing mussel-inspired
multi‑pH‑responsive hydrogels. Biomacromolecules
14, 297–301 (2013).
94. Li, G. et al. Synthesis, self-assembly and reversible
healing of supramolecular perfluoropolyethers.
J. Polym. Sci. A: Polym. Chem. 51, 3598–3606
(2013).
95. Cordier, P., Tournilhac, F., Soulié-Ziakovic, C. &
Leibler, L. Self-healing and thermoreversible rubber
from supramolecular assembly. Nature 451,
977–980 (2008).
96. Greenland, B. W., Burattini, S., Hayes, W. &
Colquhoun, H. M. Design, synthesis and
computational modelling of aromatic tweezer-
molecules as models for chain-folding polymer blends.
Tetrahedron 64, 8346–8354 (2008).

10 | ARTICLE NUMBER 0046 | VOLUME 1 www.nature.com/natrevchem

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r
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o
f
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A
l
l
r
i
g
h
t
s
r
e
s
e
r
v
e
d
.
 REVIEWS

97. Hart, L. R., Harries, J. L., Greenland, B. W.,
Colquhoun, H. M. & Hayes, W. Healable
supramolecular polymers. Polym. Chem. 4,
4860–4870 (2013).
98. Montarnal, D., Capelot, M., Tournilhac, F. & Leibler, L.
Silica-like malleable materials from permanent organic
networks. Science 344, 965–968 (2011).
99. Fortman, D. J., Brutman, J. P., Cramer, C. J.,
Hillmyer, M. A. & Dichtel, W. R. Mechanically
activated, catalyst-free polyhydroxyurethane
vitrimers. J. Am. Chem. Soc. 137, 14019–14022
(2015).
100. Snijkers, F., Pasquino, R. & Maffezzoli, A. Curing and
viscoelasticity of vitrimers. Soft Matter 13, 258–268
(2017).
101. Tsuda, M., Hata, M., Nishida, R. & Oikawa, S. Acid-
catalyzed degradation mechanism of
poly(phthalaldehyde): unzipping reaction of chemical
amplification resist. J. Polym. Sci. A: Polym. Chem. 35,
77–89 (1997).
102. Fan, B., Trant, J. F., Wong, A. D. & Gillies, E. R.
Polyglyoxylates: a versatile class of triggerable self-
immolative polymers from readily accessible
monomers. J. Am. Chem. Soc. 136, 10116–10123
(2014).
103. Sagi, A., Weinstain, R., Karton, N. & Shabat, D. Self-
immolative polymers. J. Am. Chem. Soc. 130,
5434–5435 (2008).
104. Chen, E. K. Y., McBride, R. A. & Gillies, E. R. Self-
immolative polymers containing rapidly cyclizing
spacers: toward rapid depolymerization rates.
Macromolecules 45, 7364–7374 (2012).
105. Rajendran, S. et al. Programmed photodegradation of
polymeric/oligomeric materials derived from renewable
bioresources. Angew. Chem. Int. Ed. 54, 1159–1163
(2015).
106. Hong, M. & Chen, E. Y.‑X. Completely recyclable
biopolymers with linear and cyclic topologies via ring-
opening polymerization of γ‑butyrolactone. Nat. Chem.
8, 42–49 (2016).
107. Baker, M. S., Kim, H., Olah, M. G., Lewis, G. G. &
Phillips, S. T. Depolymerizable poly(benzyl ether)-based
materials for selective room temperature recycling.
Green Chem. 17, 4541–4545 (2015).
108. Kloxin, C. J. & Bowman, C. N. Covalent adaptable
networks: smart, reconfigurable and responsive
network systems. Chem. Soc. Rev. 42, 7161–7173
(2013).
109. Polgar, L. M., van Duin, M., Broekhuis, A. A. &
Picchioni, F. Use of Diels–Alder chemistry for
thermoreversible cross-linking of rubbers: the next step
toward recycling of rubber products? Macromolecules
48, 7096–7105 (2015).
110. García, J. M. et al. Recyclable, strong thermosets and
organogels via paraformaldehyde condensation with
diamines. Science 344, 732–735 (2014).
111. Taynton, P. et al. Re‑healable polyimine thermosets:
polymer composition and moisture sensitivity. Polym.
Chem. 7, 7052–7056 (2016).
112. Taynton, P. et al. Repairable woven carbon fiber
composites with full recyclability enabled by malleable
polyimine networks. Adv. Mater. 28, 2904–2909
(2016).
113. Ying, H. & Cheng, J. Hydrolyzable polyureas bearing
hindered urea bonds. J. Am. Chem. Soc. 136,
16974–16977 (2014).
114. Murariu, V., Svoboda, J. & Sergeant, P. The modelling
of the separation process in a ferrohydrostatic
separator. Miner. Eng. 18, 449–457 (2005).
115. Bakker, E. J., Rem, P. C. & Fraunholcz, N. Upgrading
mixed polyolefin waste with magnetic density
separation. Waste Manage. 29, 1712–1717 (2009).
116. Xiao, C., Allen, L. III, Biddle, M. & Fisher, M.
Electrostatic separation and recovery of mixed plastics.
P2RIC InfoHouse http://infohouse.p2ric.org/
ref/47/46175.pdf (1999).
117. Tilmatine, A. et al. Electrostatic separators of particles:
application to plastic/metal, metal/metal and plastic/
plastic mixtures. Waste Manage. 29, 228–232
(2009).
118. Alter, H. Application of the critical surface tension
concept to items in our everyday life. J. Adhes. 9,
135–140 (1978).
119. Hu, B., Serranti, S., Fraunholcz, N., Di Maio, F. &
Bonifazi, G. Recycling-oriented characterization of
polyolefin packaging waste. Waste Manage. 33,
574–584 (2013).
120. Gondal, M. & Siddiqui, M. Identification of different
kinds of plastics using laser-induced breakdown
spectroscopy for waste management. J. Environ. Sci.
Health A Tox. Hazard. Subst. Environ. Eng. 42,
1989–1997 (2007).
121. Sanaee, S. & Bakker, M. Ultrasound for monitoring and
quality inspection in MDS plastics recycling.
International Solid Waste Association http://www.iswa.
org/uploads/tx_iswaknowledgebase/15-191paper_
long.pdf (2009).
Acknowledgements
The authors thank C. H. Fox for insights and discussions.
Competing interests statement
The authors declare no competing interests.
Publisher’s note
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claims in published maps and institutional affiliations.
How to cite this article
Rahimi, A. & García, J. M. Chemical recycling of waste plastics
for new materials production. Nat. Rev. Chem. 1, 0046 (2017).
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