Articles

https://doi.org/10.1038/s41557-019-0249-2

Closed-loop recycling of plastics enabled by

dynamic covalent diketoenamine bonds
Peter R. Christensen   1, Angelique M. Scheuermann1,2, Kathryn E. Loeffler1 and Brett A. Helms   1,3*

Recycled plastics are low-value commodities due to residual impurities and the degradation of polymer properties with each
cycle of re-use. Plastics that undergo reversible polymerization allow high-value monomers to be recovered and re-manufac-
tured into pristine materials, which should incentivize recycling in closed-loop life cycles. However, monomer recovery is often
costly, incompatible with complex mixtures and energy-intensive. Here, we show that next-generation plastics—polymerized
using dynamic covalent diketoenamine bonds—allow the recovery of monomers from common additives, even in mixed waste
streams. Poly(diketoenamine)s ‘click’ together from a wide variety of triketones and aromatic or aliphatic amines, yielding only
water as a by-product. Recovered monomers can be re-manufactured into the same polymer formulation, without loss of perfor-
mance, as well as other polymer formulations with differentiated properties. The ease with which poly(diketoenamine)s can be
manufactured, used, recycled and re-used—without losing value—points to new directions in designing sustainable polymers
with minimal environmental impact.

C
losed-loop polymer life cycles are critical to sustainability
efforts worldwide1–7. Their integration into the global materi-
als’ ecosystem hinges on maintaining high value in recovered
materials at the end of a product’s life. Value is lost when process-
ing is costly, energy-intensive or alters the physical properties and
appearance of recovered materials8. To reduce the cost and energy
intensity of depolymerizing plastics, lowering the energetic bar-
rier to bond cleavage is critical. Advances in catalysis9 and dynamic
covalent chemistry10 have emerged as potential solutions11–35. In
particular, dynamic covalent polymers known as vitrimers have
been recently proposed as sustainable replacements for non-recy-
clable thermoset materials27–35. Vitrimers undergo associative bond
exchange reactions in the solid state, allowing crosslinked materi-
als to be thermally processed and recycled like thermoplastics while
maintaining high crosslink density. In certain cases, vitrimers have
been shown to depolymerize, yielding soluble oligomers or small
molecules (Supplementary Fig.  1)28,30–32,34,35. However, like other
plastics, it remains a challenge to depolymerize vitrimers at low
recovered using a regenerative resin-based process, closing the
loop (Fig. 2a and Supplementary Fig. 3). In 5.0 M H2SO4, complete
depolymerization occurs in less than 12 h, and pure triketone and
amine monomers are recovered in >90% isolated yields (Fig. 2b–d);
5.0 M HCl was similarly effective in PDK depolymerization.
Under the same conditions, depolymerization is not observed for
common plastics in use today, allowing PDKs to be easily sepa-
rated from mixed plastic waste streams (Fig.  2e). PDK depoly-
merization also tolerates a wide spectrum of additives, including
dyes, pigments, inorganic fillers, fibre reinforcing fabrics and
flame retardants, even when these additives comprise high weight
fractions in the polymer composite. Recovered monomers can be
re-manufactured without loss of performance, or re-formulated
with differentiated properties. The ease with which PDKs can
be manufactured, used, recycled and re-used—without losing
O O OH O

temperatures, in short reaction times, with high tolerance to addi-

tives, and from mixed plastic waste streams. Furthermore, depo-
O O
lymerization efforts have not emphasized a return to the original
monomers, which limits re-formulation opportunities by requiring
further manipulation before re-entering the supply chain.
Here we show that dynamic network polymers synthesized NH2 H3O+ H3O+ NH2
using diketoenamine bonds address these challenges by leverag-
ing their unique chemistry to uncouple the otherwise conflict-
ing demands for formulation, manufacturing, performance,
H H
recycling, re-manufacturing and re-use. Poly(diketoenamine)s, O N
NH2
O N
or PDKs, are prepared via ‘click’36 polycondensation reactions
between ß-triketones and aromatic or aliphatic amines (Fig.  1).
NH2
Notably, ß-triketone monomers are accessed in a single step from O O
widely available polytopic carboxylic acids and 1,3-diones37. In
contrast to other vitrimer platforms (Supplementary Fig.  1), Fig. 1 | Reversible, dynamic covalent diketoenamine bonds. Diketoenamine
PDKs hydrolyzse in strong aqueous acid (0.5–5.0 M H2SO4) bonds form spontaneously from triketones and both aromatic and aliphatic
at ambient temperature to yield pure, immediately reusable amines. Under strongly acidic conditions in water, the diketoenamine bond
triketones (Supplementary Fig.  2); amine monomers are then hydrolyses to the triketone and an ammonium salt.

The Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, CA, USA. 2Department of Chemistry, University of California, Berkeley, Berkeley,
1

CA, USA. 3Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, USA. *e-mail: bahelms@lbl.gov

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O NH2
a O O

N
TK-6 O O H2N NH2
O
Triketone TREN
Precipitate triketone
HCl/H2O TREN–NH2/H2O
Dry Dry
NH2
N

O O
H N
N H
O O O
O–O + K
NH2
N N + – NaOH + OH
–

– +
O–O –+ OH
O K + O O + + + +
+ –
–
+ OH
H N Poly(diketoenamine) + +
+ N H – OH
–
+ + + + + + +
– – – – PDK-6(TREN)
O O + –
–
+ + OH
+ – – OH +
– –+
–
+ +
N Ion
Extract triketone exchange
resin
K2CO3/H2O
Depolymerize
H2SO4/H2O

+ –
Crude triketone + – + + – + TREN–NH3 SO4
–
– + – –
– + +
+ – + – + +
O – –
O O + – + +
–

O O
b cO d
100 100

Triketone recovery (%)

80 80
Residual polymer (%)

NH2
N
60 60
Nylon-6

O O
H2O 0.1 M 0.5 M 1.0 M 5.0 M 40 H N 40
N H
20 O O 20

0N 0

H2O 0.1 0.5 1.0 5.0 0 2 4 6 8 10 12

H2SO4, 25 °C, 24 h
[H2SO4] (M) t (h)
e

Mixed plastic waste 5.0 M H2SO4 Filter Extract triketone PET, PA, Triketone Precipitate
25 °C,12 h solids 1.0 M K2CO3 PE, PP, PVC, PC 1.0 M K2CO3 triketone
2.0 M HCl

Fig. 2 | Closed-loop recycling from dynamic covalent PDKs. a, Network PDKs (for example, PDK-6(TREN)) are synthesized from polyamines (for
example, tris(2-aminoethyl)amine, TREN) and ditopic triketones (for example, TK-6), and are hydrolysed in strong acid. Both triketone and TREN
monomers can be recovered and re-used in a closed-loop fashion using regenerative chemical processes. b, Photograph showing the depolymerization
of PDK-6(TREN) in H2SO4 from 0 to 5.0 M. c, Corresponding data showing the amount of PDK remaining after 24 hours at room temperature as a
function of acid concentration. d, Triketone monomer recovery over time during PDK-6(TREN) depolymerization in 5.0 M H2SO4. e, Photographs
showing orthogonal depolymerization of PDKs and triketone monomer recovery from mixed plastic waste containing poly(ethylene terepthalate)
(PET), nylon-6,6 (PA), polyethylene (PE), poly(vinyl chloride) (PVC) and polycarbonate (PC). Data in b and c are the average of two trials;
error bars indicate s.d.

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a NH2

NH2
N N
H2N NH2
O
O O TREN O O
H N
N H
n n
O O O O
O
N
Ball
mill
n = 1: TK-6 n = 1: PDK-6(TREN)
n = 2: TK-8 n = 2: PDK-8(TREN)
n = 3: TK-10 n = 3: PDK-10(TREN)

15–60 min

b c 140
d 140
100
120

80 120 100
Gel fraction (%)

80

Tg (°C)
Tg (°C)

60

PDK-10(TREN)
PDK-6(TREN)

PDK-8(TREN)
1.2 equiv. NH2 100 1.2 equiv. NH2 60
40
1.1 equiv. NH2 1.1 equiv. NH2 40
20 1.0 equiv. NH2 1.0 equiv. NH2
80 20
0.9 equiv. NH2 0.9 equiv. NH2
0 0
15 30 45 60 15 30 45 60
t (min) t (min)

Fig. 3 | Synthesis of network poly(ketoenamine)s by ball-milling. a, Dynamic covalent PDKs are synthesized by ball-milling TK-6–10 with TREN,
yielding network polymers PDK-6–10(TREN). b,c, A well-controlled PDK network density is evidenced by repeatable trajectories for the gel fraction
(b) and Tg (c), each as a function of ball-milling time and the mol% (equiv.) of amine functionality relative to triketone functionality in the formulation.
Data are shown for PDK-6(TREN). d, The observed Tg of different PDK networks decreases with increasing triketone spacer length. Data in b, c are the
average of three trials; error bars are the standard deviation.

value—suggests exciting new paths for next-generation plastics
with minimal environmental impact.
Results
Polymer synthesis. The PDK platform encompasses a broad
range of polymer formulations for accessing diversity-oriented
structure–property space. To begin to explore PDK structure–prop-
erty space, we prepared three triketone dimers from adipic acid
(TK-6), suberic acid (TK-8) and sebacic acid (TK-10) precursors,
respectively (Fig.  3). Owing to the spontaneous reaction between
amines and triketones, PDK networks are easily synthesized by
mechanically grinding triketone monomers with tris(2-aminoethyl-
amine) (TREN) or with mixtures of TREN and various diamines
using a ball mill, without requiring organic solvents. In addition to
being a scalable process, we hypothesized that the extent of reaction
between amines and triketones could be controlled by adjusting the
ball-milling time. To demonstrate this, TK-6 was ball-milled in the
presence of TREN, without solvent, yielding fine powders of network
polymer PDK-6(TREN) (Supplementary Fig.  4). The glass transi-
tion temperature Tg and insoluble (gel) fraction of PDK-6(TREN)
were measured as a function of both the duration of ball-milling
and equivalents (equiv.) of amine relative to triketone functional
groups (Fig.  3e,f). PDK-6(TREN) network materials showed high
Tg (>120 °C) and gel fractions of >95% in less than 1 h of mechanical
processing. The extent of the reaction was further analysed by solid-
state NMR spectroscopy, showing no detectable TK-6 starting mate-
rial after only 45 min of ball-milling for formulations with ≥1 equiv.
amine (Supplementary Figs.  5–9). The reproducible trajectories of
both Tg and gel fraction as a function of formulation and process-
ing time are an advantage over batch processes where these cannot
be controlled, indicating that ball-milling is a powerful new tool for
controlling network density in dynamic soft matter.
Polymer compounding, de-colouration and recovery of virgin-
quality monomer. We found ball-milling to be effective in blending
various stabilizers, plasticizers, dyes, pigments and flame retardants
into the polymers to meet aesthetic, performance and regulatory
requirements without complicating recycling. To demonstrate
this, network polymer PDK-6(TREN) was recycled as a mixture
of coloured plastics containing organic and inorganic colourants
(Fig.  4). Red, blue, yellow and black samples of PDK-6(TREN)
were mixed together and depolymerized in 5.0 M H2SO4 to yield a
precipitate containing  TK-6 monomer along with carbon nanofi-
bres, TiO2 and red, blue and yellow dye molecules. From complex
mixtures, triketone monomers are easily separated from additives,
and other polymers, by extracting into aqueous base, filtering off
insoluble components and subsequently precipitating triketones
upon re-acidification (pH < 3) (Fig. 4c,d).
Closed-loop recycling of flame-retardant fibre-reinforced com-
posites. Depolymerization strategies, such as ours, are attractive for
recycling fibre-reinforced composite materials31,32, and PDKs may
be particularly well suited for these applications. To demonstrate
the ease of depolymerization and separation of all components in
such composites, woven fibreglass was impregnated with a PDK-
6(TREN) resin containing 25% (wt/wt) triphenylphosphate (TPP)
as a flame retardant (Supplementary Fig. 10). The fibre-reinforced
composite was subjected to the described aqueous processing

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a b c d e
Depolymerize Extract triketone Precipitate triketone Filter and dry
O
O O
+ + + – – – –
+ + –
+ – – – –
+ +
O O
O
TK-6

PDK-6(TREN) + colourant

Mixed polymer decolouration

Composite
recycling and flame
retardant removal

f g h i

Fibre

TK-6
Fibre +
Flame retardant Flame
TK-6
retardant

Fig. 4 | Mixed polymer decolouration, additive removal and closed-loop recycling of fibre-reinforced composites. a, A mixed-colour waste stream
consisting of PDK-6(TREN) compounded with carbon nanofibres, TiO2, blue, yellow or red organic dyes. b, Red, blue, yellow and black samples of
PDK-6(TREN) were completely depolymerized at room temperature in 5.0 M H2SO4 to yield a solid mixture of TK-6 monomer and pigments/additives.
c, TK-6 was extracted into aqueous base at room temperature and separated from additives by filtration. d,e, The basic extract was acidified, precipitating
pure TK-6 monomer. f, Fibreglass cloth, impregnated with PDK-6(TREN), containing 25% (wt/wt) TPP flame retardant. g,h, Depolymerization of
PDK-6(TREN) enables separation and recovery of undamaged fibreglass cloth. i, TK-6 monomer is separated from the flame retardant additive in
aqueous base, allowing the fibreglass cloth, flame retardant and TK-6 monomer to be isolated from each other.

sequence (depolymerize, extract and precipitate), allowing trik-
etone, flame retardant and fibre-reinforcing fabric to be recovered
(Fig.  4g–i). Specifically, the initial depolymerization of the PDK
resin allows the fibreglass cloth to be removed as a single, undam-
aged component, leaving behind a mixture of TK-6 monomers and
TPP. The triketone monomer is separated from TPP by extracting
it into the base and precipitating it using acid—effectively separat-
ing and isolating pristine fibre material, resin monomer and flame
retardant (Fig. 4i).
Recovery of virgin-quality monomer enables upcycling. It’s note-
worthy that  TK-6 monomer obtained from each of the recycling
experiments showed no detectable side products, residual amine, pig-
ments or flame-retardant additives (Supplementary Figs. 10 and 11).
The recovery of pure TK monomers enables immediate re-use for
synthesizing new polymers of the same or different formulation,
thus maximizing the inherent value of waste material. To demon-
strate that recovered triketone monomers can be re-formulated into
PDKs with the same or differentiated properties, we synthesized
PDK-6(TREN) from recycled  TK-6 as well as network polymers
PDK-6(TREN:ODA) and PDK-6(TREN:PPG) using mixtures
of TREN and 4,4′-dioxyaniline (ODA) or poly(propylene glycol)
bis(2-aminopropyl ether) (PPG, Mn = 2,000 g mol–1), respectively
(Fig.  5). Dynamic mechanical analysis (DMA) of recycled PDK-
6(TREN) shows nearly identical properties to PDK-6(TREN)
synthesized from pristine TK-6 (Fig. 5b). The storage moduli (E′)
of re-formulated PDK materials range from 0.3(±0.1) GPa for
PDK-6(TREN:PPG) to 1.8(±0.2) GPa for PDK-6(TREN:ODA)
(Supplementary Fig.  11). Formulation chemistry whereby linear
polymeric diamines are embedded into PDK networks further
allows their ductility to be readily tuned: for example, incorporation
of only 5 mol% poly(tetrahydrofuran) bis(3-aminopropyl ether)
(Mw of ~1,000 g mol–1) into PDK-10(TREN) networks improved the
toughness of PDKs without significantly sacrificing room-tempera-
ture storage and tensile moduli (Fig. 5d,e).
Dynamic covalent diketoenamine bond exchange with aliphatic
and aromatic amines. The ability to formulate dynamic covalent

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a
O
O O

Recycled TK-6 O O Recycled TK-6

O Recycled
TK-6
TREN TREN
90 mol% 90 mol%
+ +
NH2
O
O
H2N NH2
n N H2N NH2
H 2N NH2
PPG
Mn = 2,000 g mol–1 TREN ODA
10 mol% 100 mol% 30 mol%

PDK-6(TREN:PPG) PDK-6(TREN) PDK-6(TREN:ODA)

b 104 2.0 c
40

1.6 PDK-6(TREN)
103 30
PDK-6(TREN:ODA)

Stress (MPa)
E ′ (MPa)

1.2

Tan δ
2 PDK-6(TREN) 20 PDK-6(TREN:PPG)
10
virgin 0.8
101 PDK-6(TREN) 10
recycled 0.4

0
100 2.0 0.0
40 80 120 160 200 0 20 40 60 80 100
T (°C) Strain (%)

d e
104 40
2.4

2.0
103 30
Stress (MPa)

1.6
E ′ (MPa)

Tan δ

102 PDK-10(TREN) 1.2 20

PDK-10(TREN:PTHF) PDK-10(TREN)
0.8
101 10 PDK-10(TREN:PTHF)
0.4

100 0.0 0
0 40 80 120 160 200 0 1 2 3 4 5 6
T (°C) Strain (%)

Fig. 5 | Re-formulation of PDK networks. a, TK-6 obtained through depolymerization of PDK-6(TREN) was used to re-formulate PDK networks with
TREN, TREN alongside 4,4′-oxydianiline (ODA) and TREN alongside PPG. b, DMA of PDK-6(TREN) showed nearly identical properties when formulated
from either virgin or recycled TK-6 monomer. c, Tensiometry for PDK-6(TREN), PDK-6(TREN:PPG) and PDK-6(TREN:ODA). d,e, DMA showing E′
(solid lines) and tan δ (dotted lines) (d) and tensiometry (e) for PDK-10(TREN) and PDK-10(TREN:PTHF) containing 5 mol% poly(tetrahydrofuran)
bis(2-aminopropyl ether) (PTHF).

a b c 6.0
1.0 1.0
140 °C 140 °C PDK-6(TREN)
150 °C 150 °C 5.6 PDK-6(TREN:ODA)
0.8 0.8 160 °C
160 °C
5.2 60 kJ mol–1
170 °C PDK-6 170 °C
PDK-6
G/G0

G/G0

ln τ

0.6 (TREN) 0.6 (TREN:ODA) 4.8

1/e 1/e 4.4

0.4 0.4 49 kJ mol–1
4.0
0.2 0.2
1 10 100 1,000 1 10 100 1,000 2.20 2.25 2.30 2.40
t (s) t (s) 1,000 T –1 (K–1)

Fig. 6 | Dynamic covalent behaviour of PDK networks. a–c, Temperature-dependent stress relaxation for PDK-6(TREN) (a) and PDK-6(TREN:ODA)
(b) polymers shows Arrhenius-type behaviour with activation energies (c) of 49 and 60 kJ mol–1, respectively.

network polymers with both aliphatic and aromatic amine mono- exchange revealed remarkably low, catalyst-free activation ener-
mers is unusual, and a direct consequence of diketoenamine bond- gies for associative bond exchange: 29(±0.9) kJ mol–1 for aliphatic
exchange energetics38. Kinetic analysis of the diketoenamine bond amine exchange and 62(±2) kJ mol–1 for aromatic amine (aniline)

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Articles
exchange (Supplementary Figs.  13–15). We found that PDK net-
work polymers containing both aliphatic and aromatic amines yield
materials that reconfigure and relax with a temperature dependence
that follows Arrhenius behaviour, consistent with PDKs being vitri-
mers27. The temperature-dependent stress-relaxation behaviour for
PDK-6(TREN) and PDK-6(TREN:ODA) shows activation ener-
gies of, respectively, 49 kJ mol–1 and 60 kJ mol–1 for solid-state bond
exchange (Fig. 6).
Discussion
The closed-loop polymer life cycles enabled by PDKs contrast with
those for conventional polymers, which are synthesized using irre-
versible bond-forming reactions that make it difficult and costly
to recover the original monomers in high purity. Furthermore,
while dynamic covalent polymers have been designed, in principle,
around the ability to exchange bonds27, examples of energy-efficient
depolymerization and chemical separations to obtain immediately
reusable monomers are exceedingly rare. Indeed, PDKs may be
privileged in this regard. Specifically, our work provides an impor-
tant counterpoint to the observed stability of poly(ketoenamine)s
to acid-catalysed hydrolysis28,39–41, showcasing the importance of
the second keto functionality in re-directing the foundational
behaviour of our materials toward more facile recycling, separa-
tion, re-manufacturing and re-use in a fully closed-loop fashion
(Supplementary Fig. 1). As the global binge on plastics accelerates42,
PDKs stand out among a growing class of smarter plastics designed
for chemical circularity.
Data availability
The authors declare that the data supporting the findings of this study
are available within the paper and its Supplementary Information,
and also from the authors upon request. Crystallographic data for
compounds  3, 5 and TK-6 are available free of charge from the
Cambridge Crystallographic Date Centre (www.ccdc.cam.ac.uk)
under reference nos. 1891131, 1891132 and 189113, respectively.
Received: 17 May 2018; Accepted: 1 March 2019;
Published: xx xx xxxx
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Nature ChemIstry | www.nature.com/naturechemistry
NaTuRe CHemisTRy
Acknowledgements
The technical scope of this work was supported by the Laboratory Directed Research
and Development Program of Lawrence Berkeley National Laboratory under US
Department of Energy contract no. DE-AC02–05CH11231. K.E.L. was supported by
the US Department of Energy, Office of Science, Office of Workforce Development
for Teachers and Scientists (WDTS) under the Science Undergraduate Laboratory
Internship (SULI) programme. Portions of this work, including organic and polymer
synthesis and characterization, were carried out as a User Project at the Molecular
Foundry, which is supported by the Office of Science, Office of Basic Energy Sciences,
of the US Department of Energy under contract no. DE-AC02-05CH11231.
Author contributions
B.A.H. and P.R.C. designed and planned the project. P.R.C. synthesized and characterized
all PDK materials and their recyclability. A.M.S. synthesized small molecules and carried
out experiments to measure the activation energies for amine exchange. K.E.L. carried
out experiments to characterize the extent of network formation by ball-milling. B.A.H.
and P.R.C. wrote the manuscript, with contributions from all co-authors.
Nature ChemIstry | www.nature.com/naturechemistry
The Nature trademark is a registered trademark of Springer Nature Limited.
Articles
Competing interests
B.A.H. and P.R.C. are inventors on US provisional patent application 62/587,148
submitted by Lawrence Berkeley National Laboratory that covers poly(diketoenamine)s,
as well as aspects of their use and recovery.
Additional information
Supplementary information is available for this paper at https://doi.org/10.1038/
s41557-019-0249-2.
Reprints and permissions information is available at www.nature.com/reprints.
Correspondence and requests for materials should be addressed to B.A.H.
Publisher’s note: Springer Nature remains neutral with regard to jurisdictional claims in
published maps and institutional affiliations.
This is a US government work and not under copyright protection in the US; foreign
copyright protection may apply, 2019
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