Review

pubs.acs.org/CR

Catalysis as an Enabling Science for Sustainable Polymers

Xiangyi Zhang,† Mareva Fevre,‡ Gavin O. Jones,‡ and Robert M. Waymouth*,†
†
Department of Chemistry, Stanford University, Stanford, California 94305-5080, United States
‡
IBM Research−Almaden, 650 Harry Road, San Jose, California 95120, United States

ABSTRACT: The replacement of current petroleum-based plastics with sustainable

alternatives is a crucial but formidable challenge for the modern society. Catalysis
presents an enabling tool to facilitate the development of sustainable polymers. This
review provides a system-level analysis of sustainable polymers and outlines key criteria
with respect to the feedstocks the polymers are derived from, the manner in which the
polymers are generated, and the end-of-use options. Specifically, we define sustainable
polymers as a class of materials that are derived from renewable feedstocks and exhibit
closed-loop life cycles. Among potential candidates, aliphatic polyesters and
polycarbonates are promising materials due to their renewable resources and excellent
biodegradability. The development of renewable monomers, the versatile synthetic routes
to convert these monomers to polyesters and polycarbonate, and the different end-of-use
options for these polymers are critically reviewed, with a focus on recent advances in
catalytic transformations that lower the technological barriers for developing more sustainable replacements for petroleum-based
plastics.

CONTENTS 4.3. Biological Recycling 868

4.3.1. Anaerobic Bacteria 869
1. Introduction 839 4.3.2. Aerobic Bacteria 869
1.1. Definition 840 4.3.3. Cells Extracts 870
1.2. Scope of Review 840 5. Conclusions and Outlook 871
1.3. General Principles 841 Author Information 872
1.3.1. Feedstocks, Monomers, and Polymers 841 Corresponding Author 872
1.3.2. End-of-Use Options 841 ORCID 872
1.4. Challenges 841 Notes 872
1.5. Metrics Used to Evaluate Sustainability 842 Biographies 872
1.5.1. Green Design Metrics (GDM) 842 Acknowledgments 872
1.5.2. Life Cycle Assessment (LCA) 842 References 872
1.5.3. Relation Between the Two Metrics 843 Note Added after ASAP Publication 885
1.6. Commercial Examples 843
1.7. Opportunities and Challenges for the Devel-
opment of Sustainable Polyesters and
Polycarbonates 843 1. INTRODUCTION
2. Renewable Monomers 844 The development of petroleum-based plastics is one of the
2.1. Diacids, Hydroxyl Acids 845 crowning achievements of the 20th Century. Eighty years of
2.2. Polyols 847 commercial development have led to a family of materials
2.3. Cyclic Esters 847 whose low cost, processing versatility, and range of mechanical
2.4. Carbonates 848 properties have made them the materials of everyday life, from
2.5. Epoxides 850 clothing, cutlery, automobiles to healthcare, electronics, and the
3. Synthesis of Polyesters and Polycarbonates 850 materials of our modern infrastructure. From 1.65 million tons
3.1. Step-Growth Polymerization (SGP) 851 in 1950 to 311 million tons in 2014 worldwide,1 plastics usage
3.2. Chain-Growth Polymerization 853 is expanding and expected to grow at a steady pace of 3−4%
3.2.1. Ring-Opening Polymerization (ROP) 853 per year.2 The relatively low costs of energy, abundance of
3.2.2. Ring-Opening Copolymerization (ROCP) 859 waste disposal sites, and an economic and cultural focus on the
3.3. Microbial Fermentation 861 convenience of disposable items of commerce have fostered an
4. End-of-Use Options 862
4.1. Mechanical Recycling 863
Special Issue: Sustainable Chemistry
4.2. Chemical Recycling 863
4.2.1. Solvolysis 863 Received: June 8, 2017
4.2.2. Thermal Recycling (Pyrolysis) 866 Published: October 19, 2017

© 2017 American Chemical Society 839 DOI: 10.1021/acs.chemrev.7b00329

Chem. Rev. 2018, 118, 839−885
Chemical Reviews
industrial ecology based on a linear model of resource
utilization (Resource-Monomer-Polymer-Product-Waste, Fig-
ure 1, black lines).3 Petrochemical feedstocks that provide the
Figure 1. Different models of industrial ecology for plastics industry
and innovation leverage points (ILP) for the development of
sustainable polymers with closed-loop life cycles.
source of modern plastics are typically byproducts of oil and gas
refining; extraordinarily sophisticated and efficient catalytic
technologies have been developed for converting these low cost
feedstocks to plastics on a vast scale. Nevertheless, once
introduced into the marketplace, the majority of these materials
end up in the environment as waste. While the economic
benefits of this industrial model of resource utilization have
been significant in the past century, the environmental
consequences are sobering. More than 300 million metric
tons of plastic waste is generated every year, with 4.8 to 12.7
million metric tons entering the ocean, which has negatively
impacted the marine environment.4 The vast scale of
manufacturing and the environmental consequences associated
with disposal have illuminated the limits to which the planet
can cope with our current “take, make and dispose” model of
resources utilization. Furthermore, fossilized carbon remains an
abundant but finite natural resource; in the long term, the laws
of supply and demand will lead to increasing costs and volatility
for fossilized natural resources that provide the fuels and the
attendant feedstocks that form the basis of the current plastics
economy. These considerations have stimulated efforts to
develop alternative classes of materials that are both more
sustainable and not so closely tied to petrochemical resources.
1.1. Definition
In 1987, the United Nations introduced the concept of
sustainable development as “addressing the needs of the
present without compromising the ability of the future
generations to meet their needs”.5 The concept of sustainable
development6 has grown out of an appreciation that our planet
is small, its natural resources finite. The scale of human
technological activity has had a significant impact on economic
development worldwide, but the attendant environmental
impacts are becoming increasingly apparent. These consid-
erations have spawned increased attention to sustainability
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science, an effort to provide a coherent system-level analysis to
define sustainability and to identify the appropriate goals,
indices, and metrics to assess whether a particular activity is
sustainable.7−10 In this context, the definition of sustainable
polymers should be considered at a system level, encompassing
considerations such as the resources from which they are made,
the manner in which they are produced, stored, distributed,
utilized, and either recovered or otherwise released into the
environment. Concepts from industrial ecology3 and circular
economy11 can provide a useful framework for the definition of
a sustainable polymer, that is a class of materials that exhibit
closed-loop life cycles, such that they are components of a
system where “resources” and “waste” are undefined as the
waste from one process provides the resources for the next, in
analogy to highly evolved natural ecosystems (type III
ecology).3 Of course, any such system will require energy as
an input but should be optimized to keep energy inputs at a
minimum and optimally maximize the use of renewable energy.
It should be appreciated that the definition of a sustainable
polymer as members of a class of materials that exhibit closed-
loop life cycles (Figure 1, dotted lines) is not universally
accepted; few existing plastics today would meet this definition.
We have adopted this definition as an aspirational goal in the
spirit of sustainable development.
1.2. Scope of Review
This review is framed in the context of the opportunities and
challenges for the development of plastic materials that would
exhibit closed-loop life cycles as part of a future industrial
ecology where all resources, products, and “waste” form a
regenerable system sustained only by the input of energy.3,7,9
Several excellent reviews on sustainable polymers have been
published in the past few years.12−23 The majority focus on the
use of renewable resources for feedstocks and monomers,
particularly biomass-derived monomers and processes for the
generation of polymers derived from these mono-
mers.12,13,15,16,24−27 Several other reviews discuss the topic
from the end-of-use perspective, covering different families of
recyclable and biodegradable polymers.20,23,28−31 Herein, we
attempt a system-level analysis, where all aspects of the plastics
life-cycle are considered, which include the natural resources
that provide the feedstocks and monomers, as well as the means
of converting these to polymer products, their life cycles, and
potential for these to exhibit closed-loop life cycles. We have
framed opportunities and challenges in terms of “innovation
leverage points” (ILP, Figure 1)32 where the development of
new science and catalytic technologies might lower the
technological barriers to achieving closed-loop life cycles. To
develop a more cyclical model of resource utilization (Figure 1,
dotted lines), new economic and technological innovations are
needed at all steps of the plastics life cycle. For reasons we
describe in more detail below, we focus the review on two
classes of materials, polyesters and polycarbonates, as
representative materials to illustrate key principles for the
generation of sustainable polymers.
Since catalysis represents an essential facet of sustainability
and continues to drive the innovation in sustainable polymers,
we highlight recent advances in the catalytic transformations of
renewable feedstocks to monomers, monomers to polyesters
and polycarbonates, as well as the chemical and biological
recycling/degradation of these polymers. Different synthetic
routes and catalytic systems will be compared and discussed in
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the context of sustainability (i.e., atom efficiency, the use of
green catalytic systems, and mild polymerization conditions).
1.3. General Principles
1.3.1. Feedstocks, Monomers, and Polymers. One
guiding principle to sustainable development is that the rate
of natural resource consumption cannot exceed its rate of
regeneration if the system is to be sustainable in the long
term.3,7,9 This has encouraged a focus on renewable resources,
including those derived from regenerable bio-
mass,12,13,15,16,24−27 as sources of feedstocks for the next
generation of plastics (Figure 1). For bioderived feedstocks, the
rate and time scale of CO2 sequestration can, in principle, be in
balance with the use and release, resulting in an overall
“neutral” carbon footprint. This is in contrast to the carbon
cycle for petroleum feedstocks, in which the rate and time scale
of CO2 sequestration (millions of years) is much slower than
the use and release (1−10 year time frame).2 Natural polymers
such as cellulose, hemicellulose, and lignin are among the most
abundant sources of renewably sourced carbon.14,33,34 The
physical properties of these raw materials can be enhanced by
physical or chemical modifications, making them useful
materials for a variety of applications in our daily life.35−37
Small molecules including vegetable oils, terpenes, and CO2 are
also useful renewable raw materials.15,16,33 These raw materials
can be further converted to value-added chemicals in integrated
biorefineries, in analogy to that currently practiced in petroleum
refineries. Biorefinery products such as ethanol, lactic acid, and
glycerol are important building blocks for sustainable
polymers. 14 Among the different biomass sources for
biorefinery, the lignocellulosic feedstock biorefinery38 is
attractive because of the availability of feedstock (e.g., agro-
food wastes, or even paper wastes) at competitive prices and
because the use of these feedstocks does not compete with the
food supply. As the chemical composition of renewable
resources are quite different from those derived from
petroleum-based resources, new scientific and technological
innovations are needed for the development of efficient
catalytic strategies for converting these resources into platform
chemicals, monomers, polymers, and products that can be
produced economically on a scale sufficient for commodity
materials (Figure 1, ILP1−ILP4). This remains a formidable
challenge, as discussed in sections 2 and 3.
1.3.2. End-of-Use Options. New innovations are also
needed to develop strategies for the recapture and reutilization
of plastic materials at the end of their useful life. In the United
States in 2014, over 75% of plastics wastes were landfilled,39
with the remainder being either recycled (primarily HDPE and
PET) or incinerated.39,40 However, the amount of landfill space
available for discarded plastic wastes is finite. Incineration of
recovered plastic provides a potential source of energy39 but
generates CO2; moreover, rigorous purification and process
controls are needed to ensure that the hazardous substances are
not released into the atmosphere.41 Petroleum-based thermo-
plastics such as PET and HDPE are currently recycled on a
large scale through a sorting, melting, reprocessing process into
useful products.42 The current recycling system requires a
complicated sorting step which limits the types and amounts of
plastic being recycled. Thus, while many petrochemically based
polymers are recyclable, the current rates of plastics recycling
are exceedingly low (<10%) and, on a volume basis, are not
keeping pace with the increased volumes of production.39,42
This is a systems-level challenge, as the economic incentives
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and infrastructure for recovery and reuse are not nearly as well
developed as those for production of plastics. As described in
section 4, new innovations are needed to provide more
technology options for plastics recycling. New strategies are
needed for the selective depolymerization of plastics either to
their constituent monomers or other useful intermediates that
could be used as resources for other chemical processes (Figure
1, ILP 5−6). This strategy preserves part of the chemical
complexity and energy43 that was invested to create the plastics.
In order for this process to be energetically efficient, plastic
materials should optimally be derived from polymerization
reactions that are not strongly exergonic to ensure that, once
generated, the materials can be catalytically depolymerized or
chemically recycled with minimal energy inputs (ΔGp° ∼ 0,
such that ΔGrxn = ΔGp° + RT ln Q can be optimized for
polymerization or depolymerization). This latter criterion
motivates our focus on polyesters and polycarbonates.
Additionally, an effective catalytic system is needed to favor
the kinetics and the selectivity of the depolymerization reaction
to the desired feedstock.
Even under the most highly optimized circular materials
economies, some fraction of the products will eventually end up
in the environment. To mitigate the environmental impact of
plastics that end up in the environment, these plastics should be
biodegradable. This requires engineering of either the polymer
composition/formulation or its degradation pathway so that it
can be broken down by microorganisms to primarily CO2 and
H2O in a reasonable time frame.20 CO2 and H2O will re-enter
the life cycle through photosynthesis to grow plants that serve
as the biofeedstock of sustainable polymers. Although there is
no direct correlation between a plastic’s ability to biodegrade
and the resource from which it is derived, many biomass-
derived polymers have oxygen-rich backbones and are thus
more readily degraded than the all-carbon backbones of most
petroleum-based polymers. Such bioderived and biodegradable
polymers are therefore emerging as attractive alternatives to
conventional petroleum-based polymers. However, while
biodegradable plastics can mitigate some of the environmental
consequences of plastics that find their way into the
environment, it is only one of the several end-of-life strategies
to minimize the environmental impact of plastics. It is arguably
not the optimal end-of-life option in that the energy invested to
create these materials is wasted and provides benefit only to the
microbes. The end-of-life challenges and opportunities are
described in section 4.
1.4. Challenges
Development of sustainable polymers that meet all the criteria
described above is a formidable challenge that will require the
concerted effort of academic and industrial scientists and
engineers, industrial ecologists, economists, social scientists,
and policy makers. One of the most significant challenges is
that the plastics of modern society are quite remarkable
materials; more sustainable alternatives will have to meet a high
bar in terms of the cost and performance in order to be
economically competitive. Moreover, the economic ecosystem
which has led to our current plastics economy is well-
entrenched and economically successful. While considerable
research has focused on replacing petroleum raw materials with
renewable sources and developing biodegradable or recyclable
polymers that minimize waste disposal,16 ultimately the point of
maximum leverage44 is the socioeconomic system that has led
to our current model of resource utilization. The evolution of a
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socioeconomic system that provides incentives both for
environmentally sustainable as well as economically sustainable
materials will require systems-level changes at all levels of
society. Such a system would need to account for the
socioeconomic costs associated with the plastics economy, for
example the proliferation of microplastics in the environment,45
and degradation of natural capital (land, fish stocks, etc.).46
More specific challenges include the relatively high cost of
certain biofeedstocks and biorefinery technologies compared to
those that contribute to the current petroleum-based plastics
economy. Many commercially viable biorefinery processes such
as the fermentation of carbohydrates to carboxylic acids and
alcohols are energy-intensive.14 Additionally, the relatively high
energy and environmental cost associated with the production,
separation, and purification of biomass (e.g., agriculture) can
limit the overall sustainability of the polymer derived from the
biomass. Reductions in cost will require improvements of
processing technologies, developments of production processes
that tolerate lower-purity feedstocks, and the use of waste
agricultural materials (such as corn stover) as feedstocks.
Second, sustainable polymers must exhibit comparable or
better properties (mechanical and thermal properties, process-
ability, barrier properties, durability, etc.) than the conventional
fossil fuel derived plastics in order for them to be competitive in
the market. Efforts toward this goal include: (1) synthesizing
sustainable counterparts of known petroleum-based plastics
from renewable sources to replicate their performances (e.g.,
polyethylene prepared from bioethylene), (2) developing
chemically distinct materials from biofeedstocks with novel
properties (e.g., self-healing, thermo-reversible) that are not
currently available with petroleum-based plastics, (3) chemical
and physical modification of natural polymers (e.g., cellulose
and chitosan grafting).
Third, quantitative metrics of environmental sustainabil-
ity7−10 are not nearly as well advanced or universally accepted
as metrics of economic sustainability. Life-cycle assessment has
been used to assess the environmental impacts resulting from
the production, use, and disposal of a polymer product (see
section 1.5.2), but the results are variable across studies with
quantification being strongly tied to modeling assumptions and
feedstock choice.47−49 Materials in the early stage of develop-
ment, particularly in academic laboratories, are not routinely
examined by those metrics; better communication between
scientists and engineers in these traditionally separate fields
represents an opportunity for more sustainable development.
Another challenge lies in the societal factor of sustainability.
Support from public and government including favorable policy
and legislation is the key stimulator for technological
innovations on sustainable polymers and for businesses and
customers to transition toward more sustainable products.
Regardless of which new polymers are selected as alternative
materials, a significant challenge is to encourage the evolution
of a socioeconomic system that enables a high rate of end-of-life
capture and valorization. To succeed, it is vital for chemists and
engineers to work with companies and representatives from the
public sector to develop viable infrastructures and material
flows. The New Plastics Economy Initiative, led by the Ellen
MacArthur Foundation, provides one potential vision of such a
system.50 Taken together, these technical, economical, and
societal challenges explain, in part, why the development of
sustainable polymers is such as a formidable and complex
challenge.
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1.5. Metrics Used to Evaluate Sustainability
One significant challenge in the field of sustainable polymers is
the lack of a universally recognized standard system or set of
metrics for evaluating and quantifying the sustainability of a
product or process,7 partially because comprehensive and
quantitative models incorporating all aspects of sustainability
are at an evolutionary stage of development and are not
universally accepted or well-established.7−9 Two concepts that
have informed sustainable polymer design and evaluation are
based on metrics such as “Green Design Principles” and “Life
Cycle Assessment”.51
1.5.1. Green Design Metrics (GDM). Green Design
metrics embody an approach to assessing the environmental
consequences of a product and its associated processes at the
design stage. It is based on green chemistry principles that aim
to reduce the use and generation of hazardous substances in the
life cycle of chemical products. The hazards assessed include,
but are not limited to, toxicity, physical hazards (e.g.,
explosions, fires, etc.), impact on global climate, and resource
depletion.51 The commonly used green design metrics are
extracted from the well-recognized green chemistry principles
such as the “12 Principles of Green Chemistry”, the “12
Additional Principles of Green Chemistry,” and the “12
Principles of Green Engineering”. Specific contents for each
principle can be found in the literature.43,52,53 Here, we
condense these principles into themes related to the different
stage of a product’s life cycle: (1) use of renewable and local
sources, (2) atom economy, (3) less hazardous reagents and
synthesis, (4) less waste generation, (5) maximum energy
efficiency, (6) products designed for recycling and degradation,
and (7) cost efficiency.
GDM can be used to guide the design of new materials and
to provide detailed comparison of different aspect of
sustainability between materials and processes. One essential
aspect of GDM is that it evaluates the materials at the most
fundamental level (i.e., the level of chemical structures and
reactions), which determines the intrinsic properties and
environmental outcome of a product. These inherent properties
and associated environmental benefits can propagate through-
out the various life cycle stages.51 It is for this reason that
implementation of green chemistry assessment can offer
environmental benefits that propagate throughout the life
cycle. Another essential aspect is that GDM are often used at
the design stage to minimize potential problems that could
occur during product development. Therefore, GDM can be
adopted as a preventive metric to identify leverage points for
new chemistries or processes at the design stage of sustainable
polymers.
1.5.2. Life Cycle Assessment (LCA). Life cycle assessment
is a tool to characterize the range and scope of environmental
impacts resulting from production, use, and disposal of a
product or process. The procedure of LCA is specified by ISO
14040−14044 series54 as three main phases: life cycle inventory
analysis, life cycle impact assessment, and life cycle
interpretation. The inventory analysis involves compilation
and quantification of the inputs and outputs for a given
product. The data for most petroleum-based polymers and
some biopolymers are available from databases such as
Ecoinvent.55 The impact assessment is a process to assess the
significance and magnitude of the environmental impact of a
product. The most commonly used standard for assessment is
the “Tool for the Reduction and Assessment of Chemical and
environmental Impacts (TRACI)”56 that assesses the impacts
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by ten categories: acidification, carcinogenic human health
hazards, ecotoxicity, eutrophication, global warming potential,
noncarcinogenic human health hazards, ozone depletion,
respiratory effects, smog, and nonrenewable energy use. The
data for these impacts are gathered through individual studies,
and some categories are not available for certain polymers,
which makes the comprehensive comparison between polymers
difficult. The findings of life cycle inventory analysis and impact
assessment are then combined to reach a conclusion used to
inform environmental decisions.
LCA provides a standardized methodology to compare
different product choices and identifies unintended environ-
mental trade-offs between impact categories.54 Unlike the green
design metrics which are used at the design stage to reduce
potential problems through avoidance approaches, LCA is often
implemented at a later stage in the product development to
evaluate the actual environmental outcomes associated with
different products and processes. That means, LCA results are
not available before the production of a product, much less so
during the design of a product as a result of inadequate data on
environmental impacts. Although LCA ideally should take into
account all stages of the product life cycle (i.e., cradle-to-
cradle), the scope of LCA is often limited to cradle-to-gate due
to the lack of a complete understanding and inadequate data on
the environmental fate and impact of a polymer. Because of the
longevity of hydrocarbon-based plastics in the environment and
the accumulation effects such as degradation of land and
proliferation of microplastics, the long-term impacts of plastic
wastes are difficult to assess and therefore fall outside of the
cradle-to-gate analysis. In much of the literature, LCA of
different products and processes often focus only on certain
environmental impacts, such as emission of greenhouse gas and
nonrenewable-energy use.57,58
1.5.3. Relation Between the Two Metrics. Since the two
metrics focus on different aspects of sustainability, the
evaluation based on these metrics can give different results.
For example, Landis quantified the adherence to “Green Design
Principles” and the environmental impacts (assessed by LCA)
of 12 commodity polymers, seven derived from petroleum, four
derived from renewable sources, and one derived from both.59
In this analysis, biopolymers such as polylactide (PLA) and
polyhydroxyalkanoate (PHA) were ranked the highest based on
green design metrics but in the middle of the LCA rankings
whereas petroleum polymers such as PE and PP were ranked
the highest in the LCA rankings but in the middle of green
design rankings. The high ranking of PLA and PHA by the
green design metrics is mostly due to the relative weight placed
on the use of renewable materials and their biodegradability/
recycling potential, but their production involves agriculture,
fermentation, and multiple chemical processing steps that lead
to a low atom economy and an increasing potential for
greenhouse gas emission and environmental impacts such as
eutrophication, human health impacts, and eco-toxicity. There-
fore, one important message from this study is that switching
from petroleum polymers to those derived from renewable
resources does not necessarily reduce environmental impacts.
Nevertheless, there was a qualitatively positive correlation
between adherence to “Green Design Principles” and a
reduction of the environmental impacts within each category
(petroleum- or biopolymer). While laudable, this study utilized
ranking criteria for the green design metrics that are not
necessarily widely accepted. In addition, the life cycle analysis
was limited in scope of “cradle-to-gate”, due to the
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aforementioned challenge of incomplete data available on the
environmental fate and costs of discarded materials. The use
phase and disposal phase are too complicated to be included
because the same polymer can be used in multiple products and
the disposal scenarios of biopolymers are yet to be studied. In
addition, the environmental and human health impacts of the
byproducts of PLA or PHA biodegradation are not fully
understood. In light of these considerations, the reported
rankings should be viewed with some caution; nevertheless, this
study illustrates some of the challenges in assessing the
environmental impacts of plastics and underscores the
importance and rich opportunities for developing more
quantitative analyses on the environmental costs and impacts
of plastics in the environment.
1.6. Commercial Examples
In the past decade, a number of synthetic bioderived plastics
have been commercialized. One important example is PLA
produced from starch-rich crops such as corn, for example that
developed by Natureworks LLC under the brand name Ingeo.60
Its physical properties allow it to replace petroleum-based
plastics in some types of packaging and fiber applications.16,61
Other commercial examples are poly(butylene succinate) and
poly(butylene succinate adipate) (Bionolle),62 poly(ethylene-
2,5-furandicarboxylate) (Avantium’s YXY technology),63 bio-
polyethylene (I’m green by Braskem),64 polyhydroxyalkanoate
(Mirel),65 polyamide 11 (Rilsan),66 and polyamide 410
(EcoPaXX).67 Some commercial polymers are partially renew-
able, such as poly(trimethylene terephthalate) (Sorona),68 a
polymer alloy of starch and modified poly(vinyl alcohol)
(Mater-Bi),69 and the first-generation PET PlantBottle.70 The
use of CO 2 as a renewable resource for sustainable
polycarbonates has stimulated several commercialized develop-
ments like QPAC71 and Converge.72 Due to the relatively high
costs and limited material properties, renewable plastics
currently make up only a small share of the global plastics
market. For example, in 2014, only 1.7 megatons of more than
300 megatons of polymers produced globally were bioderived,
of which the three main products were PLA, biopolyethylene,
and bioPET.17 As more advanced and efficient agriculture
processes and synthetic approaches become available, biofeed-
stocks and their conversion to plastic materials should become
more cost-efficient, and we would thus anticipate a larger
amount of and more versatile renewable plastics coming onto
the market.
However, it should be noted that plastics derived from
renewable feedstocks are not necessarily sustainable. Although
biobased polymers save nonrenewable resources and generally
emit less greenhouse gases for their production, studies have
shown that they may exert higher environmental impacts in the
categories of eutrophication and stratospheric ozone deple-
tion.73 Therefore, a thorough analysis of all environmental
impacts of biobased materials in comparison with their fossil
fuel-based counterparts is required for strategic decision
making.
1.7. Opportunities and Challenges for the Development of
Sustainable Polyesters and Polycarbonates
While the sustainability of a polymer should be considered on a
systems level that encapsulate a variety of factors in its
feedstock, synthesis, and end-of-use options, two important
criteria are the use of renewable feedstock and the degradability
or recyclability of the polymer.16 The former reduces the
dependence of polymer production on fossilized carbon sources
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Figure 2. Classification of polymers based on feedstock renewability and polymer degradability (adapted from renewability/polymer degradability
matrix defined by Miller74). Traditional polymers are derived from fossil fuels and are nondegradable in nature (lower left quadrant), whereas
sustainable polymers are sourced from renewables and can readily degrade in the environment.
and enables an overall “neutral” carbon footprint on the
environment,2 and the latter is the key to build a circular
economy that increases resource utilization and reduces waste
generation. As summarized in Figure 2, synthetic plastics on the
market can be classified into four categories according to their
feedstock renewability and polymer degradability.74 Among the
families of polymers that can be both renewable and degradable
(upper right quadrant), polyesters and polycarbonates have
attracted the most attention, with a great many of them
successfully used as substitutes for plastics of petroleum origin.
They have met several key principles outlined for a sustainable
polymer (section 1.3), which enables a potentially cyclic model
of resource utilization. First, the monomers of many polyesters
and polycarbonates can be derived from biomass or waste gases
via biological or chemical transformations. This allows a faster
rate of resource regeneration than resource consumption.
Second, the conversion of these renewable monomers to
polyesters and polycarbonates can be achieved via a variety of
polymerization methods, which enables diverse backbone
structures and side-chain functionalities that in turn give rise
to versatile physical properties of these polymers. Third,
because of the ester or carbonate linkages in the main chain and
the relatively flexible backbones, aliphatic polyesters and
polycarbonates can be enzymatically degraded by naturally
occurring microorganisms such as bacteria, fungi, and algae to
primarily CO2 and H2O,75,76 which can be converted back to
biomass through photosynthesis to complete a cradle-to-cradle
life cycle of these materials. Alternatively, these are attractive
candidates for feedstock recycling as the polymerization
thermodynamics are not as exergonic as those of conventional
commodity plastics (PE, PS, and PVC).
In the following sections, the catalytic transformations of
feedstocks to monomers (ILP2), monomers to polymers
(ILP3), and end-of-use recycling (ILP5, ILP6) or biodegrada-
tion of polyesters and polycarbonates are discussed in detail.
The challenges and opportunities in these steps are highlighted.
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2. RENEWABLE MONOMERS
Due to the oxygen-rich character of polyesters and poly-
carbonates, they can be readily sourced from a wide variety of
renewable feedstocks. Carbohydrates are the most exploited
and abundant biofeedstock for producing building blocks for
these polymers.77 Currently, most of the renewable monomers
are produced from sugar- or starch-rich crops such as corn and
sugar cane. Transition to nonfood sources such as lignocellu-
losic biomass is an important direction to lower the production
costs78−80 and to avoid resource competition with the food
supply. The two major components of lignocellulose, cellulose
and hemicellulose, provide an almost unlimited source of C5
and C6 sugars, provided efficient strategies can be devised to
recover and purify these feedstocks effectively. Lignin is a
complex aromatic polymer that can be broken down to various
phenolic monomers. Another common renewable resource is
plant oil, which is converted to fatty acids and glycerol for
biodiesel and oleochemical production.16,25,81 Oilseed crops
such as soybean, rapeseed, and oil palm are the major supply of
oils at present, but algae has turned up as a cheaper alternative
due to its nonfood nature, fast production and recycle rate, and
low use of production inputs.82 In addition to these two major
classes of biomass, terpenes and CO2 are also useful feedstocks
for polyesters and polycarbonates.16,83
The conversion of renewable feedstocks to monomers
focuses on two directions: to replace the existing petroleum-
derived monomers with their renewable counterparts and to
develop new bioderived monomers and polymers with unique
structures and properties that current commodity plastics do
not have. Identifying the best pathway to convert the
aforementioned feedstock to a given monomer is one of the
first challenges for the development of sustainable polymers.
The conversion typically involves a mechanical/physical
pretreatment (milling, extraction, and steam reforming),
followed by multiple biological, chemical, or thermochemical
processes.77 This provides a range of platform chemicals, which
can be directly employed as monomers, or serve as precursors
for monomer synthesis. The role of catalysis in these
conversions is critical, and many research efforts are focusing
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Figure 3. Structures of diacids, triacids, and hydroxyl acids derived from renewable sources.
Scheme 1. Chemical Conversions of Unsaturated Fatty Acids to α,ω-Diacids, α,ω-Diols, or ω-Hydroxyl Acids
on developing green catalytic processes with high efficiency and
low cost.84−86 This section intends to give a concise overview
on the different classes of renewable monomers that have been
or can potentially be utilized for the synthesis of sustainable
polyesters and polycarbonates, with a focus on chemical
catalysis involved in their productions. More comprehensive
discussions on this topic can be found in several excellent
review articles.12,33,87−89
2.1. Diacids, Hydroxyl Acids
Diacids and hydroxyl acids, especially those derived from
carbohydrates, are arguably the most important chemicals
derived from biomass (Figure 3). They are not only key
monomers for various commodity polyesters and polycarbon-
ates but also serve as a platform for a multitude of high-value-
added products by means of chemical and biological trans-
formations.77 In fact, 10 out of the 15 target biobased building
blocks in the 2004 DOE “Top 10” report are carboxylic acids.90
1,4-Diacids, including succinic, fumaric, and itaconic acids,
are some of the most successful platform chemicals obtained
from carbohydrate biorefinery.91 The generation of these
diacids from different natural or engineered microorganisms
has been extensively studied and reviewed.88,92−95 Succinic acid
is used in the production of biobased PBS; it is also a versatile
precursor for monomers such as 1,4-butanediol (BDO), γ-
butyrolactone (γ-BL), maleic anhydride, and maleic acid.91
Fumaric acid and itaconic acid are useful monomers for the
synthesis of unsaturated polyesters and can be converted to
multifunctional monomers such as malic acid and aspartic
acid.94 Adipic acid, a monomer used for the production of
nylon, polyurethane, and polyesters, is one of the most
important diacids in industry and ∼2.5 million tons are
produced annually from petrochemicals.96 Several renewable
routes to adipic acid have been reported, including a microbial
synthesis from glucose or fatty acid using engineered
microorganisms, and chemical transformations from bioderived
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succinic acid, muconic acid, or glucaric acid.97 However, none
of these routes are economically feasible yet.
Fatty acids obtained from transesterification of plant oils have
been a long-standing biofeedstock for polymer production.25,98
Unsaturated fatty acids containing 1−3 double bonds are
particularly attractive substrates since the internal alkene
functionality provides a versatile handle for chemical
modifications (Scheme 1). A variety of long-chain α,ω-diacids
can be produced through oxidative cleavage of the alkene group
of fatty acids.33 For example, azelaic (C9) and sebacic acid (C10)
are obtained by oxidation of oleic acid and castor oil,
respectively. Sebacic acid has been used in the production of
bionylon and polyesters that feature excellent flexibility and
chemical resistance. One disadvantage of this transformation is
that only part (about half) of the fatty acid chain is utilized in
the α,ω-difunctional product and the rest is lost as a coupling
product of less value. Recently, Mecking et al. developed an
elegant approach to incorporate the entire length of the fatty
acid based on a catalytic isomerization of the internal alkene to
the chain end and subsequent ω-functionalization of the
terminal double bond.99 In one example, they showed that
isomerizing alkoxycarbonylation of methyl oleate catalyzed by a
palladium catalyst bearing phosphorus ligands can convert the
internal double bond deep in the hydrocarbon chain to a
terminal ester group with high yield and selectivity.100 Another
approach based on enzymatic ω-oxidation of the terminal
methyl group of fatty acids has been reported for the synthesis
of α,ω-diacids.101 This requires, however, engineering of yeast
and complex downstream processing to extract the desired
product. These fatty-acid-derived α,ω-difunctional monomers
provide access to a class of long-chain aliphatic polyesters with
unique properties that bridge the gap between semicrystalline
polyolefins and the traditional polycondensates.102
Furan-2,5-dicarboxylic acid (FDCA) is a useful biobased
feedstock for the production of aromatic polyesters.103
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Poly(ethylene furandicarboxylate) (PEF) produced from
FDCA is regarded as a renewable substitute for PET.104
Many routes to FDCA have been developed (Scheme 2).105
Scheme 2. Different Synthetic Routes to FDCA via Either a
HMF or a Furfural Intermediate
The most well-established approach is based on a dehydration
process to convert C6 sugars to hydroxymethylfurfural (HMF),
which is then oxidized to FDCA.106 Typically, the two steps are
performed separately, with the dehydration catalyzed by acids
and the oxidation carried out under basic conditions using a
metal catalyst. The use of lignocelluose as the carbon source
has been demonstrated,107,108 but fructose is the most common
source for HMF production.104 The oxidation step can be
mediated by a variety of heterogeneous Pt, Au, and Pd catalysts
with high yield.109 Recently, mild catalytic systems have been
developed to mitigate the nonproductive degradation of HMF
under strongly basic conditions. For example, a MnCo2O4
supported Ru catalyst was found to afford excellent yield of
FDCA (99%) from base-free air-oxidation of HMF in water.110
One-pot dehydration and oxidation of fructose to FDCA is
challenging due to the oxidation of sugar, but recent catalytic
development has improved the efficiency of this process.111
Vanadyl phosphate catalysts can convert fructose to FDCA in
97% selectivity at 84% conversion;112 Co(acac)3 in a silica sol−
gel system gives 99% selectivity to FDCA from fructose at 72%
conversion.113 Alternatively, FDCA can be produced from
furfural through oxidation and carboxylation.114 Since furfural is
Figure 4. Structures of polyols derived from renewable sources.
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industrially produced from lignocellulose on a scale of 400
kilotons a year, this provides a potentially cheaper route to
FDCA.115 A recent strategy based on CO32−-promoted C−H
carboxylation enables an efficient and sustainable synthesis of
FDCA.116 The reaction of furoic acid with molten Cs2CO3
under a CO2 flow or 8 bar CO2 can give FDCA2− in 70−89%
yield within 12 h. This affords a simple way to transform
inedible biomass and CO2 into a valuable feedstock chemical.
An important low-cost, bioderived triacid is citric acid, which
has been frequently used for the synthesis of biodegradable
thermosetting polyesters for drug delivery, tissue engineering,
and high-tech coating applications.88 Citric acid naturally
occurs in citrus fruits and is industrially produced by sugar
fermentation with a worldwide production of ∼9 million tons
per year. It can use inexpensive carbon sources such as
corncobs and brewery wastes as the feedstock.117
Biomass-derived hydroxy acids provide useful AB-type
monomers for renewable polyesters. Lactic acid is a well-
recognized biobased chemical, currently produced from starch
crops via bacteria fermentation.91 The bioconversion of xylose
to lactate using engineered yeast has also been reported,118
which offers the possibility of using lignocellulose as the
feedstock. Lactic acid is a versatile precursor to a variety of
monomers, including lactide, propylene glycol, propylene oxide,
and acrylic acid.33 A structural isomer of lactic acid, 3-
hydroxypropanoic acid, can also be obtained from glucose
fermentation. It is the monomer for a biodegradable plastic,
poly(3-hydroxypropanoic acid),119 as well as a renewable
precursor for 1,3-propanediol, malonic acid, and acrylic
acid.33 Another important hydroxyl acid is ricinoleic acid
isolated from castor oil. It has been used for the synthesis of
renewable, degradable elastomers through lipase-catalyzed
polycondensation followed by radical cross-linking.27,120 Its
copolymerization with other acids has led to interesting
copolyesters as tunable delivery systems.121,122 Tartaric acid is
a widely available and cheap hydroxyl diacid present in many
fruits and is a principal byproduct of the fermentation process
in the wine industry. It can also be synthesized from maleic acid
through epoxidation and hydrolysis.123 Its hydroxy-protected
derivative, 2,3-O-isopropylidine-tartarate, has been used to
synthesize polyesters with pendant hydroxyl groups.124
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Figure 5. Structures of cyclic esters that can be derived from renewable feedstocks.
2.2. Polyols
Polyols are another important class of building blocks that can
be derived from renewable resources. The most common bio-
derived polyols are summarized in Figure 4. Diols are key
components for linear step-growth polyesters and polycar-
bonates. Ethylene glycol (EG), a component for PET, is
traditionally produced from petroleum-based ethylene, via the
intermediate ethylene oxide. An alternative biobased route is
through the conversion of bioethanol to ethylene then to
ethylene oxide. This process has been used by Coca-Cola in
their PlantBottle packaging since 2009.125 Another promising
route is the hydrogenolysis of sugar-derived polyols (glycerol,
xylitol, and sorbitol) catalyzed by supported transition-metal
catalysts, mostly Ru, Cu, Ni, under basic conditions.126,127 This
process provides a direct and potentially cheaper route to EG
but is complicated by the concurrent generation of other
polyols, like propylene glycol (PG). More selective catalysts are
required in order for this route to become more industrially
relevant. In addition to hydrogenolysis from glycerol,128,129 PG
can be selectively produced from the reduction of lactic acid, via
both chemical130−132 and biological catalysis.133 1,3-Propane-
diol (PDO) can be produced via many different microbial
fermentation processes from glycerol or glucose.134−136 It has
been industrially produced on a large scale (over 50000 tons
annually) by aerobic fermentation of glucose from corn syrup
by a genetically modified strain of E. coli, developed by DuPont
Tate & Lyle BioProducts.137 1,4-Butanediol (BDO), an
important component for commodity plastics such as PBS
and PBT, is mainly prepared from maleic anhydride by Myriant
and Davy Process Technologies. Although maleic anhydride is
currently produced from petrochemicals, its synthesis via
catalytic oxidation of sugar-derived furfuraldehyde by hetero-
geneous metal oxides is known.138−141 A leading technology for
the synthesis of BDO from renewable resources is through
reduction of biobased succinic acid.142 Alternatively, BDO can
be directly prepared from sugar fermentation by engineered E.
coli.143,144 Longer alkanediols such as 1,5-pentanediol (PTDO)
and 1,6-hexanediol (HDO) are not directly available from
biomass but can be produced from hydrogenation of key
platform chemicals of biorefinery. PTDO is synthesized from
glutamic acid;33 HDO can be prepared from HMF or adipic
acid. Long-chain α,ω-diols are obtained in a similar way
through reduction of the corresponding diacids or hydroxyl
acids derived from plant oils (see section 2.1).
Glycerol is a triol commonly used for the synthesis of
branched or cross-linked polyesters and polycarbonates. It is
produced by chemical or enzymatic transesterification of plant
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oils. A variety of acids, bases, and lipases can catalyze the
transesterification with high efficiency. In addition, a non-
catalytic supercritical methanol method has been developed to
solve the two-phase problem of normal methanol/oil
mixtures.145 Because of the growing biodiesel industry, glycerol
is an attractive platform chemical of biorefineries.91 It can not
only be chemically transformed to other monomers but also be
used as alternative substrates to carbohydrates in many
fermentation processes.
Sugar alcohols such as sorbitol, mannitol, and xylitol are
important polyhydroxy platform chemicals. Sorbitol and
mannitol can be generated from catalytic hydrogenation of
glucose and fructose,146 while xylitol is derived from xylose
hydrogenation.147 They can also be produced via a one-pot
chemical transformation of cellulose or hemicellulose combin-
ing acid-catalyzed hydrolysis and metal-catalyzed hydrogena-
tion.146,148 However, this process usually results in a mixture of
polyols, and the product distribution is governed by the balance
between the rates of hydrolysis and hydrogenation, which is
catalyst-dependent.126 Sugar fermentations to produce these
polyols are also feasible although it cannot yet compete with
the chemical reduction economically.149−151 These platform
polyols can be further converted to lower alcohols (EG, PG,
and glycerol) or to a family of C6 diols 1,4:3,6-dianhydrohex-
itols (DAHs) through acid-catalyzed dehydration. Solid acid
catalysts based on phosphated or sulfated metal oxides (e.g.,
phosphated Nb 2 O 5 ) have been developed as greener
alternatives to traditional liquid acids (e.g., H2SO4).146
Recently, catalyst-free conditions such as microwave heating
were also reported.152 Isosorbide can also be synthesized
directly from cellulose via a cascade catalytic process employing
a molten salt hydrate ZnCl2 medium.153 These rigid diols have
proven particularly useful for the synthesis of polyester and
polycarbonates with high glass transition temperatures.88,154
2.3. Cyclic Esters
Most cyclic ester monomers employed for the synthesis of
polyesters are not directly available from biomass but can be
synthesized from platform chemicals in one or multiple steps
(Figure 5). The sustainability of these monomers largely
depends on the efficiency and environmental impact of the
catalytic transformations. Despite the successful demonstration
of many bioderived lactones in the laboratory setting, more
straightforward and selective synthetic routes need to be
developed in the future in order for these processes to become
industrially relevant.
The most successful cyclic ester derived from biomass is
lactide (LA), the monomer for commodity polylactides (PLAs).
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It is prepared from lactic acid through two steps.155 First,
lactide acid is converted to PLA oligomers (molecular weight =
1−5 kDa) through polycondensation. The oligomers are then
selectively depolymerized to LA through an intramolecular
transesterification process. This second step requires the use of
a selective catalyst, typically tin octoate,156 and continuous
removal of lactide (e.g., by distillation) to achieve good yield.
Both steps are time- and energy-intensive owing to their
reliance on high temperatures and vacuum. Recently, a less
energy-intensive one-step conversion of lactic acid to LA was
reported using microporous zeolite catalysts.157 The shape-
selective property of zeolites enables high selectivity for LA
(∼79% at full conversion), devoid of racemization and side-
product formation. Another commonly used six-membered
cyclic ester, glycolide (GA), is prepared in a similar way from
glycolic acid via the low molecular weight poly(glycolide)
intermediate. Glycolic acid is naturally occurring in sugar cane
or fruits but can also be produced biologically from sugars using
a genetically modified microorganism158 or chemically from
cellulose using heteromolybdic acid catalysts.159 However, the
yields of these processes are typically low, which makes them
hard to compete with the current petroleum-based synthesis.
Recently, β-methyl-δ-valerolactone (MVL) has been identified
as a renewable lactone that can be produced from glucose
through either a biological or a semisynthetic pathway.160 The
biosynthetic route is based on the mevalonate pathway of
engineered Escherichia coli strain while in the semisynthetic
route the mevalonate intermediate produced from fermentation
is subjected to acid-catalyzed dehydration and Pd/C catalyzed-
hydrogenation to yield MVL. This lactone has been used in the
synthesis of thermally recyclable thermoplastics 161 and
elastomers.162
Seven-membered lactones including ε-caprolactone (CL)
and its derivatives can also be generated from biomass through
multistep synthesis. CL is industrially produced by Baeyer−
Villiger oxidation of cyclohexanone. While cyclohexanone is
currently produced from petro-derived cyclohexane or phenols,
its synthesis from lignin-derived aromatic ethers has been
demonstrated using a bromide salt modified Pd/C catalyst in
H2O/CH2Cl2 medium.163 Alternatively, CL can be synthesized
by oxidative lactonization of HDO. Buntara et al. reported four
routes to HDO from HMF via repetitive hydrogenations using
a Rh−Re catalyst on a silica support.164 Several substituted CLs
have been synthesized from renewable sources. Racemic CL-1
can be prepared from naturally occurring β-pinene through a
high-yielding (64%) four-step process.165 Disubstituted CL
derivative CL-2 was generated from the natural product
(−)-menthol via Baeyer−Villiger oxidation,166 while CL-3 was
derived from carvone, a natural product found in plant oils, via
hydrogenation followed by oxone oxidation.167 Given the
multiple-step nature of the synthesis from not readily available
platform chemicals, these monomers are not ideal candidates
for sustainable polymers.
Cyclic esters synthesized directly from sugar precursors have
been reported.89 Their syntheses typically involve elaborate
protecting group chemistry, which compromises the atom
economy and production cost of these monomers. Several 1,5-
lactones were prepared from the corresponding glycosides, but
the homopolymerization of these monomers turned out to be
challenging. One successful example is a sugar lactone (SL-1,
Figure 5) prepared in two steps from D-gluconolactone with
90% overall yield,168 which was furthered polymerized using a
Sn(OBu)2 catalyst. A 1,6-lactone (SL-2, Figure 5) can be
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prepared from D-galactono-1,4-lactone in three steps and 47%
yield169 or from reduced sugar D-dulcitol in four steps and 30%
yield.170
Nonstrained five-membered lactones have recently been
demonstrated as appealing monomers for fully recyclable
polyesters. γ-BL is a key downstream chemical of succinic
acid.171 Hydrogenation of succinic acid to γ-BL has been
investigated with a variety of metal catalysts.172 Au/TiO2
catalysts with addition of small amount of Pt can convert
succinic acid to γ-BL with 97% selectivity at 97% conversion.173
α-Methylene-γ-butyrolactone (MBL) is naturally occurring in
tulip and can also be readily synthesized from sugar-derived
itaconic acid.174 Its derivative, γ-methyl MBL, can be prepared
from levulinic acid,175 a biorefinery platform chemical obtained
from C6 sugars or cellulose.91 These monomers can undergo
polymerizations at both the alkene and ester site, making them
potential substitutes for petroleum-based polyacrylates and
polyesters.176,177 Another five-membered lactone, α-Angelica
lactone (AL), can also be obtained from levulinic acid through
acid-catalyzed dehydration.33
A few four-membered lactones have been reported to be
synthetically accessible from renewable feedstocks. β-Propio-
lactone (PL) is produced from 3-hydroxypropanoic acid by
cyclization.78 β-Malolactonates, a useful class of monomers for
water-soluble poly(malic acid) and amphiphilic PHA-type
architectures, can be synthesized from sugar-derived malic
acid, aspartic acid, or maleic acid.178 However, the overall yields
of all these routes are below 10%.
Macrolactones are less explored for polymerizations not only
due to their difficult synthesis but also because of their low
enthalpies of polymerization179 necessitate polymerization at
high monomer concentrations in the melt (entropy-driven
polymerization).180 The most investigated macrolactone for
polyester synthesis is pentadecalactone (PDL). It occurs
naturally in angelica root essential oil, from which PDL is
isolated at an annual volume of around 1000 t.181 Ambrettolide
is an unsaturated lactone found in the vegetable oil of ambrette
seed.182 Access to larger rings is limited by the availability of
α,ω-functionalized starting materials. Recently, macrolactones
with ring sizes of 19 and 23 were synthesized via acyloin
condensation of α,ω-diesters prepared from isomerization
alkoxycarbonylation of oleic and erucic acid, respectively.181
ROP of these macrolactones generates long-chain polyesters
with higher and more predicable molecular weights than the
ones prepared from the polycondensation of fatty acids.
2.4. Carbonates
Dialkyl carbonates are considered as green substitutes for
phosgene for the step-growth synthesis of polycarbonates.
While dialkyl carbonates used to be prepared industrially from
phosgene, they can now be produced on a large scale using
CO.183 New synthetic technologies that use CO2 as a
renewable carbonyl source are also emerging.184 Dehydrative
condensation of CO2 and alcohols is the most straightforward
and green route to dialkyl carbonates, but the reaction is
severely limited by the unfavorable equilibrium. An effective
dehydrating agent such as acetal, orthoester, and a high-
performance catalyst, usually a metal alkoxide (e.g., Sn, Ti, and
Zr) with an acidic cocatalyst [e.g., Sc(OTf)3], are required to
drive the equilibrium toward carbonate formation. Dimethyl
carbonate (DMC) can be produced by this method in yields of
40−60% based on acetal.185
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Scheme 3. Different Synthetic Routes to Six-Membered Cyclic Carbonatesa
a
Only representative or the most recent catalytic and non-catalytic systems are presented.
Figure 6. Cyclic carbonates derived from renewable diols.
Cyclic carbonates are typically synthesized from the
nucleophilic substitution between a diol and a carbonyl source,
traditionally phosgene183,186 or its safer substitutes such as
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triphosgene,187 di-tert-butyl dicarbonate,188 1,1′-carbonyldiimi-
dazole,189 aromatic carbonates,190,191 and ethyl chlorofor-
mate.192 Other synthetic routes using CO or ureas as the
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carbonyl source are also known (Scheme 3). Since a variety of
diols can be chemically or microbially prepared from
carbohydrates, cyclic carbonates derived from these diols are
partially renewable (Figure 6). PDO and 1,3-butanediol provide
trimethylene carbonate (TMC) and α-methyl trimethylene
carbonate (α-MeTMC). Dihydroxyacetone (DHA) generated
by selective oxidation of glycerol via Pd-catalysis193−195 or
microbial fermentation196 is used to synthesize six-membered
cyclic carbonates 2,2-dimethoxypropylene carbonate
(MeO2DHAC)195−197 and 2,2-ethylenedioxypropane-1,3-diol
carbonate (EOPDC)198 after ketone protection. A series of
seven-membered carbonates (7CC, α-Me7CC, β-Me7CC)
have been prepared from 1,4-diols derived from succinic,
levulinic, or itaconic acid.199 Synthesis of cyclic carbonates
directly from sugar molecule is also possible, but because of the
presence of multiple hydroxyl groups, selective protection is
required. Several cyclic carbonates (Figure 6) prepared by
multistep synthesis from glucose, xylose, or mannose have been
utilized in ring-opening polymerizations.89
The use of CO2 as a safe, cheap, and renewable carbonyl
source for the cyclic carbonate synthesis has been recently
explored (Scheme 3E). The thermodynamics of this
dehydrative cyclization reaction is unfavorable, similar to the
synthesis of dialkyl carbonate from CO2.184 A strategy based on
the activation of the hydroxyl group for CO2 addition along
with in situ formation of an effective leaving group to facilitate
ring-closure has proven successful. Zhang found that the
coupling of 3-chloro-1-propanol with CO2 in the presence of
1.1 equiv of Cs2CO3 proceeded efficiently under mild
conditions (40 °C, 1 atm CO2) to provide trimethylene
carbonate in 95% yield.200 The use of halide is crucial for the
conversion, highlighting the importance of the leaving group. A
slightly different system based on Cs2CO3 was reported by
Dyson.201 Instead of starting from haloalcohols, they used alkyl
halides to generate the leaving group in situ and a heterocyclic-
carbene based catalyst to activate CO2. Using this system, the
coupling of substituted 1,2- and 1,3-diols with 1 atm CO2
afforded cyclic carbonates in ∼60% yield. A minor pathway
based on the direct coupling of Cs2CO3 with diols and alkyl
halide in the absence of CO2 and carbene also contributed to
the formation of cyclic carbonate. Recently, Buchard reported
an efficient two-step procedure using DBU as the base in the
first step to activate the hydroxyl group toward carbonylation
and NH 3 /TsCl in the second step to facilitate the
cyclization.202 The coupling of diols with CO2 occurred at 25
°C and ambient pressure, affording cyclic carbonates in 40−
70% yields. This method can be applied to a variety of mono-
and disubstituted diols and even sterically demanding sugar
molecules.202,203 Although these approaches use cheap, safe,
and renewable feedstocks and operate under relatively mild
conditions, the generation of stoichiometric wastes and the
moderate yields of these reactions limit their atomic efficiencies.
Future work on improving the efficiency and making the
procedure catalytic is required in order for this process to be
economically competent to replace the current industrial
protocols.
2.5. Epoxides
Epoxides are used as comonomers with cyclic anhydrides or
CO2 for the synthesis of polyesters and polycarbonates through
ring-opening copolymerization. CO2 is an abundant renewable
resource, and cyclic anhydride can be readily prepared by
dehydration of renewably sourced diacids. There is also
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significant interest in sourcing epoxides from biomass to
prepare fully renewable polyesters and polycarbonates (Figure
7).
Figure 7. Epoxides derived from renewable sources.
Most bioderived epoxides are prepared by catalytic
epoxidation of alkene group present in a renewable substrate.
For example, limonene oxide (LO) and α-pinene oxide (APO)
are derived from naturally occurring terpenes. Different
stereoisomers of LO have been synthesized by stereoselective
metal-salen catalysts in the presence of an effective terminal
oxidant such as NaOCl or peroxides.204 Williams and Meier
reported the synthesis of various epoxides205 from 1,4-
cyclohexadiene (CHD), a common byproduct of olefin
metathesis of polyunsaturated fatty acids such as linoleic
acid.206 One of the most commonly used epoxides, cyclohexene
oxide (CHO), can be prepared by selective hydrogenation of
CHD followed by oxidation. Double oxidation of CHD leads to
bis-epoxides that could be used as cross-linkers. Unsaturated
fatty acids are also common precursors for biobased epoxides.
Methyl 9,10-epoxystearate (MES) derived from oleic acid has
been used to prepare polyesters with extremely low Tg (−44
°C).207 Some epoxy fatty acids are naturally occurring, such as
vernolic and coronaric acid from seed oil and 18-hydroxy-9,10-
epoxyoctadecanoate (HEOD) from plant suberin.
Epichlorohydrin (ECH), an important industrial chemical
produced on a 1.8 million tons scale annually, can be derived
from glycerin through a two-step reaction.208,209 In the first
step, glycerin is dichlorinated by HCl with the assistance of a
carboxylic acid catalyst to generate a mixture of 1,2- and 1,3-
dichlorohydrin, which is then treated with base to form ECH.
ECH can be converted to a variety of functional glycidyl ethers,
which largely increases the structural diversity of the polymers.
One such monomer is furfuryl glycidyl ether prepared from
ECH and sugar-derived furfural alcohol.210 The furan group
provides a useful handle for the postpolymerization function-
alization via Diels−Alder reaction. A complete survey of
renewably sourced epoxides and their polymerization reactivity
is available in a recent review by Coates.211
3. SYNTHESIS OF POLYESTERS AND
POLYCARBONATES
The development of petroleum-based plastics has been driven
by the innovations in catalytic petrochemistry and polymer-
ization methods. Similarly, the effective uses and trans-
formations of renewable feedstocks to sustainable polymers
rely on the development of innovative and green catalytic
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Scheme 4. Different Synthetic Routes to Polyesters and Polycarbonates
chemistries. Polyesters and polycarbonates can be synthesized
through a variety of routes summarized in Scheme 4. These
routes can be divided into two classes: step-growth and chain-
growth polymerizations. The chain-growth polymerization
methods include the ring-opening polymerization of a cyclic
monomer and the ring-opening copolymerization of two
monomers. In addition, a specific class of polyesters, PHAs,
can be synthesized through microbial fermentation. In this
section, different synthetic routes and catalytic systems are
compared and discussed in the context of sustainability (i.e., the
use of green catalytic systems, mild polymerization conditions,
and high product selectivity). The advantages and limitations of
each method are highlighted.
3.1. Step-Growth Polymerization (SGP)
The traditional way of synthesizing polyesters and polycar-
bonates is by step-growth polymerization. Polyesters are
synthesized from polycondensation reactions of diols and
diacids (or diesters) or hydroxyl acids. Polycarbonates are
prepared by polycondensations between diols and a carbonyl
source, traditionally phosgene. Although the step-growth
method has been known since the discovery of synthetic
polymers in early 20th century,212 it is still the most frequently
used method for the synthesis of polyesters and polycarbonates
in industry.
Due to the wide availability of diols, diacids or hydroxy acids,
SGP provides easy access to polyesters and polycarbonates with
diverse backbone structures and side-chain functionalities.
Given that many diols and diacids can be readily obtained
from biomass (sections 2.1 and 2.2), SGP provides a
straightforward route to renewable polyesters and polycar-
bonates. One such commercial example is biopoly(butylene
succinate). Unlike chain-growth polymerizations, SGP is not
restricted by the size and substitution pattern of the monomers,
and it is particularly useful for the synthesis of polyesters and
polycarbonates with long alkyl segments (>8 carbons) between
each ester/carbonate moiety. For example, SGP of plant oils
derived diols and diacids with >20 methylene sequences
generates polyesters with structures and thermal properties
reminiscent of PE. 213 These polyesters are otherwise
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inaccessible through the chain-growth method. SGP also allows
easy tuning of the physical properties of the polymers by
varying the structures of building blocks. For example, aliphatic
polyesters with high glass transition temperatures (Tg > 60 °C)
can be prepared by using a rigid diol such as isosorbide.214 The
crystallinity and biodegradation rate of poly(alkylene carbo-
nates) can be adjusted by employing diols with different chain
lengths.215,216 Moreover, the use of multifunctional monomers
such as glycerol and citric acid enables a facile synthesis of
biodegradable thermosets.217
However, the step-growth nature of SGP leads to several
drawbacks, including the difficult control of molecular weights
and the inaccessibility to block copolymers or other sequence-
specific polymer architectures. In addition, the removal of
byproducts, water or alcohol, from the polycondensation
reactions necessitates the use of high temperatures and
oftentimes vacuum conditions, which makes this approach
very energy-intensive.218 This also precludes the synthesis of
thermally unstable polymers as well as complicates the use of
volatile monomers.219 Side-reactions and evaporation of
monomers occurring at these harsh conditions can result in a
stoichiometric imbalance of reactants, which makes the
synthesis of high molecular weight polymers very difficult. To
address this problem, a two-step procedure is employed for
many polycondensation reactions.215,220−222 In the first step,
the esterification or carbonation byproduct (water or alcohol) is
distilled off at ambient pressure to form oligomers. The
reaction between these oligomers is promoted in the second
step by slowly reducing the pressure and/or increasing the
temperature. The elimination of the small-molecule byproducts
generated from the chain end coupling drives the increase in
chain length. This two-stage procedure has enabled the
synthesis of polyesters and polycarbonates with molecular
weights over 50 kDa.215,223
Metal salts such as titanium alkoxides, tin alkoxides, and zinc
or magnesium carboxylates are commonly used catalysts for the
step-growth synthesis of polyesters and polycarbonates.224−229
These catalytic polycondensations are typically conducted at
very high temperature (>200 °C) and high vacuum to reach
high conversion. For example, Ti(OiPr)4 can mediate the
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Scheme 5. Synthesis of Polycarbonates via Direct Polycondensations of Diols and CO2
polycondensation of several bioderived diesters (succinate,
adipate, and sebacate) with 1,4-butanediol under high temper-
ature (up to 240 °C) and in vacuo to generate aliphatic
polyesters with Mn > 20 kDa.225,230,231 Melt condensation of ω-
hydroxyl fatty acids [e.g., OH(CH2)13COOH], catalyzed by
Ti(OiPr)4 via a two-stage polymerization (200 °C under N2
then 220 °C under 0.1 mmHg) generate polyesters with
molecular weights ranging from 50 to 110 kDa.232 Meier
recently used Sn(Oct)2 to polymerize dimethyl itaconate and
long chain diols in the presence of 0.5 wt % of 4-
methoxyphenol as a radical inhibitor to make linear unsaturated
polyesters with Mn up to 11500 Da.233 This was the first time
that a high-molecular-weight linear polyester was produced
from itaconic acid without isomerization or cross-linking of the
vinylic double bond. Further modification of the resulting
unsaturated polyesters by Michael addition yielded polyesters
with different substituents dangling off the backbone, which
provided a means to tune the thermal property of the
materials.233
The development of catalytic processes that can operate at
lower temperatures will reduce the energy input and thus
increase the sustainability of the step-growth synthesis. Metal
triflates have become a class of popular polycondensation
catalysts for this reason. Because of their strong Lewis acidity,
they can catalyze polycondensation reactions at much milder
temperatures (<100 °C). Among different metals, bismuth
triflate [Bi(OTf)3] has received particular attention due to its
low toxicity (Bi3+ is among the least toxic heavy metal ions),
low cost, and stability.234 Using Bi(OTf)3 as the catalyst, the
polycondensation of sebacic acid and various α,ω-alkanediols
can be performed at 80 °C under vacuum for 48 h to afford
polyesters with Mn up to 30 kDa.235,236 A few studies using
Bi(OTf)3 to polymerize plant oil-237 and suberin-derived238
long-chain fatty acids generated highly crystalline polyesters
with high melting and degradation temperatures as attractive
alternatives to petroleum-based polyolefins.
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Review
Many biobased carboxylic acids and alcohols contain
multiple hydroxyl groups. The use of a chemoselective catalyst
is critical to eliminate the need for tedious and uneconomical
protection chemistry239,240 and to enhance the product
specificity. Takasu found that scandium triflate (Sc(OTf)3)
selectively esterifies primary hydroxyl groups over the
secondary or tertiary alcohol.241 They developed a chemo-
selective polycondensation of tartaric acid or malic acid with
polyols such as glycerol and sorbitol under mild conditions [60
°C, 0.3−3.0 mmHg, 0.5 mol % Sc(OTf)3] to afford linear
polyesters (Mn between 4 and 26 kDa) with negligible
branching or cross-linking. The pendant hydroxyl groups not
only enable postpolymerization functionalization but also
provide a handle to tailor the crystallinity of these aliphatic
polyesters.242
Recently, there has been a surge of interest in developing
organocatalytic processes for the synthesis of polyesters and
polycarbonates due to their wide applications in biomedical
devices, food packaging, and electronic devices. Several classes
of organocatalysts have been used to catalyze the SGP of diols
with diacids or carbonates, including strong Brønsted acids such
as H2SO4, triflic acid, p-toluenesulfonic acid (PTSA), bis-
(trifluoromethanesulfonyl)-imide (Tf2NH),243,244 and organic
bases such as TBD,221,245−247 MTBD,248 and 1-n-butyl-3-
methylimidazol-2-carboxylate.249 Kobayashi developed a unique
catalytic system250−252 using a surfactant-like acid, such as
dodecylbenzenesulfonic acid (DBSA), to mediate the emulsion
polycondensation of aliphatic carboxylic acids and alcohols in
water. Since the water byproduct is expelled out of the
hydrophobic interior of micelles, this reaction can proceed
effectively at low temperature (40−80 °C) and 1 atm. This
mild and environmentally benign system has been successfully
applied to several fatty-acid type monomers.253,254 To date, the
activity of organocatalysts for SGP and the molecular weights of
the resulting polyesters and polycarbonates are not yet
comparable to the most efficient metal catalysts. SGP mediated
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Scheme 6. Fundamental Steps of ROP of Cyclic Esters (Or Cyclic Carbonates)
by mild and selective enzyme catalysis also provides a metal-
free and eco-friendly route to polyesters and polycarbon-
ates.255−259 However, the high costs and long reaction times of
enzyme catalysts largely limit their utility in large-scale
manufacture.257,260
For the step-growth synthesis of polycarbonates, the
replacement of hazardous phosgene with more renewable and
eco-friendly carbonyl reagents is a subject of intensive research.
Organic carbonates such as dimethyl carbonate (DMC) are
currently employed as a safer and greener substitute for
phosgene. They can be produced on a large scale from CO, or
potentially from CO2.183,184 Recently, several studies have
demonstrated the potential of using CO2 as a renewable and
safe carbonyl reagent for the synthesis of polycarbonates
(Scheme 5). The direct coupling of CO2 and diols is severely
limited by the reaction equilibrium and requires an effective
dehydration system. Kadokawa reported a PR3/CBr4/base
system (Scheme 5a) to facilitate the direct polycondensation of
CO2 with alkane diols at room temperature and ambient
pressure.261,262 Only moderate yields (<60%) and low
molecular weights (Mn up to 6 kDa) were achieved. The
polymerization also generated quantitative wastes including
CHBr3, R3PO, protonated bases. The first catalytic approach
for the polycondensation between CO2 and diols was reported
by Tomishige in 2016 using CeO2 as the catalyst and 2-
cyanopyridine as the dehydrating agent (Scheme 5b).263
Quantitative conversions of diols were achieved under 5 MPa
CO2, but the molecular weights of the obtained polycarbonates
were extremely low (Mn < 1700 Da). In comparison to the
direct coupling of CO2 and diols, the use of alkyl dihalides as a
third condensation component has been more successful to
generate polycarbonates with higher molecular weights.264−266
The first system was reported by Inoue in 1994 (Scheme
5c).264 They found that treatment of a mixture of diol, alkyl
dihalide, and K2CO3 with atmospheric pressure CO2 in an
aprotic polar solvent generated polycarbonates with 25−90%
yields and Mn of 5−15 kDa (Scheme 5c). Characterizations of
the resulting polymers suggested an alternating incorporation
of diols and dihalides into the polycarbonates. This method was
recently revisited by Feng and Gnanou, who improved the
reaction efficiency by using Cs2CO3 as the base and 10 bar CO2
(Scheme 5d).265 High yields (>90%) and high molecular
weights (Mn in the range of 10−40 kDa) were achieved for a
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Review
variety of diols and dihalides substrates. In another study, Du
employed CH2Cl2 as the dihalide and condensed it with various
diols and 1 atm of CO2 to give polymers with Mn up to 11 kDa
(Scheme 5e).266 In this case, alternating ether and carbonate
linkages were observed in the polymer. Although the direct use
of CO2 as a monomer for the synthesis of polycarbonates has
limited success thus far, more effective catalytic systems will
likely enable a more effective synthesis of polycarbonates in the
future.
3.2. Chain-Growth Polymerization
3.2.1. Ring-Opening Polymerization (ROP). Ring-open-
ing polymerization of cyclic esters and carbonates is an efficient
method for the synthesis of aliphatic polyester and poly-
carbonates. It is a type of chain-growth polymerization in which
an initiator is used to ring-open a cyclic monomer to generate a
reactive center to which further cyclic monomers are added to
form a longer chain (Scheme 6).218 Depending on the nature of
the initiator, the propagating species can be radical, cationic,
anionic, or covalent. With the proper choice of an initiating/
catalytic system, ROP of cyclic esters and carbonates can be
performed under mild conditions (room temperature, ambient
pressure) to give high yield and 100% atom economy, which
makes ROP a highly efficient and green route for the synthesis
of polyesters and polycarbonates. As opposed to step-growth
polymerizations, ROP allows for a fine degree of control over
several important macromolecular parameters including mo-
lecular weight, polydispersity, end-group fidelity, regio- and
stereoselectivity, and architecture (block, cyclic, star,
etc.).267,268 For this reason, ROP has been the method of
choice for the synthesis of tailor-made drug delivery systems
where complex architectures and precise molecular weights are
essential to their performance.269,270 Although cyclic esters and
carbonates are usually not directly available from nature, some
of them can be synthesized from platform chemicals of
biorefinery,160,164−167,171,181,271,272 with lactide being the most
successful example.
Because the thermodynamic driving force for ROP is highly
dependent on the ring size and substitution pattern of the
monomer,273 only a limited set of cyclic esters and carbonates
can be polymerized under practical conditions. Some
representative standard enthalpies and entropies for the ROP
of cyclic esters with various ring sizes are shown in Table 1.
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Table 1. Standard Thermodynamic Parameters for the ROP of Cyclic Esters with Different Ring Sizes273−276
monomer ring size state transitiona
β-propiolactone 4 l→c
γ-butyrolactone 5 s→s
δ-valerolactone 6 s→s
L-lactide 6 s→s
ε-caprolactone 7 s→s
tridecanolide 14 l→l
pentadecanolide 16 l→l
a
State of monomer and polymer: l (liquid), s (solution), and c (semicrystalline solid). bEquilibrium monomer concentration at 298 K. cDetermined
in CD2Cl2, [M]0 = 10 M. dDetermined in dichloromethane/toluene (70:30 v/v), [M]0 = 0.35 M. eDetermined in 1,4-dioxane, [M]0 = 1.0 M.
f
Determined in dichloromethane/toluene (70:30 v/v), [M]0 = 2.0 M. gAt 430 K. hAt 370 K.
More extensive tabulations can be found in the litera-
ture,273−276 and it should be appreciated that the values are
sensitive to the standard states specified or the conditions in
which they are measured (solvent, state of monomer/polymer).
For small- and medium-size rings (ring size <8), ring-opening is
driven by enthalpy as a result of release of ring strain. Four-,
six-, and seven-membered rings are favorable for ROP due to
their large ring strains while five-membered lactones such as γ-
butyrolactone (γ-BL) exhibits a less favorable enthalpy of
polymerization and is usually considered as nonpolymeriz-
able.277 However, Chen recently found that at low temper-
atures (e.g., −40 °C), the ROP of γ-BL mediated by
La[N(SiMe3)2]3 or tert-Bu-P4 can proceed to high conversions
(60−90%).278 In contrast, for cyclic esters with large ring sizes,
the ΔHp0 of ring-opening is minimal and polymerization
becomes entropy-driven as a result of the increase of
conformational freedom.180 ROP of a few macrolactones
(ring size = 14, 16) have been successfully applied to prepare
long-chain polyesters with similar structures but higher and
more predictable molecular weights than the ones obtained
from the polycondensation of fatty acids.279−281
Similar limitations on ring size exist for cyclic carbonates.
While the ROP of five-membered cyclic carbonates is
enthalpically disfavored, six- and seven-membered cyclic
carbonates (6CCs, 7CCs) can undergo facile and controlled
ROP under mild conditions. The synthetic versatility of 6CCs
allows the incorporation of a wide range of functional groups to
the resulting polycarbonates, which has led to a versatile
material platform for biomedical applications. A comprehensive
list of these functional 6CCs is available in a recent review by
Dove.282 Recently a class of strained 8-membered cyclic
carbonates derived from diethanolamine were prepared and
polymerized to well-defined N-substituted polycarbon-
ates.283,284 The N-substitution not only enhances the ring
strain but also provides a synthetic handle to introduce
functionality to these polycarbonates.
Common to all chain-growth polymerizations, chain transfer
can compete with chain propagation to undermine the control
on the structure and molecular weight distribution of the
resulting polymers.273 As depicted in Scheme 6, intramolecular
chain transfer such as cyclization (kcy) and backbiting (kbb) of
chain end onto an internal ester group leads to the formation of
cyclic polyesters; intermolecular chain transfer (transesterifica-
tion) results in chain scrambling (ksc) and broadens the
molecular weight distribution. The relative rates of these steps
are mainly controlled by the catalytic processes. Therefore, the
development of selective catalysts that favor the chain
propagation over any chain transfer and termination events is
critical for the synthesis of polyesters and polycarbonates of
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Review
ΔH0p (kJ/mol) ΔS0p (J/mol K) [M]eq (mol/L)b
−82.3 −74 3 × 10−11
−5.4c −39.6c 13.24c
−8.4d −14.7d 0.18d
−22.9e −41.1e 1.2 × 10−2e
−14.0f −6.0f 7.0 × 10−3f
−8 26 2.3 × 10−2g
3 23 0.70h
well-defined structures and architectures. In addition, catalytic
processes performed at mild temperature, low catalyst loading,
and solvent-free conditions are particularly attractive from a
sustainability standpoint.
A variety of initiator/catalyst systems have been developed
for ROP of cyclic esters and carbonates.268,270 Alkali metal
complexes such as butyllithium285 and potassium methoxide286
can mediate anionic ROPs via a nucleophilic or enolate-type
initiating mechanism. Because of the strong nucleophilic and/
or basic character of the anionic initiator/chain ends,
transesterification and epimerization are commonly observed
for these anionic ROPs. The aggregation of alkali metal salts,
lithium in particular, often complicates the polymerization
kinetics.287 Strong acids and acylating agents can polymerize
cyclic esters and carbonates through a cationic pathway.273 The
synthesis of high molecular weight polymers is rather difficult
with these catalysts due to the strong tendency of intra-
molecular transesterification (cyclization) and proton transfer
reactions of the cationic propagating species.288 The most
commonly used catalysts for ROP are transition and post-
transition metal complexes, which mediate the ROP through a
“coordination−insertion” type mechanism (Scheme 7).289 As
Scheme 7. Typical “Coordination−insertion” Mechanism for
Metal-Catalyzed ROP
the monomer and alkoxide chain end are both covalently
bound to the metal center, the catalyst can exert a great level of
control on the rate and selectivity of the polymerization. Simple
metal alkoxides and carboxylates such as tin octoate are cheap
and convenient catalysts for ROPs and are used industrially to
produce PLA. However, when it comes to selectivity, especially
stereoselectivity, those well-defined single-site metal catalysts
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Figure 8. Representative metal catalysts with ancillary ligands for stereoselective ROP of LA.
with ancillary ligands are more competent. The ancillary ligand
has proven to be an important element in ROP catalysis to fine-
tune the electronic and steric properties of the metal center and
to control the selectivity of polymerization. Many review
articles268,290−296 have been published in the past decade on the
synthesis and catalytic performance of different types of metal
catalysts, with Al, Zn, group 3, group 4 metals supported by N-
or O-type multidendate ligands receiving the most attention.
Some of these catalysts show not only extremely high reactivity
(TOF > 1000 h−1) but also high regio-/stereoselectivity for the
ROP of asymmetric monomers. For example, a zinc catalyst
with β-diiminate amido ligand (BDIiPr)Zn[N(SiMe3)2] ex-
hibits excellent reactivity and selectivity for the ROP of a variety
of lactones and cyclic carbonates.296 With only 20 ppm of this
catalyst, poly(trimethylene carbonate) with Mn as high as 237
kDa and Đ = 1.68 can be synthesized in quantitative yield
within 2 h.297 No appreciable amount of ether linkage was
detected in the resulting polymers, indicating the absence of a
decarboxylation reaction. In addition, this catalyst showed
exceptionally high regioselectivity (<1% regio-defects) for the
ROP of methyl-substituted cyclic carbonates.298
Given that many cyclic esters and carbonates derived from
plants contain stereocenters, the stereoselective ROP is an
important aspect for the controlled synthesis of sustainable
polymers. Among all chiral monomers, the stereoselective ROP
of lactide has been most extensively studied because of the
important application of PLAs. PLAs with different types of
stereosequences (isotactic, heterotactic, syndiotactic, and
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Review
stereocomplex) have been successfully synthesized by metal-
based catalysts.294,299 Studies of the resulting polymers have
shown a strong correlation between the thermal and
mechanical properties of PLAs and their stereosequences.300
Some representative metal catalysts with high stereoselectivities
are shown in Figure 8. Aluminum complexes supported by
SALEN-type ligands301−309 are some of the most stereo-
selective catalysts for the ROP of racemic LA, but their low
reactivities (typical reaction conditions: Al loading >1 mol %,
70−130 °C, and long reaction time) limit their applicability.
Rare-earth metal catalysts supported by phosphasalen ligands
(such as Ln-phosSALEN in Figure 8) displayed both high
reactivity and stereoselectivity (Pi up to 0.84 at 25 °C) with the
ability to produce high molecular weight isotactic PLAs (Mn >
100 kDa) with extremely narrow polydispersities (Đ <
1.1).310,311 Other metal catalysts such as zirconium complexes
with bispyrrolidine-salan ligand312 and zinc complexes with
chiral or achiral auxiliary ligands313−316 (Figure 8) have also
been used to generate iso-enriched stereoblock PLAs from rac-
LA. Another important bioderived and biodegradable plastics
on the market is poly(3-hydroxyalkanoates) (PHAs). PHAs are
naturally produced by various bacteria (section 3.3) but only
isotactic microstructures are made biologically.317 Syndiotactic
poly(3-hydroxyalkanoate)s (PHAs) have been synthesized by
stereospecific ROP of racemic β-lactones by several rare-earth
metal catalysts.318 This provides new possibilities for engineer-
ing the properties and applications for these plastics.
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Scheme 8. Representative Examples of Using Switchable Metal Catalysts for Monomer Sequence Control319,320,322

Scheme 9. Different Catalytic Mechanisms for the ROP of Cyclic Esters

Recently, the use of switchable metal catalysts to strategically
modulate the rate and monomer selectivity of ROP is
emerging.267 This innovative catalytic strategy has enabled
the facile one-pot synthesis of block copolymers of polyesters
856
and polycarbonates. Diaconescu reported several redox-switch-
able group 4 metal complexes supported by ferrocenyl-based
ligand (Scheme 8A).319 They found that the reduced form was
much more active toward LA than CL while the oxidized form
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Chemical Reviews
had the opposite selectivity. This distinct substrate selectivity
allowed the one-pot copolymerization of the two monomers by
in situ switching of the redox state of the catalyst to synthesize
poly[(LA-minor-CL)-block-(CL-minor-LA)]. In the similar
vein, Byers developed a chemoselective copolymerization of
LA and epoxides using a redox-switchable iron catalyst
(Scheme 8B).320 Unlike the previous case, the two monomers
exhibited orthogonal reactivity with one being completely
inactive during the polymerization of the other. This allowed
the formation of clean diblock copolymers. Similar copoly-
merization of LA and epoxides were obtained using a redox-
switchable zirconium complex.321 Williams developed a strategy
using CO2 as a chemical switch as well as a comonomer for the
one-pot chemoselective polymerization of epoxide and CL
(Scheme 8C).322 They found that the dizinc acetate catalyst
was an excellent catalyst for the ring-opening copolymerization
of epoxide and CO2 but not for the ROP of CL. But as soon as
CO2 was removed, the catalyst turned on the ROP of CL with
no incorporation of epoxide. Thus, repetitive introduction and
removal of CO2 resulted in the formation of multiblock
poly(carbonate-block-ester). Recently, this approach was
extended to a monomer mixture of epoxide, lactone, anhydride,
and CO2 to synthesize a variety of block copolymers with great
sequence control and predictable compositions in the polymer
chains.323
The replacement of metal catalysts with organic catalysts has
emerged for the synthesis of plastics, especially for those used
in biomedical and microelectronic applications. Since the
pioneering work of Hedrick in 2001,324 the application of
organic catalysts to ROP has witnessed significant progress in
the last 15 years and this field has grown to the point that it
now provides a powerful and, in some cases, better alternative
to the use of traditional metal-based catalysts.325,326 Several
attributes of organic catalysts, including their low cost and wide
availability, easy removal from polymers, low toxicity, and
versatile catalytic mechanisms, make possible a greener and
more versatile synthesis of polyesters and polycarbonates.
Depending on the nature of the catalyst, organocatalysts can
operate through a variety of mechanisms (Scheme 9).326
Organic bases such as N-heterocyclic carbenes (NHCs) and
amidines can activate the alcohol initiator/chain ends through
hydrogen bonding interactions. Alternatively, they can activate
the monomer through nucleophilic addition. This has led to the
development of zwitterionic ring-opening polymerization for
the synthesis of high molecular weight polyesters327 and
polycarbonates284 with cyclic topology. Organic acids such as
sulfonic or phosphoric acid can catalyze the polymerization
through electrophilic activation of monomers. Catalytic systems
combining both H-bond donor and H-bond acceptor moieties,
such as thiourea/amine, can simultaneously activate the
monomer and alcohol initiator/chain end. These systems
have proven especially selective for chain propagation over
transesterification, affording narrowly dispersed polyesters and
polycarbonates. The diversity in mechanistic pathways not only
provides new opportunities for enhancing the rate and
selectivity of polymerization but also enables the synthesis of
polymer architectures that are difficult to access by metal-
mediated processes. Many review articles have covered different
aspects of this topic.325−332 Herein, we aim to highlight some
recent catalytic developments that feature improved produc-
tivity and/or higher level of control on the macromolecular or
microstructural parameters of polymers.
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Review
The synthesis of well-defined linear polyesters or polycar-
bonates with molecular weights over 100 kDa has been difficult
using organocatalysts due to the competitive catalyst-initiated
process at low alcohol initiator concentrations. Coulembier
developed a zwitterionic ammonium betaine catalyst that
exhibited high selectivity for the ROP of lactide.333 PLA of
Mn = 97 kDa (DP = 750) with molecular weight conformed to
the monomer-to-alcohol ratios and Mw/Mn = 1.18 can be
synthesized by this catalyst. They proposed a charged-assisted
hydrogen-bonding mechanism for this catalyst where it
activates the alcohol initiator/chain-end through a combination
of hydrogen bonding between the aryloxide group and the
H(δ+) of ROH and the Coulomb attraction between the
ammonium group and the O(δ-) of ROH (Scheme 10).
Despite the weak basicity of aryloxide, these catalysts showed
good reactivity toward L-LA owing to the supplementary ionic
activation.
Scheme 10. Proposed Interactions between Ammonium
Betaine and Alcohol Initiator/Chain End333
Recently, N-heterocyclic olefins (NHOs) have emerged as a
class of active and versatile catalysts for the ROP of cyclic esters
and carbonates.334,335 These catalysts can function by different
mechanisms: activating the alcohol initiator through hydrogen-
bonding (Scheme 11A), deprotonating monomers to form
enolate-type initiator (Scheme 11B), or activating monomer
through nucleophilic pathway (Scheme 11C). Their catalytic
behavior largely depends on the ring size, (un)saturation of the
backbone, and the steric environment of the exocyclic carbon.
While nonsubstituted NHOs (at the exocyclic carbon, NHO-
1,3) were ineffective for ROP due to catalyst deactivation
(Scheme 11C), NHO bearing dimethyl substituents (NHO-2)
proved highly active for the ROP of LA and VL.334 In the
presence of an alcohol initiator, the ROP of 50 equiv. L-LA by
as low as 0.2 mol % NHO-2 reached quantitative conversion in
less than a minute, resulting in PLAs with low molecular weight
distributions (Đ < 1.2). Under the same conditions, the ROP of
VL is fast but poorly controlled due to the more significant
enolate-based initiation. Chen recently combined NHOs with a
Lewis acid Al(C6F5)3 to develop a highly efficient catalytic
system.335 The living polymerizations of VL and CL mediated
by NHO-1/Al(C6F5)3 generated linear polyesters with high
molecular weights up to 855 kDa (DP = 3200) and narrow
molecular weight distributions (Đ = 1.03−1.63). End-group
analysis revealed an imidazolium enol-like chain end of the final
polymers, indicative of an intramolecular proton transfer within
the zwitterionic intermediates generated from the nucleophilic
addition of NHOs to the monomer (Scheme 11D). The high
activity and the ability to operate through different polymer-
ization mechanisms make NHO an attractive motif for future
catalyst design and optimization.
Typical nucleophilic organocatalytic ROP is subject to a
trade-off between rate and selectivity: the most active catalysts
(i.e., NHCs, TBD) tend to promote side reactions such as
chain transfer and epimerization especially at high conversions
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Scheme 11. Structures of NHOs and Their Different Catalytic Pathways for the ROP of Lactones334

while the most selective systems, such as TU/amines, suffer
from slow kinetics. Recently a class of (thio)urea anions
catalysts were disclosed that exhibit both high activity and
selectivity for the ROP of a variety of cyclic esters and
carbonates (Scheme 12).321,336 These ionic catalysts are
Scheme 12. Family of (Thio)urea Anions for Both Fast and
Selective ROP
prepared by simple deprotonation of the neutral ureas or
thioureas. The rate of the polymerization can be tuned over
several orders of magnitude by modifying the urea or thiourea
substituents. The urea anions are more active than the
corresponding thiourea anions, with the ability to polymerize
all tested monomers in just seconds (<12s) with excellent
control on molecular weight distributions (Đ = 1.06−1.14).336
DFT calculations suggested a bifunctional mechanism analo-
gous to that of TBD,321 where the (thio)imidiates behave as a
proton shuttle to pick up the proton from the initiator/chain
end, to stabilize the tetrahedral intermediate via double H-
bonds, and to deliver the proton back to the chain end after
ring-opening. The operational simplicity of these urea or
thiourea anions coupled with their high activity, selectivity, and
versatility illustrate the potential of these catalysts for the
sustainable synthesis of polyesters and polycarbonates.
Kiesewetter reported a series of bis- and tris(thio)urea based
H-bond donors (Scheme 13), which exhibited dramatic rate
acceleration compared to the mono-TU/amine systems, yet
retaining the high selectivity for propagation over trans-

Scheme 13. Proposed Monomer Activation Mechanism for bis- and tris-(Thio)ureasa

a
Adapted with permission from ref 338. Copyright 2016 American Chemical Society.

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Figure 9. Chiral organocatalysts with high stereoselectivities for the ROP of rac-LA. kL/kD value for the exo-PRO system was not reported.
Figure 10. Representative catalysts for the ROCP of epoxides with CO2 or cyclic anhydrides.
esterification.337,338 The most active one, a tris-urea/MTBD, is
approximately 100 times faster than mono-TU/MTBD for the
ROP of CL, with equally good control on molecular weights
and molecular weight distributions (Đ < 1.05). The rate
acceleration is proposed to arise from an “activated (thio)urea”
mechanism in which each additional (thio)urea moiety
enhances the acidity via intramolecular H-bond activation
(Scheme 13), supported by DFT calculations.
While low stereocontrol at ambient temperature has been a
long-standing problem for organocatalytic ROP, recent
advances in catalyst design have demonstrated the potential
of organocatalysts to rival the state-of-the-art metal catalysts.
Terada and Satoh reported a binaphthol-derived chiral
phosphates (BINOL-PP, Figure 9) for the enantioselective
polymerization of rac-LA (kD/kL up to 28) at 75 °C to generate
isotactic PLAs (Pm = 0.86) at 49% conversion.339 Chen
developed a bifunctional catalyst that combines β-isocupreidine,
a previously reported chiral ROP catalyst with low
enantioselectivity (kL/kD = 4.4),340 and a chiral thiourea
based on the binaphthyl scaffold.341 This catalyst exerts double
stereodifferentiation for the ROP of rac-LA with kL/kD up to 53
(for TU-ICD, Figure 9). The ROP of rac-LA mediated by TU-
ICD generated isotactic PLAs (Pm = 0.88) at 25 °C and 50%
conversion. Mecerreyes and Cossió found that a cocatalytic
system consisted of a densely substituted proline (PRO, Figure
9), and DBU was able to kinetically resolve racemic lactide. exo-
PRO exhibited a strong preference for L-LA, and the ROP of
rac-LA by this catalyst at 50% conversion generates a highly
isotactic PLAs with Pm up to 0.96 at 25 °C.342
3.2.2. Ring-Opening Copolymerization (ROCP). An
alternative chain-growth route to aliphatic polyesters and
polycarbonates is the alternating copolymerization of epoxides
and cyclic anhydrides (for polyesters) or epoxides and CO2 (for
polycarbonates). While the field of epoxide/CO2 copolymeriza-
tion is quite mature, with several technologies commercialized,
the progress in epoxide/cyclic anhydride copolymerization is
more recent.211,343 Because of the limitation on the ring size of
epoxides (3,4-membered) and cyclic anhydrides (mainly 5,6-
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membered) that can be incorporated, ROCP is restricted to the
synthesis of polyesters and polycarbonates whose ester/
carbonate moieties are 2 or 3 carbons apart. On the other
hand, it is often the only route to polycarbonates whose
carbonates are 2 carbons apart since these polymers are
otherwise difficult to obtain from the ROP or step-growth
method for the reasons mentioned above.
One obvious advantage of epoxide/CO2 copolymerization is
the utilization of CO2 as a monomer. Upcycling of waste gases
such as CO2 to useful and valuable plastics has long been of
interest to researchers, and the ROCP of epoxides and CO2
represents one of the most successful examples of CO2
utilization in polymer synthesis.83,344−352 Depending on the
epoxide, this method enables 30−50% of a polymer’s mass to
be derived from CO2, with the rest derived from cheap platform
petrochemicals or potentially from renewable biomass. Because
of the large economic and environmental benefits of this
process, it has stimulated a number of commercialization, such
as QPAC by Empower Materials71 and Converge by Saudi
Aramco.72
The success of ROCP is largely driven by the development of
efficient and selective catalysts. Because of the mechanistic
similarities between epoxide/CO2 copolymerization and
epoxide/cyclic anhydride copolymerization, the two can be
mediated by a similar array of catalysts.343 Early studies focused
on heterogeneous catalysts such as zinc glutarate353,354 and
double metal cyanides.355,356 While these catalysts can show
good reactivities, they lack sufficient control on the polymer-
izations and the structures of the active species are ill-defined.
The development of single-site metal complexes with ancillary
ligands has largely boosted the understanding and the scope of
ROCP.343 In most cases, a nucleophilic cocatalyst is used to
increase the activity of the metal complexes, the most common
ones being bis(triphenylphosphine) iminium salts ([PPN]X)
and 4-dimethylaminopyridine (DMAP). Among the different
metal catalysts, β-diiminate (BDI) zinc complexes and metal
complexes (Al, Cr, and Co) with Schiff-base ligands (salen and
their derivatives) are the most successful ones (Figure 10).
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Scheme 14. Proposed Mechanism for the ROCP of Epoxides with CO2 or Cyclic Anhydridea
a
Three common side reactions are highlighted in color boxes.
Recently, a series of multinuclear catalysts have been shown to
display superior performance than their mononuclear ana-
logues. A comprehensive discussion of these catalysts can be
found in many review articles.83,211,343−345,348,349,351,352
Although the exact mechanism for each catalytic system may
vary, ROCP of epoxide with CO2 or cyclic anhydride generally
follows the coordination−insertion mechanism shown in
Scheme 14.344 The polymerization is initiated by the
nucleophilic attack of a ligand (X) or an exogenous nucleophile
onto a coordinated epoxide. This leads to a metal bound
alkoxide to which CO2 (or cyclic anhydride) readily inserts to
form a metal carbonate (or carboxylate) species. Chain
propagation proceeds by the alternative insertion of epoxide
and CO2 (or cyclic anhydride) to the metal−oxygen chain end,
which leads to the desired formation of polycarbonate (or
polyesters) backbones. However, several competitive side
reactions can occur to compromise the selectivity and yield
of these polymerizations. The most common side reaction is
the consecutive insertion of epoxide molecules to the metal
alkoxide intermediates, which leads to ether linkages in the
resulting polymer backbone (Scheme 14, green box). This is a
problem for many ROCP catalysts since they can also mediate
the homopolymerization of epoxides. 350 Although this
polyether formation can be mitigated by using specific metal
catalysts that are highly selective for copolymerization over
sequential epoxide enchainment, this is still a prevalent problem
in the ROCP literature. Chain transfer of the propagating
chains is another side reaction that occurs in the presence of
protic impurities such as water and alcohol (Scheme 14, red
box). This can cause the molecular weight of the resulting
polymers to be lower than that expected.357−359 On the other
hand, the exploitation of chain transfer phenomenon enables
immortal polymerization conditions, where the chain transfer
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agents are added in large excess compared to the catalyst to
increase the polymerization rate and control the molecular
weight of products.360
One detrimental side reaction for the ROCP of epoxide/CO2
is the formation of five-membered cyclic carbonates (5CCs) as
a result of intramolecular cyclization (Scheme 14, yellow
box).352 Because 5CCs are thermodynamically stable and
cannot be reincorporated into the chains, this elimination
causes irreversible loss of yield. The extent of this reaction
depends on the nature of the epoxide, the catalyst, and the
reaction conditions.83,361 For example, the introduction of
positively charged moieties (e.g., ammonium) to the ligand can
suppress the 5CC formation.362−364 ROCP of cyclohexene
oxide/CO2 is less susceptible to backbiting than that of
propylene oxide/CO2 due to the unfavorable ring strain of
cyclohexene carbonate. It is also found that lower temperature
and higher CO2 pressure favor the propagation over
cyclization.83
One appealing aspect of the ROCP approach is the common
availability and structural diversity of epoxide and cyclic
anhydride monomers, which can be easily prepared from
olefins and dicarboxylic acids, respectively. This is in contrast to
the ROP method, where the preparation of functionalized
lactones/cyclic carbonates can be a challenging and tedious
process, often requiring multiple-step synthesis. The structures
of epoxides and cyclic anhydrides that have been employed for
ROCP have been recently reviewed by Coates.211 Among them,
propylene oxide (PO), cyclohexene oxide (CHO), and phthalic
anhydride (PA) are the most widely studied. Some epoxides
and anhydrides can be prepared from biomass (Figure 7) such
as limonene oxide (from terpene)365,366 and maleic anhydride
(from furfuraldehyde),138 which are attractive monomers for
fully renewable aliphatic polyesters and polycarbonates. Addi-
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Scheme 15. Examples of Terpolymerization of Epoxide, Cyclic Anhydride, and CO2 for the One-Pot Synthesis of Poly(ester-b-
carbonate)
Scheme 16. Overview of Microbial Synthesis of PHAs
tionally, many epoxides and cyclic anhydrides contain
unsaturated moieties that can be utilized for postpolymerization
modifications and cross-linking,211 which increases the range of
architectures and functionalities that can be achieved through
the ROCP method.
The large variety of structures yields a diverse set of polymer
properties that can be easily controlled by the choice of
monomer. For example, switching the epoxide from PO to
CHO significantly increases the Tg of polycarbonates from 30−
40 °C to 80−120 °C.351 By using a different combination of
epoxide and cyclic anhydride, Tg of polyesters can be tuned to
almost any value from −44 to 184 °C.211 A number of studies
have demonstrated the effect of backbone structure and length
and rigidity of side chains on the thermal and mechanical
properties of the resulting polyesters and polycarbonates. A
detailed survey on the structure−property relationship of these
materials can be found in a recent review by Coates.211
Copolymerization of different epoxides or anhydrides provides
even more possibilities of structures and properties that can be
tuned by the ratios of different monomers.83 This leaves many
opportunities for creating polyesters and polycarbonates with
unique physical properties.
Terpolymerization of epoxide, cyclic anhydride, and CO2 is a
facile strategy for the one-pot synthesis of poly(ester-
carbonate),211,343 a class of biodegradable polymers that have
garnered considerable interest due to their possible superior
properties than pure polyesters and polycarbonates. Interest-
ingly, cyclic anhydride almost always gets incorporated first
followed by CO2, leading to the formation of diblock or tapered
block poly(ester-co-carbonates) (Scheme 15). This selectivity is
attributed to the faster rate of anhydride insertion than CO2
insertion into the metal-alkoxide intermediate.367 When the
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two blocks are miscible, only one intermediate Tg higher than
that of the pure polyester and lower than the polycarbonate is
obtained.368 Therefore, the addition of CO2 to an epoxide/
cyclic anhydride copolymerization is a simple way to improve
the thermal properties of polyesters for many applications that
do not require pure polyesters.
3.3. Microbial Fermentation
The microbial synthesis by naturally occurring or genetically
modified microorganisms has been practiced industrially for the
production of bioplastics.369,370 The polyesters produced by
bacteria are polyhydroxyalkanoates (PHAs). PHAs are an
important class of biodegradable plastics commonly used for
packaging, bottles, cutlery, furniture, biomedical implants, drug
delivery vehicles, and animal food supplements.371−374 It is
among the few plastic materials of which a complete cradle-to-
cradle life cycle have been established.375
PHAs are produced by a variety of microorganisms as a
carbon and energy storage material in times of unbalanced
nutrient availability.376 On the basis of the type of carbon
source, the microbial synthesis of PHAs is carried out by either
of the following two classes of bacteria: heterotrophic bacteria
(defined broadly as a wide variety of bacteria using multicarbon
as their primary growth substrates) that utilize carbon sources
such as glucose and fatty acids377 and methanotrophic bacteria
that utilize methane as a primary carbon substrate.378 A general
procedure for PHA biosynthesis is summarized in Scheme 16.
The carbon feedstock is transformed to a common precursor
acetyl CoA, which is converted to the 3-hydroxyacyl monomer
through key metabolic cycles. The specific pathways of these
transformations from different carbon sources have been
reviewed.376,379 The subsequent biotic polymerization of
monomers by a PHA synthase generates intracellular PHA
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Table 2. Different Polymerization Methods for Polyesters

polymerization method advantages drawbacks
polycondensation of diols readily available and renewable monomers; structural diversity of poor control on molecular weight, polydispersity, architecture;
and diacids, or hydroxy polymers energy-intensive reaction conditions
acids
ROP of cyclic esters ability to control molecular weight, polydispersity, microstructure; limited monomer scopes (mostly 4,6,7-membered rings); few
easy access to complex architectures; versatile mechanisms and monomers can be bioderived; difficult to introduce functional
catalysts groups
ROCP of epoxides and easy synthesis of monomers; readily tunable polymer structures and limited to polyesters whose ester moieties are 2 or 3 carbons
cyclic anhydrides properties; ability to control molecular weight, polydispersity, apart; formation of ether linkage
microstructure
microbial synthesis renewable feedstock; bioreactor; low cost and energy input lack of generalizability; difficult control on molecular weights,
polydispersity; extraction of PHAs from bacteria

Table 3. Different Polymerization Methods for Polycarbonates

polymerization method
polycondenstaion of diols with
phosgene/organic carbonate/
CO2
ROP of cyclic carbonates
ROCP of epoxide and CO2
advantages
readily available diols; renewable monomers
ability to control molecular weight, polydispersity, microstructure;
easy access to complex architectures; versatile mechanisms and
catalysts
use of CO2 as a monomer; ability to control molecular weight,
polydispersity, microstructure; versatile catalysts
drawbacks
poor control on molecular weight, polydispersity,
architecture; energy-intensive reaction conditions
limited monomer scopes (mostly 6,7-membered rings);
synthesis of monomers from renewable resources is not
trivial
Limited to polycarbonates whose ester moieties are 2 or 3
carbons apart; formation of ether linkage

granules which consist of a PHA core surrounded by a
phospholipid layer with attached proteins. The polymer is then
extracted and isolated from the bacteria to provide pure PHA
resin. For certain bacteria under optimized growth condition,
the yield of PHA obtained from the intracellular inclusions can
be as high as 89% of the organism’s dry weight.380
One important advantage of this biosynthetic route is that
the feedstock can be completely sourced from biomass (sugars,
oils) or methane waste. The methanotrophic bacteria that
produce PHAs can be found at wastewater treatment plants,
which are often geographically close to sources of waste
methane.375,381,382 This provides an opportunity for trans-
forming waste gas to valuable plastic materials.383 The most
commonly occurring PHA through bacteria synthesis is poly(3-
hydroxybutyrate) (PHB). Depending on the organism and the
conditions of growth, the molecular weight of PHBs can vary
from 50 000 Da to over a million Da.384 Methanotrophic
bacteria have been mainly limited to the synthesis of PHB,
although recent work has demonstrated the possibility to
expand the scope of this synthesis through the utilization of
cosubstrates.382 In contrast, a much broader substrate scope is
found for heterotrophic bacteria. Collectively, these bacteria
have led to the biosynthesis of over 150 different types of PHA
copolymers.385
Although PHA has been industrially produced through
bacteria fermentation since the 1980’s, there are still several
challenges for the PHA industry.373 First, the production of
PHAs is still costly compared to the traditional fossil fuel-based
commodity plastics. The extraction step that uses a large
quantity of organic solvent is a particularly costly step.
Innovation in the extraction techniques, together with
improvement in fermentation and the source of feedstock
from wastes, are key factors to drive down the manufacturing
cost of PHAs. Second, the structures and properties of PHAs
currently produced are quite limited. Plenty of opportunities
exist for the rational engineering of bacteria to produce tailor-
made PHAs with more complex structures and functionalities.
To conclude this section, the different polymerization
methods for polyesters and polycarbonates are summarized
and compared in Table 2 and Table 3, respectively. Each
862
method has its advantages and limitations. Collectively, these
methodologies provide a powerful toolbox for the synthesis of
polyesters and polycarbonates.
4. END-OF-USE OPTIONS
Recycling is one of the most important end-of-use options to
reduce the environmental impacts and resources depletion of
plastics. It is a necessary path to realize a close-loop life cycle of
plastics consistent with the principles of circular economy386
and industrial ecology,3 where there are no wastes but only
products. A high level of recycling can potentially allow for
lower energy and material inputs for a given level of products
and thus improve eco-efficiency.387 Currently, there are four
main types of recycling processes. (1) Mechanical recycling: on
the basis of mechanical reprocessing of plastic wastes into a
product with equivalent or lower qualities, this is the shortest
path to construct a circular flow of plastics as depicted in
Scheme 17, but because of the complications in the segregation
Scheme 17. Different Routes of Recycling
of different types of plastics and the contamination by
nonplastic materials, only PET and HDPE in the form of
relatively pure packaging materials are currently recycled
routinely,388 and the majority of the recyclates is repurposed
for lower grade materials.389 (2) Chemical recycling: the
selective depolymerization of a plastic into its chemical
constituents (monomer, oligomers) provides feedstocks for
repolymerization to the original products or for the trans-
formation to other chemicals for repurposing. In order for this
process to be energetically feasible, the polymerization
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thermodynamics should not be highly exergonic, to enable
facile depolymerization or feedstock recovery. This approach is
considered uneconomical for petroleum plastics due to the low
price of petrochemical feedstock compared with the process
costs incurred to depolymerize and recover the monomer.388
However, for polymers derived from less exergonic polymer-
ization reactions, chemical recycling can provide an attractive
option to recover value, provided that efficient processes can be
developed and implemented. (3) Biological recycling: the
degradation of plastics by natural or engineered micro-
organisms generates primarily CO2 and H2O (sometimes
CH4) as end-products, which can return to the life cycle via
photosynthesis. This strategy is critical for the biodegradable
plastics that are released into the environment (soil and ocean).
However, this is the longest path for building a circular flow of
the plastics (Scheme 17), and the energy and environmental
prices paid to build the chemical complexity of monomers are
completely lost during the degradation processes. Therefore, it
should only be considered when the first two recycling options
are not available. (4) Energy recovery via incineration:
incineration provides a means of capturing the energy value
of waste plastics. However, this process is destructive and does
not facilitate a close-loop life-cycle for plastic materials. In
addition, while efficient processes have been developed,
sophisticated purification and process controls are needed to
ensure that the hazardous substances are not released into the
atmosphere.41 Nevertheless, it is the most suitable way for
dealing with highly mixed plastics.388
This section is intended to provide an overview on the first
three recycling options for polyesters and polycarbonates. We
will focus on the chemical and biological recycling of these
polymers since these processes involve different chemical or
biological catalysis. The nature and mechanism of the catalysts
or microorganisms used to depolymerize these polymers in a
“controlled” fashion (i.e., that allows for the valorization of the
obtained synthons or degradation to CO2 and H2O) is
emphasized. The biodegradation of aliphatic polyesters and
polycarbonates for biomedical applications has been reviewed
elsewhere390−392 and is out of the scope of this review.
4.1. Mechanical Recycling
Mechanical recycling has been applied to packaging materials
such as PET and HDPE as a quick way to integrate them back
into the production cycle. In accordance with the National
Association for PET Container Resources (NAPCOR), ∼30.1%
PET plastic bottles were mechanically recycled in 2015 in the
United States.393 The majority (>70%) of recycled PET
(rPET) is used for production of lower-grade products, mainly
polyester fibers, and only a small fraction (∼10%) is used for
closed-loop bottle-to-bottle recycling.394 This is due to a
common downgrading problem of mechanical recycling, that is,
the recovered plastics tend to lose some quality attributes of the
virgin plastics, such as color, clarity, or mechanical proper-
ties.395 Since closed-loop mechanical recycling requires the
polymers to be effectively separated from sources of
contaminations (other plastics, metals, pigments, adhesives,
etc.) and stable during reprocessing (grinding and melting), the
only postconsumer plastic wastes that have routinely been
recycled in a closed-loop fashion are clear PET bottles and
more recently HDPE bottles.388
Mechanical recycling of PET comprises several key steps:
collection, sorting, size reduction and cleaning, further
separation, and drying.388 Sorting of mingled recyclables are
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done by both automatic and manual methods, which are used
to separate PET from other materials such as glass, metals, and
papers as well as other polymer types. The sorted plastics are
then ground into flakes and cleaned to remove food residues
and additives. After size reduction, several separation
techniques are further applied to remove impurities from
PET. The isolated PET is then dried and sold as pellets or
flakes. The most challenging step is sorting/separation, which
limits the type of polymers that can be recycled and also
determines the quality of recyclates. Current techniques of
sorting are based on both the physical properties and chemical
attributes of the plastics.396 For example, sink/float separation
can effectively separate polyolefins and PS from PVC and PET
due to their different densities. Fourier-transform near-infrared
spectroscopy (FT-NIR) is the most frequently used technique
to determine the polymer type. X-ray detection is particularly
useful to detect PVC, which are 59% chlorine by weight.
Optical sorters such as a color recognition camera are used to
differentiate between clear and colored PET.388
Since the postconsumer plastics can hardly have the exact
content and purity grade of the virgin materials, the recycled
plastics often come with at least some downgrading of
properties and consequently less-valuable end products. One
cause for the decrease in mechanical properties after recycling is
the contamination of main polymer with other polymers. For
example, a small amount of PVC contaminant present in a PET
recycle stream will degrade the recycled PET resin owing to
evolution of hydrochloric acid gas from the PVC at a higher
temperature required to melt and reprocess PET.388 Addition-
ally, the ester bond of PET is sensitive to hydrolytic
degradation. The presence of water could result in chain
scission and decrease in molecular weight during the melting
reprocessing.395 Therefore, intensive drying of PET is necessary
to lower the moisture level prior to melt extrusion.
Since the ability to substitute recycled plastic for virgin
polymer depends on the purity of the recovered plastic feed,
mechanical recycling of rigid plastic bottles consisting of a
single polymer are much simpler and more economical than
those multilayer and multicomponent packages. The key to
enlarge the scope of mechanical recycling rests on improved
collection schemes and innovative sorting and separation
technologies (i.e., more versatile and reliable detectors, more
sophisticated decision and recognition software, and coupled
detection and separation instrument).
4.2. Chemical Recycling
Chemical recycling has attracted increasing scientific and
commercial attention as an alternative with the potential to
absorb and circulate very large amounts of plastic wastes. The
application of catalysis is a key to the success of chemical
recycling and is expected to put this technology at the forefront
of plastic management for sustainable polymers.
4.2.1. Solvolysis. Solvolysis using water, methanol, and
glycol has been the most common chemical recycling strategy
for step-growth polyesters and polycarbonates.41,397 A number
of companies have implemented PET depolymerization at pilot
or commercial level, including Loop Industries,398 Carbios,399
Ioniqa,400 and Gr3n Project.401 Different solvolysis processes of
PETs and bisphenol A (BPA)-type PCs have been developed to
recover suitable monomers for the production of new PETs
and PCs.402,403 However, the industrial applications of this
recycling approach are quite limited due to the higher cost of
recycled monomers compared to virgin feedstocks. The
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Scheme 18. One-Pot Chemical Recycling and Repurposing of PET
Scheme 19. One-Pot Chemical Repurposing of PC
depolymerization is typically catalyzed by acids or bases. For
example, the alkali-catalyzed methanolysis of PC in THF at 40
°C provides BPA and dimethyl carbonate in over 95% yield
within 35 min.404 Achilias developed an efficient depolymeriza-
tion method of PET and PC into their monomers and
oligomers under microwave irradiation catalyzed by
NaOH.405,406 Glycolysis of PET by a variety of metal or
organic catalysts yields bis(2-hydroxyethyl)terephthalester
(BHET) as the major product.403,407 Computational chemistry
provides a useful tool to study the depolymerization
mechanism, which can in turn guide the development of new
recycling strategies. In one example of glycolytic depolymeriza-
tion of PET by TBD or DBU, Horn et al.408 showed that the
rate-determining step for the depolymerization is the ethylene
glycol involved nucleophilic attack. The calculations suggest
that these reactions likely involve a bifunctional mechanism in
which the alcohol reactant activates the carbonyl group of these
polyesters while the organocatalyst activates the reacting
alcohol. The insights derived from this study led to the
development of a variety of amine-based catalytic systems for
PET depolymerization.409 The catalyst-free depolymerization
of PET and PC in supercritical alcohol410,411 or high-pressure
steam412,413 has also proven efficient for recovering high-quality
monomers equivalent to the virgin monomers produced from
petroleum.
In addition to monomer recovery, repurposing of waste
plastics into other valuable feedstocks or into value-added
polymeric materials is an attractive option for plastic recycling.
Colonna reported a two-step one-pot strategy for converting
PET to new polyesters using monomers available from
renewable sources.414 In the first step, PET was depolymerized
using isosorbide to oligomers, which were chain extended by
succinic acid in the second step to form a novel copolyester
(Scheme 18). Monobutyltin oxide was identified as the most
active catalyst for both steps and resulted in minimal
discoloration. The obtained copolyesters demonstrate proper-
ties suitable for powder coating applications.415 A similar
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strategy was applied to BPA-PC.416 Postconsumer compact
discs, mainly composed of PC, was depolymerized with
ethylene carbonate and repolymerized with isosorbide and
succinic acid to generate copolyesters for coating applications.
Recently, a quantitative one-step transformation of PC into
high-value poly(aryl ether sulfone)s in the presence of a
carbonate salt was developed as another strategy for
repurposing these plastic wastes.417 This approach uses a
cascade reaction involving the depolymerization of PC by
K2CO3 and formation of reactive phenoxides, which are then
polycondensed in situ with bis-fluorinated aryl sulfones to form
poly(aryl ether sulfone)s (Scheme 19). Computational studies
revealed that this reaction proceeds by the nucleophilic attack
of the metal carbonate on the PC and the evolution of CO2 gas
as the byproduct. Both the metal carbonate and PC are
degraded in this process, which leads to the formation of a
metal phenoxide salt that is activated for subsequent reaction
with the aryl fluoride. The computational investigation showed
that stoichiometric amounts of metal carbonate are needed for
the reaction to proceed to completion, but insights provided by
investigating the mechanism also led them to develop a
catalytic process using 12 mol % K2CO3 with lower reaction
efficiency.
The acid- or base-catalyzed hydrolysis of aliphatic polyester
and polycarbonates has also been widely explored, the results of
which have been used to guide the design and application of
these polymers for therapeutic delivery and medical im-
plants.418 The overall degradation process is a complicated
interplay between the intrinsic degradation kinetics and the
diffusive rate of water to the polymer.419,420 The rate of water
diffusion depends on the hydrophobicity of the polymer and its
shape or surface area while the intrinsic degradation kinetics is
affected by the pH421 and temperature of the medium422 as well
as the molecular weight423 and microstructures of the
polymer.424 The degradation of polyesters and polycarbonates
is in general much faster under basic conditions than acidic
conditions and under acidic conditions than neutral con-
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Scheme 20. Different Chain-Scission Mechanisms for the Hydrolysis of PLA Catalyzed by an Acid or Base
Scheme 21. Catalytic Alcoholysis of PLA to Generate Value-Added Lactate-Type Esters
ditions.421 Jung compared the hydrolytic rate of poly(D,L-lactic
acid) (PLA), poly(ε-caprolactone) (PCL), and poly(propylene
carbonate) (PPC) at various pHs (1−13).425 They found that
PPC was less susceptible to degradation in acidic medium than
PCL and PLA, with increased degradation rate as PPC ≪ PLA
< PCL. In contrast, PPC was more readily hydrolyzed in basic
conditions, with increased degradation rate being PCL ≪ PLA
< PPC. The mechanism of chain scission has been debated for a
long time. A random backbone scission and a chain-end
scission (“unzipping”) mechanism were proposed for these
polymers. Although the two mechanisms operate simulta-
neously during hydrolysis, several studies have found that the
chain-end scission is significantly faster than the random
backbone cleavage.424,426,427 This is attributed to the hydro-
philic nature of the COOH and OH chain ends compared to
the hydrophobic backbone. A detailed chain-scission mecha-
nism for PLA has been established based on model studies of
PLA oligomers.421,424,428 Interestingly, the exact chain-end
scission mechanism depends on the pH of the medium
(Scheme 20). While at acidic pH, the hydrolysis proceeds
through a preferential scission of the end groups and spits out
one lactic acid unit at a time; the base catalyzed hydrolysis
proceeds preferentially via a backbiting process from the OH
chain end leading to the formation of lactide, which is
eventually hydrolyzed to lactate. These mechanisms are
supported by the fact that when the OH chain end is capped
via acetylation, the degradation rate significantly decreases and
the relatively slow random chain scission becomes dominant.428
The conversion of aliphatic polyester wastes to value-added
small molecules and polymer precursors has been well-
demonstrated in the alcoholysis of polyesters, commodity
PLAs in particular. It provides a strategy for the production of
industrially useful small esters (Scheme 21). For example, alkyl
lactates, the alcoholysis products of PLAs, are green substitutes
for petroleum-derived esters in applications such as solvents429
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or diluents for polymeric resins,430 low-temperature lubri-
cants,431 and emulsifiers or dispersants in pharmaceutical
compositions.432 The alcoholysis of PLAs have been achieved
under different conditions,433−436 and the efficiency of these
processes is highly condition-dependent. In the early 1990’s,
Du Pont developed a method using 2−3 equiv of alcohol
(ROH for R = Me, Et, Bu) per polymer unit at 150−190 °C
with H2SO4 as the catalyst. 69−87% conversion of high-
molecular-weight PLA to lactates is achieved within 2 h.437,438
Leibfarth reported a very efficient way to recycle PLAs and
PGA to small esters using TBD as the catalyst.439 With only 1.5
equiv of alcohol per ester bond, quantitative alcoholysis to small
esters was observed in only 2 min at room temperature with
nearly complete retention of stereochemistry. The functional
group tolerance of TBD allows the introduction of different
polymerizable groups (e.g., olefin) to the ester products
(Scheme 21), which provides a number of opportunities in
the production of new polymer materials. The alcoholysis of
PLA under catalyst-free, solvothermal conditions (4 equiv of
ROH, 200−260 °C) or catalyzed by metal salts (2 equiv of
ROH, 140−200 °C) were systematically investigated by
Sobota.440 The presence of catalyst enables milder reaction
conditions and among the screened metal catalysts, magnesium
and calcium alkoxides generated in situ from the metallic
precursors and alcohols gave the best yields (>90%) and
negligible epimerization. Compared to the traditional bulk
production of lactate esters based on the esterification of lactic
acid,441,442 these catalytic alcoholyses of PLAs provide a
number of advantages, including starting materials derived
from PLA wastes, reduced reaction time and high yield, simple
purification, and retention of stereochemistry.
In addition to the production of small-molecule esters,
alcoholysis of PLAs by a substoichiometric amount of
multifunctional alcohols or amines can degrade the polymer
chains to lower-molecular-weight telechelic polyols that can be
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used for a variety of industrial processes. Plichta showed that
the degradation of PLA with less than 10 wt % diols or
diamines occurred readily in xylene at reflux or in bulk at 180−
200 °C in the presence of Sn(Oct)2, affording hydroxyl-
terminated PLAs with molecular weights significantly lower
than the pristine samples.443 The diols or diamines were
quantitatively incorporated into the degradation products. This
strategy provides a facile access to polymers with various
architectures. For example, the use of multihydroxyl com-
pounds such as dipentaerythritol results in star polymers with
six short arms of PLA. When macrodiols such as PEG are used,
a variety of triblock copolymers can be synthesized. However,
this method exerts little control over the chain length of each
block as the insertion of the diols to the PLA is random. In all
cases, the products obtained are not pure triblock structures but
contain some molar fraction of homopolymers of PLA.
Nevertheless, this study presents a practical method of chemical
repurposing of PLA to polymers and oligomers that can be
useful precursors for other processes.
4.2.2. Thermal Recycling (Pyrolysis). While monomer
recovery cannot be achieved through direct pyrolysis for step-
growth polyesters and polycarbonates, this is an attractive
recycling option for chain-growth polymers. An emerging
frontier in sustainable polymers is the design and synthesis of
thermally recyclable polymers that can be depolymerized to
their monomers in high yields, which can then be reused to
produce virgin quality polymers.23 However, controlled
depolymerization through chain-end unzipping (the exact
reverse process of chain-growth) depends on the thermody-
namics of the polymerization: for polymerization reactions that
are highly exergonic (ΔG°p ≪ 0) at normal operating
temperatures, the reverse processes are energy intensive
under similar conditions. Even so, in many cases the
depolymerization may be kinetically slow or unselective,
requiring the use of a catalyst. Catalysts developed for
polymerization can also be used for depolymerization as they
reduce the kinetic barrier of both polymerization and
depolymerization to the same extent. It will be seen from the
examples below that the use of a proper catalyst not only allows
milder depolymerization conditions but also can improve the
selectivity of depolymerization reactions.
For polyesters and polycarbonates with large polymerization
enthalpies, a simple pyrolysis process leads to undesired
products. For example, pyrolysis of PLLA at ambient pressure
leads to uncontrolled degradation through various nonradical
and radical pathways that yield a mixture of products consisting
of L-LA, meso-LA, cyclic oligomers, acetaldehyde, acrylic acid,
CO, and CO2.444−446 To drive the equilibrium toward the
formation of monomer and suppress other unwanted
degradation reactions, the thermal recycling is often performed
at lower temperature and reduced pressure to distill the volatile
monomer from the polymer melt. The use of a trans-
esterification catalyst is a key factor in promoting the selective
depolymerization under milder conditions. Kopinke et al.
compared the thermal degradation of PLAs in the absence and
presence of Sn(Oct)2.446 While the degradation without the
assistance of catalyst was slow and uncontrolled, the presence
of residual Sn (from the polymerization process) reduced the
depolymerization temperature by 60 °C and increased the
selectivity for lactide recovery. Several groups further studied
the effect of the Sn concentration on the depolymerization
efficiency. It was shown that both the depolymerization rate
and selectivity increased with Sn concentration.447−449 For Sn <
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20 ppm, the degradation proceeded mainly via random intra-
and intermolecular ester exchange, generating a significant
amount of diastereomers and cyclic oligomers.448 In contrast,
for samples with Sn > 480 ppm, the degradation kinetics
indicated an unzipping depolymerization mechanism along with
minor bimolecular transesterification reactions, leading to the
predominant production of L-LA.448,449 Acetylation of the OH
chain end significantly increased the polymer stability and
impeded the thermal recycling, consistent with an unzipping
mechanism initiated from the OH chain end.444 Other
transesterification catalysts have been used for the depolyme-
rization of PLA.450−453 Noda compared the catalytic efficiency
of a series of metal alkoxide, enolate, halide, and oxide salts for
the monomer recycling of PLLAs at 190−245 °C under 4−5
mmHg. They found that the yield and selectivity for L-LA were
dependent on the nature of the metal and increased in an order
of Al < Ti < Zr < Zn < Sn. In the presence of 1 wt % Sn(Oct)2
or zinc naphthenate, L-LA was recovered within 2 h in ∼90%
yield and over 95% selectivity.450
Selective thermal recycling of other thermodynamically stable
polyesters and polycarbonates has also been reported.454 For
example, the thermal depolymerization of PCL and poly(2,2-
dimethyl trimethylene carbonate) can be achieved in bulk at
temperature around 250 °C in the presence of a trans-
esterification catalyst. The use of Bu2Sn(OMe)2 or NaOH
facilitated a nearly quantitative depolymerization to CL, while
Ti(OiPr)4 gave almost equal amounts of CL and its cyclic
dimer. When the depolymerization of PCL was performed in
toluene with Bu2Sn(OMe)2 at 110 °C, the products were,
however, a mixture of cyclic oligomers with little formation of
CL.455 These studies once again highlight the importance of the
choice of catalyst and reaction conditions to achieve selective
depolymerization to monomer.
The recycling of long chain polyesters derived from step-
growth polymerization of ω-hydroxy fatty acids is an important
aspect of increasing the degree of sustainability of these
renewable polymers. In addition to recovering the linear repeat
units by hydrolysis, the depolymerization of these polymers
through either thermal depolymerization or solution depolyme-
rization to specific cyclic oligomers provide an attractive option
since the resulting cyclic oligomers are difficult to synthesize
through traditional cyclization methods and they can be
repolymerized to the original polymers through entropy-driven
ROP180 in a more controlled fashion than the step-growth
method. Back in 1939, Carothers has described the selective
depolymerization of polydecanoate, polytridecanoate and
polytetradecanoate at 270 °C and 1 mmHg pressure using
MgCl2 or SnCl2 as the catalyst.456,457 Depending on the starting
polyesters, either cyclic monomer or dimer were obtained in
moderate yield (50−70%) and selectivity (50−90%). Various
families of macro-lactones have later been synthesized via the
depolymerization of poly(hexamethylene succinate), poly-
(tetraethylene glycol succinate), poly(ω-hydroxy acids)
([−(CH2)x−1-CO2-]n, x = 8, 10, 11, and 12).458,459 Hodge
showed that the depolymerization of polyundecanoate in 2%
w/v chlorobenzene in the presence of a tin catalyst produced
90% yield of cyclic oligomers with cyclic dimer being the major
product (56%). The isolated cyclic dimer can undergo ROP in
neat with a tin catalyst to regenerate polyundecanoates. The
molecular weights of these polymers can be significantly higher
than the original step-growth polymers.459
Recently, Chen discovered appropriate thermodynamic and
catalytic conditions to polymerize the low-strain γ-BL into high
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molecular weight poly(γ-BL)s with cyclic or linear topologies
(Figure 11).278,460 At −40 °C and ambient pressure, the ROP
Figure 11. Chemical recycling of monomers with low enthalpies of
polymerization.
of γ-BL proceeded smoothly in the presence of a catalyst
(La[N(SiMe3)2]3 or tert-Bu-P4) to high conversions within 24
h, generating poly(γ-BL) with Mn up to 30 kDa and Đ ∼ 2.0.
The topologies of the products can be controlled by the
La[N(SiMe3)2]3/ROH ratios, with excess ROH favoring the
formation of linear chains. A clean and quantitative thermal
recycling of these polymers was achieved by simply heating the
bulk material at 220 °C (for the linear polymer) or 300 °C (for
the cyclic polymer). Alternatively, the polymer can readily be
depolymerized back to the monomer at room temperature in
the presence of a metal or organic catalyst. Chen later extended
this recycling strategy to α-methylene-γ-butyrolactone (MBL),
which is even more challenging to polymerize than γ-BL due to
the additional complication of controlling the chemoselectivity
between a reactive exocyclic olefin and a stable five-membered
lactone.177 Using similar conditions (−60 °C, Ln/ROH = 1/3)
to that of γ-BL, they were able to achieve the selective ROP of
MBL to produce poly(MBL) with Mn up to 21 kDa, which can
be facilely recycled back to the monomer MBL by heating the
polymer ≥100 °C for 1 h in the presence of catalysts. These
olefin containing polyesters present a class of useful polymer
precursors for cross-linking or thiol-addition to make functional
thermoplastics and thermosets. Hillmyer and Albertsson have
independently measured the thermodynamics of a variety of
substituted lactones and elucidated the effect of the sterics and
position of the substituent on the thermodynamics of ring-
opening.274,275 In general, substituted lactones have relatively
low polymerizability compared to the unsubstituted ones and
are thus potential candidates for thermal recycling. Hillmyer
found that β-methyl-δ-valerolactone (MVL) can be polymer-
Scheme 22. Thermal Degradation of PHBs in the Absence and Presence of a Catalyst
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ized by a highly active catalyst TBD in bulk at room
temperature to obtain a rubbery polyester,461 which can then
be selectively depolymerized back to MVL in 97% yield at 225
°C, 100 mTorr.161 On the basis of this chemistry, they
developed chemically recyclable thermoplastic polyurethanes161
and novel polyester elastomers.162 The former case exploited
the reversibility of the urethane bond to generate the OH end
group to initiate the depolymerization of PMVL block while in
the latter case a small amount of alcohol is intentionally added
to the elastomers to form the OH chain end for recycling. In
both cases, the thermal depolymerization of the materials leads
to complete recovery of MVL. Another monomer, benzodiox-
ipinone (BDP, Figure 11), was utilized by Shaver to establish a
clean and selective polymerization and recycling process using
an aluminum-salen catalyst.462 The resulting polyesters with
integrated aromatic groups are potential recyclable alternatives
for commodity polyesters like PET. These examples clearly
demonstrate the advantage of using monomers with low
polymerization enthalpies for the feedstock-recycling process.
However, their exceptional recyclability comes with several
intrinsic drawbacks. First, because of the low polymerization
enthalpy of the monomer, the polymerization reactions and
formulation/processing have to be performed at low temper-
ature (often below room temperature) in order to achieve
decent yields. This increases the energy cost of the products.
Second, the polymers are intrinsically unstable and tend to
degrade in the environmental stresses such as heat or moisture.
The low thermal stability of these materials could limit their
practical use and shelf life.
While the closed-loop recycling of PHA can be realized by
several biotic pathways,463,464 the chemical recycling of PHAs
to the constituent monomers can provide a time-efficient
option.375 Thermal recycling is the most common approach to
recycle PHAs. While uncatalytic pyrolysis performed by heating
the polymer to 500 °C under vacuum or N2 leads to the
formation of PHA oligomers, crotonic acid, and several volatile
side products (Scheme 22A),465 catalytic pyrolysis provides a
more efficient and selective degradation behavior. For example,
the use of MgO or Mg(OH)2 as the catalyst enables a selective
thermal degradation of PHB to trans-crotonic acids (Scheme
22B).466 The presence of catalyst not only allowed the pyrolysis
to be conducted at lower temperature than without a catalyst
but also suppressed the formation of oligomeric species. Similar
trend was observed for Ca2+ containing PHB.467 It is proposed
that the Lewis acidic nature of Ca2+ and Mg2+ facilitates the
activation of the six-membered transition state in the unzipping
depolymerization of PHA (Scheme 23), and thus leads to a
more selective degradation process than in the absence of
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Scheme 23. (A) Chain-End Unzipping Mechanism for Selective Thermal Degradation of PHB and (B) Influence of Mg2+ on the
Unzipping of PHB

catalysts. This catalytic pyrolysis strategy (using Mg(OH)2 as

the catalyst) was used to recycle a variety of short- and
medium-chain length PHAs and further proved the utility of
the recovered monomers as feedstocks for the microbial
synthesis of PHAs.375,381 In this way, a time- and energy-
efficient recycling between monomers (hydroxyalkanoate or
alkenoic acids) and PHAs is established.
4.3. Biological Recycling
Microbial degradation has attracted considerable interest, as
bacteria are responsible for any degradation occurring to
plastics that end up in the environment,75,76 as well as in
industrial composting settings. The first report of microbial
degradation of polyesters dates back to the early 1960’s.
Merrick and Doudoroff et al. noticed that polyhydroxybutyrate
(PHB) “granules” isolated from microbial cell extracts could be
hydrolyzed to β-hydroxybutyric acid while the polymer was
incubated with part of the cell extracts it had been purified
from.468,469 Since then, numerous studies have focused on the
degradation of aliphatic polyesters and polycarbonates by Figure 12. Aliphatic polyesters and polycarbonates amenable to
depolymerization or mineralization by microbial systems.
microbes (mainly bacteria, yeast, and fungi) or cell extracts
from these organisms, in laboratory settings or in the
environment (e.g., marine470 or soil degradation471). The
occurrence of polyesters-degrading microorganisms in the
environment has been classified as follows: PCL = PHB >
PES (polyethylene succinate) > PBS (polybutylene succinate)
> PLA.472 The structure of the aliphatic polyesters and
polycarbonates which have been shown to be susceptible to
biodegradation are depicted in Figure 12. Most experiments
have been performed in aqueous settings (i.e., aqueous
solution, sludge, or soil) with water-insoluble polymers, even
though organic solvents have also been used.
In all cases, enzymes, which are naturally occurring in
microbes (i.e., hydrolases), catalyze the material’s hydrolysis. Figure 13. Classification of the enzymes that trigger the depolymeriza-
These enzymes are either esterases, which hydrolyze esters tion of aliphatic polyesters and polycarbonates and polymers against
bonds, or proteases, which are used by microbes to cleave which activity has been demonstrated.
peptidic bonds. The most commonly studied protease is
proteinase K, which uses serine as a nucleophile. Esterases enzymes exhibit a substrate binding domain (SBD) in addition
relevant to the field of biodegradation of polyesters and to their catalytic domain, which facilitates the adsorption of the
polycarbonates, on the other hand, can be mainly categorized enzyme on the water-insoluble polymers. For the same reason,
into lipases, which cut esters of fats or PHA-depolymerases, the degradation of polyesters and polycarbonates by enzymes
which hydrolyze PHAs. These enzymes were shown to exhibit generally proceeds through surface erosion: the bulk of the
different efficacies depending on the nature of the ester/ material is not affected and the properties (e.g., molar mass,
carbonate bonds and are summarized in Figure 13.471,473 Since crystallinity, etc.) are maintained, while lower molar mass
most aliphatic polyesters and polycarbonates are hydrophobic, fragments are released from the surface.
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Microorganisms degrade polymers to use the degradation
products as carbon and/or energy source(s). High molar mass
polymers are unable to penetrate the membrane of microbial
organisms and so are not as susceptible to microbial attack by
intracellular enzymes. Therefore, microbes first express
extracellular enzymes, in order to decrease the polymer’s
molar mass and allow for solubilization and assimilation of the
oligomers through their cellular membrane. When the chains
are short enough to be soluble in the media and cross the
membrane, further degradation/digestion might take place with
the help of intracellular enzymes. If the degradation stops at the
monomeric or oligomeric stage, the process is then called
depolymerization, while mineralization is a process that further
transforms the monomeric units into CO2, H2O, and/or CH4
as end-products. The working mechanism of microorganisms
on hydrophobic polyesters and polycarbonates is summarized
in Figure 14. Noteworthy, when cell extracts are used to
depolymerize water-insoluble polymers, only steps 2 and 3 are
observed (see Figure 14).
Figure 14. Biodegradation of a water-insoluble polymer by a
bacterium (if purified enzymes are used, only steps 2 and 3 are
observed).
Various test methods have been developed to assess the
efficacy of the biodegradation, including, just to name a few,
weight loss measurements, quantification of the amount of
produced CO2 and/or CH4, analysis of the surface of the
polymer after exposure to microorganism/enzyme by micros-
copy, and analysis of the supernatant by spectroscopy or
chromatography.474,475 The efficiency of microorganisms at
biodegrading plastics have been tested in anaerobic (no O2) or
aerobic conditions (i.e., composting), as well as mesophilic
(20−45 °C) or thermophilic (≈ 55 °C) conditions. Most of
these experiments have been performed on a lab scale using soil
or sludge collected from waste treatment plants.
4.3.1. Anaerobic Bacteria. PLA, PCL, and polyhydrox-
yalkanoates (PHAs) have been shown to be susceptible to
mineralization in anaerobic conditions. The products of
anaerobic bacterial digestion are energy, which is used by the
microorganism, and CO2, CH4, and biomass. Kim et al. have
studied the biodegradation of PLA with different mesh sizes
with an initial weight content of PLA versus media of 10 wt %
and reported that the production of CO2 and CH4 could go up
to 0.21 mmol/day m2 and 0.24 mmol/day m2, respectively, for
the smaller PLA particles.476 Kunioka et al. and Itävaara et al.
showed that PLA and PLLA, respectively, could be degraded by
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soil bacteria in aquatic conditions (up to 90% after 60 days for
PLA and 50% after 40 days for PLLA).477−479 Moreover, faster
mineralization of PLLA was demonstrated in thermophilic
conditions because of the close proximity of experimental
temperatures to the Tg of PLLA.479 PCL and PHB could also
be biodegraded in similar settings (up to 90% degradation after
14 days for PHB), while PBS remained mostly intact (3%
degradation after 96 days).478 In contrast, Massardier-Nageotte
et al. reported that their inoculum was inefficient to biodegrade
both PLA and PCL in anaerobic conditions, evidencing that the
experimental settings, as well as the origin of the inoculum,
have a tremendous impact on the rate of degradation.480
Overall, anaerobic microbial degradation of aliphatic
polyesters and polycarbonates remains poorly studied, despite
several advantages such as high efficiency, especially for PLA
and PHAs, and fast rates.
4.3.2. Aerobic Bacteria. Aerobic degradation tests are
either performed in composting or aquatic conditions, mostly
using soil inocula. Because the microorganism has access to O2
in aerobic conditions, the end-products of mineralization are
CO2 and H2O, instead of CO2 and CH4 in anaerobic
conditions. The mineralization of polyesters has been evaluated
using soil (i.e., compost) or diluting the inoculum in growing
medium enriched with minerals and the rates decreased as
follows: PHAs > PCL > PLA.481−484 Similarly to anaerobic
conditions, the nature and provenance of the inoculum, as well
as the experimental setup, considerably influence the
biodegradation’s efficiency. For instance, Enoki et al. isolated
Pseudomonas, Alcanivorax, and Tenacibaculum, which were able
to partially degrade PCL and PHB fibers in deep seawater.
They found that the bacteria, after isolation, were more efficient
in experimental conditions close to their natural occurrence
[i.e., low temperature (4−10 °C) and high pressure (30
MPa)].485
A variety of soil microorganisms have also been isolated and
proved efficient for the mineralization of PLLA on agar plates
or in growing medium.486,487 Depending on the experimental
conditions, the isolation of the microorganisms/enzymes that
are thought to be responsible for the polyesters degradation can
be beneficial or detrimental. For instance, the mineralization of
PHVB was shown to be faster in fertile soil versus isolated
enzymes, owing to a more diverse population of degrading
enzymes in the soil.484 In contrast, Fukushima et al. found that
the isolation of microorganisms was advantageous to the
mineralization of PLA and PLA nanocomposites.488 Moreover,
the rate of degradation was found to be faster for PLA
nanocomposites than for pure PLA, owing to the presence of
hydroxyl moieties at the surface of nanoclay that can act as
nucleophiles.
Finally, even though most polyesters and polycarbonates are
mineralized by microorganisms, Lee et al. showed that
enantiomerically pure (R)-(−)-3-hydroxycarboxylic acids
could be produced by in vivo depolymerization of P3HB,
both in anaerobic and aerobic conditions, in Alcaligenes latus.489
They did so by suppressing the intracellular activity of (R)-
(−)-3-hydroxybutyric acid dehydrogenase, which allows
metabolizing (R)-(−)-3-hydroxycarboxylic acids to acetoace-
tate. A higher yield was observed when the bacterium was
deprived of nutrient and of light in order to block normal
pathways. This contribution elegantly showed that useful
chemicals that could be reused as monomers or in other
chemical industries could be the end-products of microbial
degradation. Ren et al. later extended this concept to a broader
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range of PHAs, allowing for the synthesis of a variety of R-
hydroxyalkanoic acids, the structures of which depend on the
parent PHA.490
4.3.3. Cells Extracts. 4.3.3.1. Depolymerases. Merrick and
Doudoroff et al. showed that a mixture of trypsin, a serine
protease, and depolymerase or cells’ extracts from Rhodospir-
illum rubrum composed of an “activator”, “depolymerase”, and
“esterase” could digest the inclusion bodies of Bacillus
megaterium containing PHB to produce D(−)-β-hydroxybutyric
ester, with up to 90% hydrolysis after 100 min.469 Since this
first report, several PHA depolymerases have been isolated on
agar plates, mainly from Alcaligenes, Pseudomonas, and
Comamonas, and their structures and properties have been
extensively reviewed.491,492 PHA depolymerases usually exhibit
a catalytic domain containing an esterase sequence, often
similar to lipase, and a substrate-binding domain (SBD) to
enable adsorption of the enzyme at the surface of hydrophobic
PHAs.493 Several studies have been dedicated to the substrate-
binding domain of PHA depolymerases. For instance, Maeda et
al. showed by AFM that the adhesive force of the SBD of
PhaZRpiT1 was around 100 pN and that single mutations in the
SBD to more hydrophobic amino acids allowed for faster rates
of hydrolysis.494,495 Moreover, the polymerase’s SBD and
insoluble PHA are thought to interact through hydrophobic
effects but also molecule-specific contacts.496 Because of this
mechanism of action, adding a higher amount of enzyme
increases the efficiency of the degradation up to an inhibitory
concentration that is detrimental to the degradation rates,
owing to saturation of the substrate that prevents the catalytic
site from interacting with the polymer.497
The efficiency of depolymerases was mostly evaluated in Tris
or PBS buffer solutions with pH ranging from 7.5 to 9.8, to
ensure stability of the enzyme. In a systematic study, Doi et al.
demonstrated that PHB-depolymerase of Alcaligenes faecalis,
Pseudomonas stutzeri, and Comamonas acidovorans could only
degrade polyesters with 2 or 3 carbon atoms between each ester
bond and only −H or −CH3 substituents on their backbone
[i.e., poly-3-hydroxybutyrate (P3HB), poly-3-hydroxypropio-
nate (P3HP), and poly-4-hydroxybutyrate (P4HB)], or AA/BB
polyesters exhibiting a −O−CH2−CH2−O− motif (i.e.,
polyethylene succinate and polyethylene adipate).493 The
rates for the best depolymerase/polyester pairs were up to
0.28 g/h/cm2. Depending on the provenance of the PHB
depolymerase, either monomer and dimer of 3-hydroxybutyric
acid497 or oligomers can be obtained.498−500 Doi et al. also
reported that the surface erosion of P3HB and P3HB-co-P4HB
was faster while carrying surface erosion with PHB-depolymer-
ase at 37 °C than by uncatalyzed hydrolytic bulk erosion at 55
°C.498
Several reports mentioned that the purity and crystallinity of
the PHAs had an influence on the efficacy of the
degradation.469 PHB depolymerase hydrolyses PHB chains
both by exo (chain ends) and endo (middle of the chain)
attacks, as both linear and cyclic PHB could be hydrolyzed by
this enzyme. Interestingly, PHB depolymerase can disturb the
molecular packing of P3HB in crystals, thus facilitating
hydrolysis.501,502 Lenz et al. studied the effect of tacticity and
crystallinity of PHB on the efficiency of PHB depolymerase and
showed that the rates of degradation were decreasing following
the trend: atactic> isotactic> syndiotactic. They also concluded
that PHB-depolymerases needed at least a [R]-unit diad in
order to catalyze hydrolytic cleavage.503
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4.3.3.2. Lipases. Lipases are the most-studied enzymes for
the hydrolysis of polyesters and polycarbonates as they degrade
a broad spectrum of polymeric structures. Commercially
available lipases mainly originate from porcine pancreas,
Pseudomonas, or the yeast Candida antarctica. Lipase B from
Candida antarctica was expressed in Aspergilus niger and
immobilized on acrylics beads and is commercialized as
Novozym 435. Lipases were shown to degrade PCL,504−508
PLA,504,505 PLLA,509 poly(γ-butyrolactone),507 PHB,508,510
poly(butylene succinate adipate),511 PCL/PBS blend,511 and
poly(propylene carbonate)508 in PBS at 37 °C, producing
mainly short oligomers. The rates of hydrolysis varied
tremendously with the microorganisms/tissue the lipase was
extracted from and the polymer.507,512 Overall PCL degrades
the fastest with quantitative depolymerization obtained with
Pseudomonas lipase after 4 days in aqueous media, and the
addition of PLA or PPC to PCL greatly decreases this rate.
Noteworthy, Vert et al. showed that Pseudomonas lipase could
break down the crystalline domains of PCL within days in
contrast to hydrolytic degradation that would take several years
to do the same.504 Finally, the ability of lipases to degrade
polycarbonates in buffer has been linked to the glass transition
temperature of the polymer.513
The influence of organic solvents on the degradation of
aliphatic polycarbonates and polyesters with lipases has been
investigated. The addition of organic solvents is advantageous
to the solubilization of the polymers but can have a detrimental
effect on the stability of the enzyme. Lipases are thought to
only trigger esterification and transesterification reactions in dry
organic solvents, while the presence of water allows for
hydrolysis.514 In early studies, Kobayashi et al. showed that the
water/organic solvent ratio and the chosen organic solvent had
a strong influence on the degradation products of PCL:
macrocycles were obtained in toluene and in dry isopropyl
ether, while the addition of ≈0.2% H2O in isopropyl ether led
to the formation of linear oligomers.515 After solvent
evaporation, these oligomers could be repolymerized in bulk
using the same lipase catalyst. The same strategy was applied to
PBA and polyesters made from a 13-membered lactone with
lower yields. The specific chain cleavage of lipases, as compared
to random scission for uncatalyzed hydrolysis, was demon-
strated. Madras et al. reported the coefficients of enzyme
deactivation and of polymer degradation, kd and ks, respectively,
for PLA, PCL, PGA, and their copolymers using Novozym 435
and Lipolase, an engineered lipase from fungus, in several
organic solvents and at different water contents.516,517 Acetone
allowed for the faster degradation and DMSO was the less
efficient solvent, evidencing that overall, the depolymerization
rate increased with higher solvent polarity and lower solvent
viscosity. PTMC could be depolymerized to TMC in
acetonitrile at 70 °C with recovery yields up to 80%.518
Matsumura et al. investigated the degradation of PHB, PCL,
and PBA in mixtures of supercritical CO2 (sCO2) and organic
solvents or water with lipase from Candida antarctica. In flow
conditions (15 MPa) with 80% sCO2 and 20% toluene at 40
°C, more than 99% of the products were cyclic oligomers (210
< Mn < 1010 g/mol).519 In contrast, traces of H2O in sCO2 (18
MPa) triggered the formation of dicaprolactone (i.e., 1,8-
dioxacyclotetradecane-2,9-dione) from PCL in yields higher
than 90%, therefore allowing for a full recycling cycle.520 Using
the same lipase, Joly et al. demonstrated that PBS could be
transformed to succinic acid (44% yield) by reactive extrusion
at 120 °C (30 min, 10 wt % lipase).521 Finally, lipases are also
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Chem. Rev. 2018, 118, 839−885
Chemical Reviews
thought to catalyze the hydrolysis of lipid ester groups in water
insoluble aggregates like membranes and vesicles.522
4.3.3.3. Proteases. Proteases which use serine as the
nucleophile for the hydrolysis of peptidic bonds, also called
serine proteases, also showed activity for the depolymerization
of aliphatic polyesters and polycarbonates. The most potent
one, proteinase K, was first extracted from the fungus
Tritirachium album and is a broad-spectrum protease known
to hydrolyze keratin. Proteinase K is stable in the 8−8.6 pH
range and is particularly efficient to degrade PLA.523,524 In
contrast, the depolymerization of poly(glycolic acid),525
PCL,523,524 PHB,523 or poly(trimethylene carbonate)525 with
proteinase K is slower than with the aforementioned enzymes.
As for most enzymes, the efficiency of proteinase K at
degrading semicrystalline polymers increases with decreasing
crystallinity contents. For instance, crystalline PLA could not be
degraded by proteinase K.525,526 However, Wei and Li et al.
showed that proteinase K degraded PLLA faster than PDLA,
mostly owing to higher adsorption of the enzyme at the surface
of PLLA as compared to PDLA.527 In a thorough study on the
influence of the chirality of PLA on the degradation activity of
proteinase K, they also evidenced that LL, DL, and LD diads
could be cleaved but not DD diads.
5. CONCLUSIONS AND OUTLOOK
In this review, we describe the challenges and opportunities in
the design and development of sustainable polymers that
exhibit closed-loop life cycles. These challenges were discussed
in the context of polyesters and polycarbonates as representa-
tive materials to illustrate key principles for the generation of
sustainable polymers. “Innovation leverage points” (Figure 1)44
were introduced to describe where new science and catalytic
technologies might lower the technological barriers to achieving
closed-loop life cycles in a systems-level analysis where all
aspects of the plastics life-cycle are considered, which include
the natural resources that provide the feedstocks and
monomers, as well as the means of converting these to
polymer products, their life cycles, and the end-of-use options.
One of the most formidable challenges for the development
of sustainable polymers is the economic vitality and success of
the current plastics industry, whose development over the past
half century was spawned by access to relatively cheap energy
and feedstocks derived from petrochemical refining and 60
years of breathtaking scientific and technological develop-
ments.528 The evolution of the successful socioeconomic
ecosystem that has led to our current model of resource
utilization to one that provides incentives both for environ-
mentally sustainable as well as economically sustainable
industrial processes and materials will require systems-level
changes at all levels of society, including academic and
industrial scientists and engineers, industrial ecologists,
economists, social scientists, policy makers, and consumers.
Critical to that evolution are technology options for more
sustainable alternatives to our current practices.
Additional challenges for sustainable polymers are ongoing
developments to establish quantifiable goals, indices, and
metrics to assess whether a particular activity or plastic is
more sustainable than existing processes or materials.7−10 This
is an important and active area of research and will be critical to
guide future research and industrial development.3 The
development of materials that exhibit closed-loop life cycles
will require scientific and economic innovations at every stage
of a plastics life cycle.
871
Review
Catalysis is an enabling science that impacts every step of the
plastics life cycle. Many catalytic approaches have been
developed to transform renewable raw materials to versatile
monomers and to further convert these monomers to existing
or new polymer materials. The development of renewable
monomers, the versatile synthetic routes to convert these
monomers to polyesters and polycarbonate, and the different
end-of-use options for these polymers are critically reviewed,
with a focus on recent advances in catalytic transformations that
lower the technological barriers for developing more
sustainable replacements for petroleum-based plastics. Among
the potentially sustainable alternatives to current commodity
plastics, aliphatic polyesters and aliphatic polycarbonates are
highlighted as they can be derived from renewable resources,
they can be produced by a variety of versatile synthetic
methods, they exhibit a wide range of useful properties, and
they can be repurposed to versatile synthetic intermediates or
environmentally degraded if they end up in the environment.
The different catalytic routes to synthesize these polymers from
renewable monomers are surveyed in this review. Significant
progress has been made in increasing the catalytic activity
(turnover frequency), productivity (turnover number), and
selectivity toward desired product formation over side reactions
and regio- or stereoselectivity. Recently, catalytic systems that
enable the control of polymerization on a more sophisticated
level such as architectures and monomer sequences are
emerging. While metal-based catalysts are in general more
competent in tackling the aforementioned challenges, organo-
catalysts have emerged as an efficient alternative. While a
variety of active and selective catalysts are available for
converting renewable monomers into well-defined polymers,
data to assess their environmental impacts or sustainability are
incomplete. Nevertheless, some sustainability metrics and
indicators such as green design principles can be used to
assess different catalytic methods based on their adherence to
green design principles.
The end-of-life options of plastics are critical for the
development of circular plastics economies, but economic
disincentives have contributed to the modest rates of recycling
and material recovery. More efficient chemical and biochemical
processes are needed to provide better technology options for
preserving and recapturing the value of plastics at the end of
their useful life. Considerable efforts have been focused on
biodegradable polymers that can be decomposed naturally or in
composting sites by microorganisms. The end products are
primarily CO2, H2O, and other metabolites that can re-enter
the life cycle. Although this end-of-life option mitigates some of
the issues associated with indiscriminate disposal of plastics in
the environment, it is not the only or even best option for
capturing value. Further developments in the generation of
polymers that can be selectively depolymerized to the original
monomers or other building blocks are needed to provide more
energetically efficient means of preserving the economic and
chemical investments made in generating these materials.
Materials that are designed to be both chemically recyclable and
environmentally biodegradable are excellent candidates for
circular material economies and represent the ideal end-of-life
option for sustainable polymers. For such system to work at
scale, we envision the need for an integrated infrastructure that
takes on waste collection and sorting, depolymerization, and
purification of recovered feedstocks. Similar to mechanical
recycling, plastic sorting and tolerance to contaminants in the
plastics feeds presents a significant challenge for chemical
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Chem. Rev. 2018, 118, 839−885
Chemical Reviews
recycling. Ideally, mixed chemical recycling facilities that are
able to handle multiple depolymerizations from mixed materials
flows are preferable.
The development of more sustainable alternatives to our
current model of linear resource utilization is a crucial but
formidable challenge for the development of sustainable
industrial processes, including those involving the production,
use, and recycling of plastics. The innovations over the past 60
years that have provided the economic engine for our current
plastics economies have been breathtaking. Future innovations
are needed to ensure that the materials of the next century will
not only be economically sustainable, but will be sourced,
produced, utilized, and repurposed such that they can address
the needs of current and future generations.
AUTHOR INFORMATION
Corresponding Author
*E-mail: waymouth@stanford.edu.
ORCID
Xiangyi Zhang: 0000-0003-4290-1600
Mareva Fevre: 0000-0001-6460-9227
Robert M. Waymouth: 0000-0001-9862-9509
Notes
The authors declare no competing financial interest.
Biographies
Xiangyi Zhang received her Bachelor’s Degree in 2008 from Nanjing
University, China, where she did her undergraduate research with
Professor Jing-lin Zuo on electroactive diruthenium complexes for
molecular electronics applications. She obtained her Ph.D. in
chemistry from Stanford University in 2017 under the supervision of
Professor Robert M. Waymouth. Her doctoral research focuses on the
development of organocatalytic approaches for the synthesis of
functional polyesters and polycarbonates as sustainable alternatives
to petroleum-based plastics. She is currently working as a Senior
Chemist at the Dow Chemical Company in Midland, MI.
Mareva Fevre received her Ph.D. in Chemistry 2012 from the
University of Bordeaux, France, working on organocatalyzed polymer-
ization reactions and the precise synthesis of polymeric ionic liquids,
under the supervision of Prof. Daniel Taton. In 2012, she moved to a
postdoctoral position at Duke University to study elastin-like
polypeptides-containing recombinant proteins for anticancer applica-
tions. Since joining IBM Almaden Research Center in 2014, she’s been
part of some of IBM’s programs leveraging polymer science for the
preparation of high performance materials, as well as for biomedical
applications, including the design of new antimicrobial and antiviral
materials.
Gavin O. Jones is a research staff member in the Computational
Chemistry and Materials Research group at IBM Research−Almaden.
He earned his Bachelor’s degree at Bard College and completed his
Ph.D. in theoretical/computational organic chemistry at the University
of California Los Angeles with Prof. Kendall Houk. He performed
postdoctoral research with Prof. Stephen Buchwald at the
Massachusetts Institute of Technology. He has interests in
mechanisms, catalysis, molecular properties, and polymer formation
and degradation. He was awarded with Foreign Policy Magazine’s
Global Thinker Award (Innovator Category) in 2016.
Robert M. Waymouth received bachelor’s degrees in mathematics and
chemistry from Washington and Lee University and his Ph.D. from the
California Institute of Technology in 1987 with Professor Robert H.
872
Review
Grubbs. Following a year of postdoctoral research with the late
Professor Pino at the ETH in Zurich, he joined the faculty at Stanford
University in 1988, where he is now the Robert Eckles Swain Professor
of Chemistry. His research interests are in homogeneous catalysis and
polymer chemistry.
ACKNOWLEDGMENTS
We thank Professor Geoffrey W. Coates and Dr. Scott Allen for
their insights and discussions in framing the content of this
review. We also acknowledge the Ellen MacArthur Foundation
for their constructive comments in revising the manuscript. The
authors thank the National Science Foundation (GOALI CHE-
1607092) and the Department of Energy (DE SC0005430) for
financial support. X.Z. acknowledges a Stanford Graduate
Fellowship and a LAM Graduate Fellowship.
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NOTE ADDED AFTER ASAP PUBLICATION

This paper was published to the Web on October 19, 2017,
with errors in Figure 3 and Scheme 3. These were corrected in
the version published to the Web on October 24, 2017.

885 DOI: 10.1021/acs.chemrev.7b00329

Chem. Rev. 2018, 118, 839−885