Review

pubs.acs.org/IECR

New Chemistry in Functional Aliphatic Polyesters

Rong Tong*
Department of Chemical Engineering, Virginia Polytechnic Institute and State University, 635 Prices Fork Road, Blacksburg, Virginia
24061, United States

ABSTRACT: Aliphatic polyesters are important biodegradable poly-

mers with wide applications. Polyesters prepared by ring-opening
polymerization often have a limited range of properties, because of the
minimal functional diversity of available lactone monomers. In this
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review, synthetic strategies in preparing functional lactone monomers

are highlighted, as well as recent controlled polymerization strategies to
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synthesize functional aliphatic polyesters, which include proton-transfer

polymerization, ring opening polymerization of O-carboxyanhydrides,
radical ring-opening polymerization of cyclic ketene acetals, and copoly-
merization of epoxide/anhydride.

1. INTRODUCTION because of the minimal functional diversity of available lac-

Polyesters can generally be divided into semiaromatic and
aliphatic polyesters. Semiaromatic polyesters such as poly-
(ethylene terephthalate) are used in a variety of bulk applications,
because of their good mechanical strength and other character-
istics, which will not be discussed here. Aliphatic polyesters are
widely used in everyday applications ranging from clothing and
packaging to agriculture and biomedicine.1−7 They are regarded
as potentially sustainable alternatives to petroleum-based poly-
mers, because of their numerous renewable sources, hydrolytic
degradation to benign products, and high biocompatibility.8
One of the most common routes to polyesters in industry
is the step-growth polymerization of diacids or diesters with
diols. However, such method is energy-intensive because a small-
molecule byproduct, water or an alcohol, is removed at high
temperature. In addition, this polymerization usually have a
broad molecular weight distribution (dispersity (Đ) or Mw/Mn,
where Mw is the weight-average molecular weight and Mn the
number-average molecular weight), ∼2.9,10
Alternatively, aliphatic polyesters are preferred to be prepared
through chain-growth ring-opening polymerization (ROP) of
lactones.11 Such polymerization has been studied extensively,
and a wide variety of initiators, including organocatalysts, metal
alkoxides, and various metal complexes, has been explored
and reviewed elsewhere (Figure 1).12−21 However, polyesters
prepared by this method often have a limited range of properties,
tones, which further prevents the post-polymerization function-
alization. Besides the ROP of lactones, other polymeriza-
tion pathways such as proton-transfer polymerization, ROP of
O-carboxyanhydrides, radical ROP of cyclic ketene acetals, and
copolymerization of epoxide/anhydride have been recently
developed to prepare functional polyesters. In this review, I will
not only discuss the preparation of functional lactone monomers
but also highlight recent strategies to synthesize functional aliphatic
polyesters via controlled polymerization.
2. FUNCTIONAL LACTONES FOR RING-OPENING
POLYMERIZATION
One general strategy to prepare functional polyesters is to
polymerize functional lactone monomers. Prior to the discussion
of synthetic strategies, it is worth mentioning that the thermo-
dynamic polymerizability of lactones is strongly related to ring
size; and computational studies show that ring strain is highest
for β-propiolactone (4-membered ring) and much lower for
γ-butyrolactone (5-membered ring) and δ-valerolactone
(6-membered ring).22 This explains that only a limited number
of 5-membered lactone monomers were reportedly used for
ROP.23 Notably, the modification of polyester by transforming
functional groups post-polymerization has been extensively
reviewed24−27 and will not be discussed here.
2.1. β-Lactone. β-lactone can usually be prepared via the
catalytic asymmetric [2 + 2] cycloadditions of ketenes and
aldehydes,28−32 which, in most cases, require the isolation of
enolate equivalents such as silyl ketene acetals.33 Carbonylation
of epoxides using catalysts of the form [metal-based Lewis
acid]+[Co(CO)4]− has recently emerged as a reliable direct

Received: February 6, 2017

Revised: March 22, 2017
Accepted: March 23, 2017
Figure 1. Ring-opening polymerization of lactone and lactide. Published: March 23, 2017

© 2017 American Chemical Society 4207 DOI: 10.1021/acs.iecr.7b00524

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Figure 2. Regioselective synthesis of β-lactone via the carbonylation of epoxide.
approach to β-lactones when using terminal or symmetrically
2,3-disubstituted epoxides as substrates (Figure 2).34,35 Regio-
selective carbonylation of asymmetric disubstituted epoxides can
also be achieved to prepare either cis- or trans-β-lactones using
the same catalyst system.36,37
2.2. Lactide. Homobifunctional lactide can be prepared via
the dimerization of functional α-hydroxyl acids catalyzed by
p-toluenesulfonic acid under reflux (Figure 3a).38−41 The yields
of these lactides were relatively low (<40%). On the other hand,
heterobifunctional lactides can be prepared by condensation
of functional α-hydroxyl acids with α-haloacyl halides or
α-halocarboxylic acids to form functional esters, followed by
ring cyclization reaction of these esters (Figure 3b).39,40,42−50
Figure 3. Strategies of lactide functionalization.
The first condensation step could usually achieve high yields
whereas the ring cyclization step was often performed via the
intermolecular nucleophilic substitution with moderate or low
yields (<60%), which impede the scaleup.
Another approach to prepare functional lactide is to modify
the concomitant lactide. Monobrominated lactide can be pre-
pared by bromination of L-lactide with N-bromosuccinimide, and
an exomethylene lactide can be further obtained by simple
dehydrobromination (Figure 3c).51 The alkene bond generated
from those reactions can be utilized for a broad variety of reac-
tions, including Diels−Alder reactions with various dienes.52,53
2.3. Medium-Sized Lactone (6- to 9-Membered).
2.3.1. Cyclization. Similar to the lactide synthesis, the ring
cyclization of lactone (or lactonization) is challenging. The main
problem arising in the lactonization is the competition between
intramolecular and intermolecular reactions leading to the
formation of diolide and oligomers.54 The lactonization can be
achieved either through the activation of an acid or the activation
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of an alcohol,55 via a “high dilution technique” by slowly adding
reagents to a large volume of solvent over many hours.56
To intermolecular side reaction, a “pseudo-high-dilution
technique” was developed by immobilizing the seco-acid
(the carboxylic acid for the lactonization), or an activated inter-
mediate, on a solid support.57−60 The use of a metal ion can
function as a “template” to accelerate the intramolecular reac-
tion.61−64 Other methods that stimulate high dilution conditions
have also been described for the synthesis of lactones,65−68
including solid−liquid phase-transfer catalysis, and reactions in
microemulsions, in inverse micelles and in zeolites.
2.3.2. Baeyer−Villiger Oxidation of Cyclic Ketone. The most
applied approach to produce lactones, e.g., ε-caprolactone, is the
Baeyer−Villiger oxidation of cyclic ketones that are prepared by
cyclic alcohol via Chapman−Stevens oxidation (Figure 4a).69−72
Figure 4. Strategies of functionalization of medium-sized lactone.
Especially, the asymmetric Baeyer−Villiger oxidation of racemic
or prochiral cyclic ketones to optically active lactones provides a
simple and attractive methodology; moreover, numerous
catalysts, including biocatalysts,73,74 chiral metal catalysts,75−79
and organocatalysts,80−82 have been developed. Outstanding
examples using such oxidation pathway to prepare lactones for
polymerization include 1,5-dioxepan-2-one,83,84 α-chloro-cyclo-
hexanone,85 γ-bromo-ε-caprolactone,86 and 2-oxepane-1,5-
dione.87
2.3.3. Alkylation of α-Position in Lactones. Alternatively, the
α-position of lactone can be alkylated or halogenated via the
use of a strong base (e.g., lithium diisopropylamide) to intro-
duce various functional groups,88−94 such as the alkyne group
(Figure 4b). The click chemistry can be achieved after the
polymerization of alkyne-functional ε-caprolactone to graft PEG,
chemotherapy drugs, lipids, or peptides onto the polyester.91,95−97
2.3.4. Other Methods. Recently, the Michael addition of
nucleophile (e.g., thiol) to α,β-unsaturated δ-lactone has been
exploited to graft functional groups onto lactone,98 which allowed
for the scalable synthesis of functional lactones to build a polyester
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library for siRNA delivery (Figure 4c). In addition, several
other interesting methodologies, including metal-catalyzed ring
expansion of cyclobutanones,99 metal-catalyzed carbonyla-
tion,100−103 and N-heterocyclic carbene catalyzed ring expansion
of aldehydes104 have been developed to expand the scope to prepare
lactones.
3. PROTON-TRANSFER POLYMERIZATION
Proton-transfer polymerization is a polymerization in which each
propagation step involves a proton transfer, which regenerates
the active propagating species or activates the monomer or the
nucleophile.105 Early examples of base-catalyzed proton-transfer
polymerization mainly focused on the polymerization of
acrylates to polyesters, e.g., acrylic acid to poly(β-propiolactone),
instead of polyacrylate via vinyl addition pathways.106−115
The monomers for the proton-transfer polymerization are
usually acrylic and epoxide monomers bearing acidic protons
such as hydroxyls.116 Recently, a new type of proton-transfer
polymerization has been developed to allow for the polymer-
ization of acyclic acrylate monomers without protic groups
into unsaturated polyesters catalyzed by N-heterocyclic carbenes
(see Figure 5).117,118 The selected N-heterocyclic carbene
Figure 5. Scheme of proton-transfer polymerization of dimethyl acrylate
catalyzed by N-heterocycle carbene.
catalyst promoted umpolung intermolecular condensation
coupling via proton transfer; the addition of phenol into the
reaction eliminated the radical-induced polymerization and
facilitated the proton transfer in the chain propagation. The
resulted polyester had a high thermal stability and can be readily
cross-linked to robust polyester materials.
4. RING-OPENING POLYMERIZATION OF
O-CARBOXYANHYDRIDES
O-carboxyanhydrides (OCAs) have emerged as an alternative
class of highly active monomers for the synthesis of poly(α-
hydroxy acids).119−122 OCAs can be readily available from α-
amino acid precursors, which inherently possess rich side-chain
functionality,119,121 including aromatic groups,123−126 carboxylic
acids,127,128 alcohols,129 and amines.127 OCAs thus provide
significant potential for building complex structures for various
applications, including drug delivery, gene delivery, and tissue
Figure 6. Ring-opening polymerization of O-carboxyanhydrides: (a) epimerization of the polymerization catalyzed by organocatalyst
4-dimethylaminopyridine, and (b) stereoregularity control of polymerization catalyzed by the (BDI)Zn complex (where BDI represents a
β-diiminate ligand).
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engineering.122 Of note, to my knowledge, no six or higher-
membered OCA monomer has been reported for ROP.
4.1. Polymerization of OCAs by Organocatalysts. OCAs
are mostly polymerized by N-heterocyclic carbenes130 or
pyridine-based organocatalysts, such as dimethylaminopyridine
(DMAP),121 into the corresponding polymers through a non-
covalent basic/alcohol activation mechanism, using primary or
secondary alcohols as initiators (Figure 6a).131 The ROPs are
well-controlled in most cases with narrow Đ (<1.2). However,
DMAP showed less efficiency when a tertiary alcohol was used as
initiator.127 Moreover, DMAP caused significant epimerization of
the stereogenic center (α-proton) and loss of isotacticity in the
polymerization of malic-OCA,128 mandelic-OCA,124,132 and Ser-
(Bn)-OCA.132 The increased acidity of α-proton in these OCAs
proposedly interfered with basic DMAP catalysts; the use of ion pair
of pyridine with an equimolar mandelic acid improved the con-
trolled ROP of mandelic-OCA (Đ ≈ 1.1−1.2; Mn up to 48 kDa)
with high levels of isotacticity.124 In addition, only a few examples
using organocatalysts can mediate the preparation of high-
molecular-weight polyester (over 100 kDa),129 suggesting that the
transesterification might occur in the high degree of polymerization.
4.2. Polymerization of OCAs by Organometallics. An
alternative to the use of organocatalysts for the ROP of
OCAs involves the use of organometallic catalysts,123 such as
metal alkoxides that have been shown to polymerize lactones in a
highly controlled manner.12 However, currently, only a few
metal catalysts can mediate controlled ROP of OCAs;122,132,133
whereas many metal alkoxides that are capable for ROP of
lactones did not work for OCAs in a controlled manner.133,134
Currently, only (BDI)Zn-based complexes can initiate con-
trolled ROP of various OCAs without epimerization, superior to
that catalyzed by DMAP (Figure 6b).132 These Zn complexes
can also copolymerize OCA with lactide, indicating that the chain
propagation of OCAs is similar to that of lactide, through active
Zn-alkoxide chain terminus. Preliminary mechanism studies
suggest that monomeric Zn complex had better control on the
ring-opening of OCAs than dimeric Zn complex.132 However,
similar to organocatalysts, none of the metal complexes have
been used to prepare high-molecular-weight polyester. Besides,
no stereoselective organometallic complex has been developed
for ROP of OCAs, which is drastically different from enormous
studies of stereoselective ROP of lactones and lactides.
5. COPOLYMERIZATION OF EPOXIDE AND
ANHYDRIDE
Another alternative chain-growth route to aliphatic polyesters
is the alternating copolymerization of epoxides and cyclic
anhydrides.135−137 Both monomers are readily available from
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commercial resources. Numerous organometallic catalysts have

been developed for the copolymerization, including magnesi-
um,138,139 aluminum,137,140−148 chromium,144,149−153 manga-
nese,144,146,154,155 iron,141,156 cobalt,140,144−146,153,157 nickel,158
and zinc138,159−163complexes, many of which show markedly
higher activity with the addition of a nucleophilic co-catalyst such
as bis(triphenylphosphine)iminium (PPN) salts and DMAP. Of
note, at high temperatures (110 °C), PPN salts or DMAP can
catalyze the copolymerization without an organometallic Figure 8. Scheme of radical ring-opening polymerization of cyclic
complex.146,156,164 Other organocatalysts for the copolymeriza- ketene acetal.
tion include Lewis bases, such as tertiary amines, and quaternary
onium salts.164−166 Because many metal complexes can also be in the regiocontrol and stereocontrol of polymerization. Recently,
used in polycarbonate and polyester, terpolymerization of a few regioselective catalysts have been developed for the
epoxide/anhydride/CO2167,168 and epoxide/anhydride/lac- copolymerization of epoxide and anhydrides (Figure 7a).
tone154,161,169 has been developed to alter polymer backbone’s A bimetallic Cr complex was first discovered to regioselectively
functionality. Quarterpolymerization of lactone/epoxide/anhy- copolymerize (S)-phenyl glycidyl ether with maleic anhydride,
dride/CO2 was recently achieved by the use of a bimetallic Zn with 98.5% head-to-tail linkages.152 Enantiopure (salcy)CoNO3
catalyst.170 with electron-withdrawing chloro groups on the ligand yielded
5.1. Regioselective Copolymerization of Epoxide/ isotactic poly(propylene succinate) with 96%−97% head-to-tail
Anhydride. Organometallic catalysts are often advantageous linkages.157 An achiral (salph)CrCl catalyst regioregularly

Figure 7. (a) Regiochemistry and (b) stereochemistry control of copolymerization of epoxide/anhydride. (c) The elimination of epimerization of
copolymerization of epoxide/anhydride.

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Table 1. List of Glass-Transition Temperatures and Melting Temperatures of Various Aliphatic Polyesters

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Table 1. continued

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inserted (S)-propylene oxide in copolymerization with tri-
cyclic anhydride, yielding 94% head-to-tail linkages.142 The
combination of a nitro axial group and electron-withdrawing
fluoro groups on the ligand of (salcy)Co complexes yielded
the most regioregular polyesters for a wide range of anhydrides
and propylene oxide.171 For most of the regioselective
copolymerization, the ring opening of epoxide usually
happens on the methylene of epoxide with less steric bulk
groups. Studies also suggested that the increase of the
Lewis acidity of a metal complex by changes in metal and
ligand could result in an enhanced epoxide activation and
likely increase the regioselectivity of the epoxide ring-opening
step.135
5.2. Stereochemistry Control. In terms of stereochemistry
control, though isotactic polyesters can be prepared by
enantiopure epoxides and anhydrides,142,151,152,157,171 no pub-
lished results show that enantioselective or isoselective catalysts
can copolymerize racemic epoxides and anhydrides to prepare
stereoregular polyesters. A recent progress has been made on
the copolymerization of meso-epoxide with cyclic anhydride: An
(R,R,R,R)-enantiopure bimetallic Al(III) complex efficiently
catalyzed the copolymerization to form isotactic (R,R)- enriched
polyesters with 91% ee via the selective attack of the (S)-carbon
in the epoxide (Figure 7b).148
5.3. Control of Epimerization. In unsaturated polyesters,
the control of epimerization of asymmetric carbons at the
α-position becomes critical in the copolymerization, which can
dramatically affect polymer’s physicochemical properties such as
Tg. Thermodynamically, the trans configuration is more favorable
than the cis conformation, which causes the epimerization at the
α-position. The use of a chromium or cobalt catalyst in excess
epoxide reportedly led to significant epimerization, decreasing
the polymer’s Tg value by more than 30 °C. An aluminum catalyst
was found to greatly reduce epimerization for bulky anhydrides,
allowing the retention of 98% of the cis-diester linkages, even at
high conversion.142 Lately, by replacing the tert-butyl groups
in the para position of the ligand with fluoro groups in the
aluminum catalyst, the epimerization can be effectively sup-
pressed for less bulky anhydrides, suggesting that the amount
of epimerization was correlated with the electron-donating
capability of the ligand (Figure 7c).171 Besides, the ratio of
epoxide to anhydride and the exo/endo stereochemistry of the
anhydride also affect the extent of epimerization. When excess
epoxide was used, the resulting polymers were >99% trans,
whereas with excess anhydride or a 1:1 ratio of epoxide/
exoanhydride, the polymers preferentially had cis configura-
tion.142,164 In addition, only one example of controlled
cis/trans isomerization of an alkene has been reported in the
epoxide/anhydride copolymerization. In such case, catalytic
diethylamine was added to poly(propylene maleate) to give
poly(propylene fumarate), with unchanged Mn and increased
Tg values.149
5.4. Molecular-Weight and Polydispersity Control.
Many epoxide/anhydride copolymerizations have been
plagued by high Đ values, because of transesterification at
high monomer conversion. The presence of adventitious
water or hydrolyzed anhydride also lower Mn values more
than expected.140 The highest-molecular-weight polyester
reportedly has an Mn value of 167 kDa for poly(propylene
phthalate) and a relatively narrow dispersity at full conversion
(Đ = 1.21).172 The preparation of high-molecular-weight
materials (over 100 kDa) remains a key challenge to address,
particularly because the increase in molecular weight above
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the chain entanglement molecular weight can improve the
materials’ physicochemical properties for many potential
applications.135
6. RADICAL RING-OPENING POLYMERIZATION
Radical ring-opening polymerization (rROP) for polyesters was
developed in the 1980s173−175 to polymerize cyclic monomers
bearing vinyl or exomethylene groups via a radical pathway
(Figure 8).176 Therefore, the functional group (e.g., ester or
ketone) can be incorporated in the polymer main chain. One
advantage of rROP is that it allows the copolymerization of
exomethylene-bearing cyclic monomers (e.g., 2-methylene-1,
3-dioxepane, MDO) with various vinyl monomers, such as
styrene,177 methyl methacrylate,178 vinyl acetate, etc.,175,179,180
which potentially change the mechanical properties of the
polyester (e.g., the low shrinkage copolymer prepared by
rROP).181 However, most of these rROPs were performed
using conventional radical-polymerization techniques without
the control over molecular weight; side products, such as
polyacetal, were often found in the product (Figure 8). Recently,
few studies applied the modern reversible-activation radical
polymerization techniques to control the rROP process,176
including atom-transfer radical polymerization for the copoly-
merization of MDO-type monomer with various acrylates,182−184
and reversible addition−fragmentation chain-transfer polymer-
ization for the copolymerization of MDO with vinyl acetate or
vinyl bromobutanoate.185,186 Notably, no high-molecular-weight
polyesters (over 100 kDa) with narrow Đ has been prepared via
rROP.
7. PERSPECTIVE
Because of the decreasing reliance on fossil fuels and plastic
waste problems, it is unequivocally crucial to continue to develop
biodegradable polymers from renewable sources. Currently,
aliphatic polyesters have only a few large-scale commercial
products, including polylactide and poly(lactide-co-glycolide).
Over the past 20 years, many strategies have been developed to
functionalize polyesters with various physicochemical properties
(e.g., wide range of Tg from −70 °C to 180 °C; see Table 1).
Although great progress has been achieved, a few synthetic
challenges still await solutions, including (i) identification of poly-
ester with comparative physiochemical properties as polyolefin;
(ii) the control of polyester’s molecular weight (especially high
molecular weights over 100 kDa); (iii) regiochemistry and
stereochemistry control for new controlled polymerization; and
(iv) scale-up process of monomers and polymers. In addition, the
preparation of well-defined functional polyesters integrated
with therapeutic or imaging agents is of great interest for drug
delivery and tissue engineering.122,187,188
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: rtong@vt.edu.
ORCID
Rong Tong: 0000-0002-2034-9272
Notes
The author declares no competing financial interest.
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Industrial & Engineering Chemistry Research
BIOGRAPHY
Professor Rong Tong received his Ph.D. degree in Materials Science
and Engineering from the University of Illinois at Urbana−Champaign
in 2010, working on the synthesis and formulation of novel polymeric
nanomedicines for targeted cancer therapy. He then became
Postdoctoral Fellow at both Massachusetts Institute of Technology
(Langer Laboratory) and Harvard Medical School (Kohane Labo-
ratory). In 2015, he joined the Department of Chemical Engineering at
Virginia Polytechnic Institute and State University. His research
interests include polymer chemistry, nanomedicine, biomaterials, and
targeted cancer therapy. He is the recipient of the Siteman Center for
Cancer Nanotechnology Fellowship (2007), Racheff−Intel Award
(2009), and American Chemical Society AkzoNobel Award in polymer
chemistry (2010).
■
ACKNOWLEDGMENTS
This work was supported by start-up funding from Virginia
Polytechnic Institute and State University. This invited con-
tribution is part of the I&EC Research special issue for the 2017
Class of Influential Researchers.
■
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