European Polymer Journal 118 (2019) 668–684

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European Polymer Journal

journal homepage: www.elsevier.com/locate/europolj

Bio-based routes to synthesize cyclic carbonates and polyamines precursors T

of non-isocyanate polyurethanes: A review
Mehran Ghasemloua, Fugen Daverb, Elena P. Ivanovac, Benu Adhikaria,
⁎

a
School of Science, RMIT University, Melbourne, VIC 3083, Australia
b
School of Engineering, RMIT University, PO Box 71, Bundoora, VIC 3083, Australia
c
School of Science, RMIT University, Melbourne, VIC 3000, Australia

ARTICLE INFO ABSTRACT

Keywords: The synthesis of conventional polyurethanes (PUs) relies on isocyanate reactants as crucial starting materials.
Diisocyanate-free Toxicity, water-sensitivity and phosgene-based synthesis of isocyanates have made it necessary to undertake
Non-isocyanate polyurethanes systematic and focused research to develop environment-friendly processes that use ecofriendly and non-ha-
Bio-based zardous materials. Among the numerous pathways that have been proposed, the reaction between cyclic car-
Renewable materials
bonates and polyamines is shown to be the most promising route for the synthesis of non-isocyanates poly-
urethanes (NIPUs). The past decade has witnessed a consistent trend that seeks to take advantage of the vast
reserve of renewable feedstocks such as vegetable oils, terpenes, lignin derivatives, and polyols as starting
molecules for the synthesis of NIPU precursors. More recently, numerous strategies have come to the fore seeking
to utilize the abovementioned renewable resources for the synthesis of NIPUs to meet the prerequisites of green
chemistry. In this context, this review aims to shed light on recent progress that has been made in this direction.
It also critically reviews the various green routes that have been pursued towards the synthesis of NIPU and their
precursors to pave way for their applications in the PU industry. The challenges currently faced by industry in
making use of these renewable (NIPUs and their precursors) materials into large-scale production is also
highlighted.

1. Introduction
Polyurethanes (PUs) are probably the most versatile class of poly-
meric materials that possess exceptional properties such as abrasion
resistance, elasticity, durability, and toughness. In light of the benefits
that PUs offer in terms of overall performance, they have widespread
applications in many areas such as foams, footwear, coatings and
paints, industrial machinery, adhesives, packaging and medical devices
[1]. PUs are also one of the most extensively researched polymers to
meet the need of continuously growing global market. Despite offering
these advantages, the synthesis of PU suffers from several drawbacks
that if persisted, can negatively impact their future applications. The
conventional PU synthesis relies primarily on the polyaddition reaction
between a diisocyanate (or polyisocyanate) and an oligomeric polyol
(Scheme 1a). The major drawback of producing PUs using this approach
is that the key monomer (isocyanate) is derived from petrochemical
materials. Furthermore, the phosgenation reaction commonly used in
the industrial synthesis of isocyanates, makes another downside due to
the involvement of lethal and reactive phosgene gas [2]. Exposure to
these highly toxic gaseous compounds has found to be associated with
respiratory problems, eye and/or skin irritation, and even death [3].
Furthermore, the irreversible reaction of isocyanate groups with water
often results in the formation of unusable by- products. This can be-
come problematic in industrial production because it demands stringent
safety precautions during synthesis, transportation, and storage of PUs.
Moreover, there are several negative aspects associated with iso-
cyanate-based PUs, especially at the end-of-life due to the formation of
toxic substances when waste products are burned and/or landfilled [4].
Since the early 1990s, the limited availability of fossil-based feed-
stocks, the need to ensure the safety of workers and consumers, com-
bined with the growing awareness of environmental concerns have
urged industries and researchers towards developing environmentally
benign strategies to synthesize PUs. Moreover, due to increased focus
on green chemistry, research groups and industries are incentivized to
replace hazardous substances and harsh reaction conditions with safe
and green processes. Therefore, these drawbacks have motivated con-
tinued research focus in developing green routes by using renewable
and non-hazardous materials and led to the development of non-

⁎
Corresponding author.
E-mail address: benu.adhikari@rmit.edu.au (B. Adhikari).

https://doi.org/10.1016/j.eurpolymj.2019.06.032
Received 6 May 2019; Received in revised form 16 June 2019; Accepted 23 June 2019
Available online 24 June 2019
0014-3057/ © 2019 Elsevier Ltd. All rights reserved.
M. Ghasemlou, et al.
Scheme 1. Two common routes to synthesize PUs and PHUs through (a) isocyanate-based route that uses reaction between a polyol and a polyisocyanate and (b)
non-isocyanate-based route that uses reaction between a cyclic carbonate and a polyamine.
isocyanate polyurethane (NIPU). At the beginning of the 21th century,
NIPUs began to receive special attention in both academic and in-
dustrial research because of its potential impact on the global PU
market [5]. Nowadays, this route seems to be the best possible alternate
for synthesis of PUs. In the industrial practice, NIPUs can be manu-
factured by step-growth polyaddition reaction of cyclic carbonates and
polyamines leading to the formation of polyhydroxyruethanes (PHUs)
(Scheme 1b). The low reactivity of the cyclic carbonates towards
polyamines implies a low polymerization rate in comparison to the high
reactivity of isocyanate-based precursors towards polyols. Moreover,
the presence of side products such as urea, or oxazolidones may prevent
achieving the production of a desired monomer with high conversion
rate [6]. Apart from these drawbacks, the prevention to use hazardous
isocyanate reactants and more importantly the opportunity to use a
wide range of precursor materials derived from renewable resources
distinguish this route from conventional PU routes. Hybrid Coating
Technologies is perhaps the first commercial company which is man-
ufacturing polyurethane coatings and paint products produced from
renewable source under the tradename of Green Polyurethane™. Ac-
cording to this company isocyanate-free foams are still under research
development stage while hybrid coatings and acrylic polymers modified
by NIPU are commercially available [7]. The large array of publica-
tions, reviews and patents in literature on the potential replacement of
synthetic cyclic carbonates with renewable analogues can attest to the
increasing interest in this field. For example, replacement of cyclic
carbonate precursors by vegetable oils has been proposed in several
recent reviews [8–12]. Natural vegetable oils have shown to have great
promise to be used as green precursors for NIPU synthesis. These past
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European Polymer Journal 118 (2019) 668–684
few years have also seen a continuous effort in the PU industry to take
advantage of other renewable resources such as terpenes [13], iso-
sorbide [14], tannin and lignin derivatives [15,16], vanillin [17], and
glycerol [18] as raw starting materials for the cyclic carbonate and
subsequent NIPU synthesis. In conjunction with this research direction,
we have undertaken a systematic study to gain an in-depth under-
standing of the possibility of using materials from renewable resources
such as starch to improve some technical properties of both starch and
PUs. To provide a proof-of-concept and to make use of high reactivity of
precursors of polyurethanes, starch-PU thermoplastic hybrids were
produced. The improvement of various techno-functional character-
istics of these starch-PU hybrids such as mechanical, structural and
hydrophobicity validated the application of PU in renewable materials
[19–21]. Despite the ongoing interest into this area, the NIPU route
suffers from a lack of due research focus in order to find alternatives to
currently used organic amines with their bio-based equivalents. It is
noteworthy to mention that the majority of NIPU materials discussed in
the literature are only partially renewable. This is because most works,
so far, are focused on finding ways to replace synthetic cyclic carbo-
nates with the ones derived from renewable sources. That is, most of the
established NIPU methods are still using the organic non-renewable
polyamines. Therefore, it would not be appropriate to call these NIPU
materials fully renewable while synthetic materials still remain in their
backbone. The development of environment-friendly processes that use
renewable precursors for the synthesis of NIPU should place an em-
phasis on starting materials (cyclic carbonates and polyamines) and
should not be confined to only one precursor. There are several op-
portunities to obtain polyamines from renewable sources for the
M. Ghasemlou, et al.
synthesis of green NIPU materials; this aspect has not received much
attention in the recent literature. To highlight this area and to com-
plement previous reviews on this topic, this review aims to system-
atically and critically evaluates the literature that cover various routes
for the synthesis of NIPU precursors that are derived from renewable
sources. It places special focus on polyamines to pave way for their
applications in the PU industry.
2. Synthetic routes for NIPU
Groszos and colleagues are believed to be the pioneers who devel-
oped a novel process to synthesize NIPU by using aminolysis of bis
(cyclic carbonate) [22]. Since then, NIPU synthesis has become one of
the hotspots and as a consequence, several other routes have been
suggested. As summarized in Fig. 1, there are four main routes to obtain
a NIPU: polycondensation, rearrangement, ring-opening-polymeriza-
tion and polyaddition.
There are numerous reviews that have recently been published to
describe these NIPU synthetic routes in greater detail [23–26]. Re-
garding the polycondensation route, the reaction between poly-
chloroformate and polyamine, polycarbamate and polyol, poly-
carbamoyl chloride and polyol, or polycarbonate and polyamine can
lead to NIPU materials. However, because the synthesis of all involved
Fig. 1. Main synthetic routes for developing non-isocyanate polyurethanes (NIPUs).
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European Polymer Journal 118 (2019) 668–684
precursors has a connection to phosgene or its derivatives, this route
has encountered difficulties in its industrialization [27]. Moreover, the
need to conduct the reaction in the presence of a catalyst and at high
temperatures (ca. 150–220 °C) together with the release of by-products
such as HCl or alcohols, are other obstacles that have restricted the
extension of polycondensation to commercial scale [2]. The synthesis of
NIPUs by rearrangement seems to be more environmentally friendly
than conventional routes, although the presence of harmful reactants
such as acyl azides, carboxamides and hydroxamic azides makes this
route less preferable. The third route for the synthesis of NIPUs is ring-
opening-polymerization of aliphatic cyclic carbamates or aziridines.
This route not only suffers from the involvement of phosgene precursor
in the synthesis of cyclic carbamates but also carries the toxicity of
aziridines. Additionally, the need to use elevated temperatures can be
challenging even though it does not generate any by-products [27].
Finally, cyclic carbonates, either with five- or six-membered rings, can
undergo polyaddition reaction with polyamines resulting in the for-
mation of materials called polyhydroxyurethane (PHU) [28–30]. NIPU
synthesized through this route has received a great deal of interest from
both academia and industry [4]. The polyaddition reaction can be
carried out at ambient temperatures although a moderately high tem-
perature (ca. 60–80 °C) can greatly help in achieving high conversion
rate. The versatility of this route lies in the fact that no hazardous
M. Ghasemlou, et al.
Scheme 2. Mechanism of reaction between five-membered cyclic carbonates and amines through formation of a tetrahedral intermediate.
Scheme 3. Synthetic pathway of NIPU production from vegetable oil-based
materials based on refs [34,50,51].
isocyanate or phosgene are involved. The isolation or avoidance of
moisture is not necessary in this reaction system because NIPU syn-
thesized through this pathway is not susceptible to water contained in
the air or on the substrate [23]. Moreover, not only cyclic carbonates
and polyamines have limited or manageable toxicity, but a wide range
of biodegradable, renewable and sustainable resources can be con-
veniently converted into the corresponding bio-based precursors sui-
table for this reaction [2]. On the other hand, the possibility of syn-
thesizing PU materials without emission of volatile organic compounds
endorses its applications for coating purposes. The presence of hydroxyl
groups located at the β-carbon atom adjacent to the urethane group can
further contribute in intramolecular and intermolecular hydrogen
bonding with the urethane carbonyl group [8]. Due to the presence of
these hydrogen bonds, NIPUs generally exhibit higher water uptake and
enhanced resistance to organic solvents, compared to urethane groups
synthetized through conventional routes [3]. Considering excellent
benefits offered by this route and because of the current investment of
main PU industrial sections such as BASF, Bayer, Dow and Huntsman on
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European Polymer Journal 118 (2019) 668–684
this promising reaction and its potential growth in the global market,
this route is reviewed herein.
3. Polyaddition between cyclic carbonate and polyamine
Garipov et al. [31] studied the kinetic features of the reaction be-
tween cyclic carbonate and amine and proposed that the reaction can
proceed in three steps (Scheme 2).
In the first step, an amine-functionalized group attacks the carboxyl
group present in cyclic carbonate. This nucleophilic attack leads to the
formation of a tetrahedral intermediate. The deprotonation of tetra-
hedral intermediate and the removal of hydrogen ions as a consequence
of the attack from another amine group is considered to be the second
step of this process. In the third step, the presence of strong electron
withdrawing effect of nitrogen atom initiates the breakage of the
carbon-oxygen bond that ultimately yields PHU. Depending on the
structure of intermediate compounds, the reaction between cyclic car-
bonate and diamines can result in the formation of two isomers when a
five-membered cyclic carbonate is involved or a single PHU product
when a six-membered cyclic carbonate is involved. When the reaction
involved the five-membered cyclic carbonates, two isomers with a ur-
ethane moiety and a hydroxyl group in their backbone are formed. The
only difference is that one of these isomers contains a primary hydroxyl
group, whereas the other contains a secondary hydroxyl group. As
mentioned earlier, these hydroxyl groups can form intermolecular hy-
drogen bonds with the urethane group [32]. The six- and seven-mem-
bered cyclic carbonates are found to have a higher reactivity and
polymerization rate towards amines than five-membered cyclic carbo-
nates. The lower reactivity of five-membered cyclic carbonates ne-
cessitates the increase of reaction temperature to moderately high level
(e.g., 80 °C) in the presence of a catalytic system to achieve a high
conversion rate of cyclic carbonate groups [33]. Moreover, the aliphatic
polyamines are known to readily react with cyclic carbonates than
aromatic polyamines [34]. Selva et al. [35] indicated that aromatic
amines tend to react with cyclic carbonates at very high temperatures
(∼140 °C) in the presence of a phosphonium-based ionic liquid as
catalyst. It was found that decarboxylation occurred and alkylated
amines were the major components in the reaction mixture. In another
study, Guo et al. [36] demonstrated that a catalyst is required to fa-
cilitate aminolysis of cyclic carbonates by aromatic amines.
4. Cycloaddition reaction to synthetize cyclic carbonates
Cyclic carbonates are generally viewed as the primary constituents
for polyaddition with diamines. There are three main synthetic routes
to produce these reactants: (i) transesterification of diols with alkylene
carbonates, (ii) carboxylation of epoxy precursors with CO2 in the
presence of a catalytic system [13] and (iii) synthesis of cyclic carbo-
nates from diols by reacting with CO2 in the presence of a catalytic
system [37,38]. It is worth mentioning that several epoxy compounds
are quite toxic however, because of variation in their reactivity (due to
their molecular geometry) they are not equally hazardous. The highest
risk of exposure to epoxides is believed to be in workplaces where these
M. Ghasemlou, et al.
Scheme 4. Synthesis of renewable bis(cyclic carbonate) derived from creosol based on Ref. [69].
compounds are produced or used [39]. Despite these disadvantages the
production of cyclic carbonate from epoxy compounds is of particular
interest [31]. The increased interest in this reaction lies in its ability to
use the highly abundant greenhouse gas (CO2) to produce valuable
chemicals. This route sometimes uses relatively high pressure and ele-
vated temperatures [40], although atmospheric pressure and mild
temperatures are often involved [41,42]. The possibility of using var-
ious types of catalysts that can simultaneously increase the electro-
philicity of the cyclic carbonate group, or nucleophilicity of the amine
group have been recently investigated [26,43–45]. Among them, metal-
free systems such as tetrabutylammonium bromide (TBAB) were found
to be more effective than organometallic catalysts or quaternary am-
monium salts in opening oxirane rings and subsequent CO2 fixation
[25]. Additionally, because an increased utilization of bio-based and
renewable feedstocks is aligned with the mission of green chemistry,
there is an emergence of many routes that claim switching from fossil-
based cyclic carbonates to alternative green resources. To highlight this
area, we aim to overview some of the most common routes used to
develop precursors of NIPU from renewable sources.
Scheme 5. Synthesis of renewable bis(cyclic carbonate) derived from syringaresinol based on Ref. [70].
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European Polymer Journal 118 (2019) 668–684
5. Bio-based routes for cyclic carbonate synthesis
5.1. Vegetable oil derivatives
Vegetable oils (triglycerides) are promising renewable feedstocks
that can be advantageously exploited as the reliable platform to develop
NIPUs with a wide range of structural and functional properties. Due to
their non-toxicity, inherent biodegradability, eco-friendliness, low cost
and inherent functionality (ester functions and unsaturation), they
seem to be the best alternatives for replacing fossil-based feedstocks for
PU synthesis [46,47]. Due to these advantages, increasing attempts
have been made to improve the efficacy of vegetable oils as a chemical
platform for the development of thermoset and thermoplastic PHUs. It
has been shown that vegetable oils usually possess several active moi-
eties that are amenable to chemical modification and can be efficiently
converted into new precursors for NIPU synthesis. These vegetable oils
can be easily converted into epoxidized analogous which readily react
with CO2 to produce vegetable oil-derived poly(cyclic carbonate)s
(Scheme 3) [48,49]. Finally, PHUs can be produced via a reaction
M. Ghasemlou, et al.
Scheme 6. Synthesis of renewable bis(cyclic carbonate) derived from vanillin based Ref. [17].
between these poly(cyclic carbonate)s and polyamines [34,50,51]
Many different epoxidized vegetable oils are readily available com-
mercially at a low cost and can be directly used to synthetize carbo-
nated vegetable oils. To support this idea, many research groups
worldwide have intensely investigated the synthesis of PHU networks
from oils obtained from many different plants such as soybean [52–54],
linseed [55], sunflower [56,57], and palm [58], using different cata-
lysts. Non-edible vegetable oils such as rubber seed oil [59,60] and
cardanol [61,62] have also been explored as green feedstocks for the
synthesis of NIPU. For example, Tamami et al. [52] successfully de-
veloped carbonated soybean oils from their epoxidized equivalents by
incorporating CO2 at atmospheric pressure and a high temperature
(110 °C) in the presence of tetrabutylammonium bromide (TBAB) as the
catalyst.
These authors showed that the resultant carbonated soybean oils
could easily react with different amines at 60 °C to produce PHUs.
Under a similar strategy, Poussard et al. [63] synthesized fully bio-
based NIPUs by reacting epoxidized soybean oil to CO2 under super-
critical conditions (100 bar, 120 °C) using TBAB as the organocatalyst.
Further reaction was carried out with short diamines, derived from bio-
based fatty acids, to synthesize thermoplastic NIPUs. Similarly, Doley,
and Dolui [64] used sunflower oil as a raw material for the synthesis of
Scheme 7. Synthesis of bis(cyclic carbonate) from tannic acid based on Ref. [71].
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European Polymer Journal 118 (2019) 668–684
PHUs. Carbonated oils used in this study were obtained by reaction of
CO2 with pre-epoxidized sunflower oil under a high pressure (100 bar)
and high a temperature (120 °C) in the presence of TBAB. Another
successful demonstration of this concept was made by Boyer et al. [65]
who synthetized linear thermoplastic NIPUs through the transester-
ification of sunflower oil with pentane diol followed by a metathesis
reaction to incorporate terminal double bonds. These double bonds
were sequentially epoxidized, carbonated and polymerized with dif-
ferent diamines. In another study, Bähr and Mülhaupt [51] prepared
carbonated soybean oil and linseed oil in the presence of TBAB and
silica-supported alkylpyridinium iodide as catalysts. The carbonated oil
reacted with various diamines to produce NIPU. Samanta et al. [3]
adopted a similar approach but choosing two long-chained diamines
derived from two different plant oils to synthesize NIPUs. Some car-
boxylic acids can be extracted from renewable feedstocks, particularly
vegetable oils. For instance, sebacic acid is industrially manufactured at
a low cost from ricinoleic acid, which itself is extracted from castor oil.
This renewable resource has been recently shown to be capable of
forming a bis(cyclic carbonate) in the presence of glycerol carbonate. It
can then be reacted with diamine to synthesize new bio-based NIPUs
[66]. Another example of this process was reported by Liu et al. [67]
who synthesized a rosin-based cyclic carbonate via cycloaddition
M. Ghasemlou, et al.
Scheme 8. Synthesis of cyclic carbonate via catalytic conversion of the glycidyl ethers of glycerol, pentaerythritol and trimethylolpropane with carbon dioxide based
on Ref. [18].
Scheme 9. Synthesis of renewable cyclic carbonates derived from meso-ery-
thritol and D-sorbitol based on Ref. [74].
reaction of the triglycidyl ester of maleopimaric acid extracted from
rosin. This cyclic carbonate was reacted with CO2 to produce NIPUs
using ring-opening polymerization with diamines.
5.2. Lignin derivatives
Lignin-based bisphenols can be viewed as important green alter-
natives for the synthesis of cyclic carbonates. Their application as
precursors in NIPU synthesis is appreciated mainly due to their aro-
matic structure and hydroxyl functionalities [68]. For example, Chen
et al. [69] prepared a new bis(cyclic carbonate) by glycidylation reac-
tion of creosol-based renewable bisphenol, with epichlorohydrin in the
presence of NaOH, followed by a cycloaddition reaction with CO2 in the
presence of TBAB and benzyltriethylammonium chloride (BnEt3NCl)
(Scheme 4).
The resultant bis(cyclic carbonate) then contributed in a polyaddi-
tion reaction with different diamines. Janvier et al. [70] explored the
feasibility of using syringaresinol, a bisphenol lignin-based renewable
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European Polymer Journal 118 (2019) 668–684
material, to synthetize new bio-based bis(cyclic carbonate) (Scheme 5).
After incorporation of different diamines into syringaresinol-derived
cyclic carbonates, thermoplastic PHUs with glass transition tempera-
ture (Tg) ranging from 63 to 98 °C were synthesized.
Vanillin is another promising biomolecule for producing cyclic
carbonate precursors. Fache et al. [17] obtained bifunctional cyclic
carbonates from vanillin by incorporating CO2 into the epoxidized
compounds in the presence of LiBr-catalyst (Scheme 6).
Tannic acid is another bio-based polyphenol that has found in-
creasing applications as a renewable raw material for the synthesis of
NIPU. Esmaeili et al. [71] recently made use of this compound and
synthesized a bio-based cyclic carbonate through a glycidylation reac-
tion of tannic acid to transform it into an epoxidized form. This epox-
idized form of tannic acid made it reactive for chemical fixation with
CO2 in the presence of TBAB as a catalyst at 70 °C (Scheme 7). The
resultant cyclic carbonates were then allowed to react with various
aliphatic and aromatic amines to produce PHU networks.
Ferulic acid, which is easily obtained from lignocellulosic biomass,
can also be used for this purpose. This was revealed by Ménard et al.
[72] who developed a method to prepare ferulic acid-based bis(cyclic
carbonate) precursors for the synthesis of thermoset and thermoplastic
PHUs. Another study by Zhang et al. [12], reported a synthesis of bio-
based cyclic carbonate using 2,5-furandicarboxylic acid (FDCA) derived
from cellulosic biomass— via insertion of CO2 into diglycidyl ester of
FDCA in the presence of tetraethylammonium bromide (TEAB) as a
catalyst.
5.3. Polyols
Polyols such as pentaerythritol or trimethylolpropane can be pro-
duced enzymatically by first converting starch into mono-, di- or oli-
gosaccharides and then hydrogenation of the resulting product.
Fleischer et al. [18] studied the synthesis of carbonated glycidyl ethers
from renewable polyols such as glycerol, pentaerythritol and tri-
methylolpropane by catalytically adding CO2 into their oxirane rings in
M. Ghasemlou, et al. European Polymer Journal 118 (2019) 668–684

Scheme 10. A four-step process for synthesis of sorbitol tricarbonate from glycerol feedstock based on Ref. [77].

Scheme 11. Synthesis of bis(cyclic carbonate) derived from limonene based on

Ref. [13].

the presence of TBAB (120 °C for 10 h) (Scheme 8).

The resulting cyclic carbonate products were cured with hexam-
ethylenediamine and citric acid amino amides to produce NIPUs. Cyclic
carbonate precursors can also be synthesized by transesterification of
multifunctional hydroxyl compounds. For example, Fidalgo et al. [73]
converted D-mannitol into a bifunctional and linear carbamate using
phenyl orthoformate followed by a ring-opening polymerization with
diamines in the presence of N,N-diisopropylethylamine at 80 °C for 2 h
to produce NIPUs. Mazurek-Budzynska et al. [74] transformed sugar Scheme 12. Synthesis of bis(cyclic carbonate) derived from cardanol based on
polyols such as meso-erythritol and D-sorbitol into cyclic carbonates by work of Ref. [79].
carrying out reactions at 80 °C for 3 h with dimethyl carbonate (DMC)
in excess methanol and potassium carbonate acting as the catalyst
(Scheme 9). (Scheme 10).
Bis(cyclic carbonate)s derived from both sugar polyols were then
employed as new precursors to react with various diamines to synthe- 5.4. Terpene derivatives
size a wide variety of crosslinked PHUs. Recently, Furtwengler and
Avérous [75] synthesized a bis(cyclic carbonate) from D-sorbitol using Terpene substances—which are known as highly unsaturated and
an environment-friendly process in the presence of DMC under reduced ester-free— are readily available in large-quantity, and more im-
temperature (∼75 °C) and in the absence of any solvent, achieving portantly offer unique opportunities to be converted into precursors for
conversion rate of 50%. Aouf et al. [76] devised a two-step chemical NIPUs synthesis. Bähr et al. [13] reported a new terpene-based NIPU
synthetic route to exploit natural phenolic substances like gallic acid to synthetic route using cyclic limonene decarbonate. The combination of
produce bio-based epoxy groups. This route was relied on the glyci- TBAB as a catalyst, elevated pressure (30 bar) and a temperature of
dylation of gallic acid, which was performed through the alkaline-as- 140 °C enabled them to incorporate 34.4% of CO2 into limonene di-
sisted allylation of hydroxyl groups followed by the epoxidation of the oxide (Scheme 11). The authors then crosslinked these cyclic limonene
resulting double bonds. The glycidylated products were then cured with dicarbonates with various diamines to synthesize PHUs.
isophorone diamine to be converted into NIPU crosslinked materials.
Recently, Schmidt et al. [77] developed a green method to synthetize 5.5. Cardanol
sorbitol tricarbonate from glycerol feedstocks. In their method, acro-
lein— a by-product of biodiesel industry— was first dimerized and Cashew nut shell liquid (CNSL), is a non-edible byproduct of the
carbonated by transesterification with diethyl carbonate. The resultant cashew shell industries. Cardanol, a main component of CNSL, can af-
product was further oxidized to produce a new highly reactive 4,5- ford many opportunities to develop green and sustainable materi-
diepoxy-2-yl-1,3-dioxolan-2-one that could be converted into sorbitol als—including NIPUs— owing to its long unsaturated aliphatic chain
tricarbonate by exposure in CO2 at 60–80 °C in the presence of TBAB and phenolic nature [78]. Kathalewar et al. [79] studied the possibility

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Table 1
Summary of important physico-chemical properties of NIPUs that are derived from renewable-based cyclic carbonate and polyamines.
Cyclic carbonate Polyamine Reaction conditions Molecular weight (gr mol−1) Thermal properties Refs.
[Dispersity index]

1,6-hexanediamine, 1,8-diaminooctane, and DMF, 140–180 °C Mn: 3900–7000 [2.6–4.3] Tg = 63–113 °C [80]
isophorone diamine Td5% = 240–279 °C

1,6-hexanediamine DMAC, diglyme, THF, Mn: 14000–60000 [1.4–1.6] Tg = 64–79 °C [81]

25–80 °C, 12–24 h Tm = 160–190 °C
Td = 180–224 °C

Polyamine 70 °C, 8 h Mn: 432 Tg = 20–53 °C [18]

Jeffamine D-400, 1,10 diaminodecane, DMF, LiBr as catalyst, RT, Mn: 7500 and 8600 [2.6–6.3] Tg = −8–59 °C [14]
diethylenetriamine and isophorone diamine 12 h Td5% = 234–255 °C

Ethane-1,2-diamine and isophorone diamine Bulk, no catalyst, Mw: 4300–13500 [1.1–1.5] Tg = −25 to −13 °C [65]
70–115 °C, 9–12 h

butane-1,4-diamine, isophorone diamine, Bulk, 70–140 °C, 1–15 days Mn:11000–31000 [1.2–2.9] Tg = −29–55 °C [82]
the Priamine 1075 and Jeffamine 400

hexamethylene diamine and isophorone Bulk, catalyst, 120–150 °C, Mn:2857–4569 Tg = −12–31 °C [79]
diamine 0.5 h [2.71–6.80]

Priamine, 2 grades with fNH2 = 2.0 and 2.2 Bulk, 75 °C, 2 h and inert Mn:6000–9000 [2.5–3.1] Tg = −23 to −14 °C [66]
gas

tris(2-aminoethyl)amine, decane diamine Bulk, 80–160 °C, 18 h Mn:2000–5400 Tg = 47–98 °C [70]

and isophorone diamine [1.5–4.9] Td5% = 267–280 °C

Priamine 1075 and Jeffamine D-2000 Bulk, DMF, inert gas, 75 °C, Mn:4550–10750 [1.8–3.1] Tg = −50–25 °C [83]
1–12 days

1,4-butane diamine, 1,6-hexamethylene Bulk, 60 °C then gradually Mn: 960–1840 [1.2–1.5] Tg = 33–70 °C [13]
diamine, 1,12-dodecane diamine and to 120 °C Tm = 80–100 °C
isophorone diamine

(continued on next page)

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Table 1 (continued)

Cyclic carbonate Polyamine Reaction conditions Molecular weight (gr mol−1) Thermal properties Refs.
[Dispersity index]

1,6-diaminohexane and isophorone diamine DMSO, TBD (catalyst), RT- Mn: 1100–46000 Tg = 44–90 °C [69]
110 °C, 24 h Td5% = 244–308 °C

Isoidide diamine butane-1,4-diamine, Bulk, RT-110 °C, 5 h Mn: 4900–13500 [1.8–3.2] Tg = −7–66 °C [84]
pentane-1,5-diamine and nonane-1,9- Td10% = 229–259 °C
diamine

1,10-decanediamine Bulk, DMF, 70 °C, nitrogen Mn: 7500–20500 [1.4–1.9] Tg = −26–26 °C [85]
atmosphere, no catalyst, Td5% = 200–274 °C
7 days

1,4-butanediamine, isophorone diamine and Bulk, 5 h at 80 °C Mn: 4000–10000 Tg = 17–72 °C [72]

decane diamine followed by 10 h at 100 °C. Td = 241–276 °C

Scheme 13. Synthetic pathway of L-lysine from cellulose and its conversion to pentanediamine. Corynebacterium glutamicum directly converts cellulosic biomass
into L-lysine. 1,5- pentanediamine is then produced by decarboxylation of L-lysine in the presence of lysine decarboxylase.

to synthesize cyclic carbonate from CNSL and demonstrated that it
could be synthetized via CO2 addition reaction into epoxidized-car-
danol at 120 °C with an elevated CO2 pressure together with TBAB
serving as the catalyst (Scheme 12).
The cyclic carbonates obtained in this way were further allowed to
react with diamine in the presence of triethylamine as the catalyst.
Another demonstration of using cardanol was presented by
Dworakowska et al. [78] who developed new bio-based epoxy foams
using epoxidized cardanol and fatty acid-based diamine. Table 1 pre-
sents a summary of the structure, reaction condition and some techno
functional properties of NIPUs obtained from a reaction between re-
newable materials based cyclic carbonates and polyamines.
6. Bio-based routes for polyamine synthesis
While renewable bio-based materials can be utilized as building
blocks for the synthesis of cyclic carbonate, they can also be con-
currently used as building blocks for the synthesis of polyamines. As
mentioned earlier, numerous synthetic routes have been developed to
produce cyclic carbonates from bio-based renewable sources. However,
very little information is available on the synthesis of ‘green’ amines
through renewable routes. Therefore, to highlight this area, some
commonly used routes to synthesize polyamines that are applicable for
NIPU synthesis are reviewed herein.
6.1. Amino acids
Amino acids can be considered as renewable materials and can be
used to produce precursors for the synthesis of polyamines because of
the presence of the nitrogen atom in their structure. Decarboxylation of
amino acids can lead to formation of either mono- or bifunctionalized
amines, depending on the structure of the starting molecules [86].
Among others, lysine is the most studied amino acid for polymer
synthesis. Today, lysine is industrially manufactured through the fer-
mentation of sugars or other carbon sources with an impressive value of
1.2 × 106 metric tons per year. Lysine can be chemically manipulated

Scheme 14. Synthetic pathway of lysinol from L-lysine.

677
M. Ghasemlou, et al.
Scheme 15. Amination of grapeseed oil using cysteamine hydrochloride via
UV-initiated thiol-ene chemistry based on Ref. [98].
and used as a sustainable platform for the synthesis of NIPU [87]. The
abundant availability, low cost and the presence of two amine and one
acid functional groups has made lysine one of the most promising
candidates for the synthesis of polyamines. It is worth mentioning that
the polyamine precursor for NIPU synthesis is required to have at least
two amine groups in its structure in order to have more reactivity to-
wards cyclic carbonates and achieve a high conversion rate. Lysine can
undergo decarboxylation reaction and converted into 1,5-pentanedia-
mine (also known as cadaverine) (Scheme 13) [88].
Lysinol is another renewable feedstock that can be obtained via the
catalytic hydrogenation of lysine under elevated temperatures and
pressure (Scheme 14) [87].
Lysinol is an aliphatic diamino alcohol with a very similar structure
to ethylenamines and ethanolamines Lysinol has potential capacity to
be used as a precursor to react with cyclic carbonates to produce NIPU.
Cysteamine— a degraded product of cysteine— has received con-
siderable interest for PU synthesis. Thiol-ene coupling reaction of cy-
steamine by itself or its salt, is one of the well-known routes to syn-
thesize polyfunctional amines from renewable resources [89–91]. For
example, Cornille et al. [89] developed a two-step process to synthesize
bio-based amines from pentaerythritol by esterification of the hydroxyl
Scheme 16. Synthesis of 1,4-butanediol or 1,4-butanediamine from succinic acid.
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European Polymer Journal 118 (2019) 668–684
group with an alkyl chain and subsequent thiol-ene coupling reaction
with the cysteamine hydrochloride on the allyl functions.
6.2. Vegetable oil derivatives
Some research efforts were made to convert lipid-based molecules
into diamines or polyamines. Biermann et al. [92] reviewed different
routes to functionalize unsaturated fatty acids. Since then various one-
or two-step processes were developed to manipulate fatty acids to be
used as monomers for NIPU synthesis. One strategy for example, is to
convert epoxidized triglycerides into azide derivatives in the presence
of ionic liquid as a catalyst [93]. Zhao et al. [94] proposed another
interesting strategy by implementing a multistep process to synthesize
secondary amines from epoxidized triglycerides. In this pathway, the
oxirane rings were first participated in a reaction with diols and the
resultant products were brominated with the help of triphenyl phos-
phine. The replacement of the bromine groups with sodium azide and
subsequent catalytic reduction eventually led to the formation of the
desired polyamines. The application of using nitrile compounds in
connection with fatty acids as potential precursors of amine synthesis
has constantly been reported in the literature [95]. This indicates that
the addition of excess diamine to an epoxidized vegetable oil under
controlled conditions can result in amine-functionalized fatty acids
[96]. Two long-chain diamines of 1,9-nonanediamine and 1,13-tride-
canediamine have been synthesized from oleic and erucic acids, re-
spectively. [97] Another way to introduce an amine functionality into
vegetable oils would be via a thiol–ene coupling reaction [98,99].
Taking the advantage of this method, Stemmelen et al. [98] demon-
strated that a polyamine can be synthesized from unsaturated grape-
seed oil through a reaction of cysteamine hydrochloride and UV-in-
itiated thiol-ene chemistry (Scheme 15). Similarly, Turunc et al. [100]
produced a polyamine compound through the combination of cystea-
mine hydrochloride with grapeseed oil.
6.3. Sugar derivatives
Succinic acid is a four-carbon dicarboxylic acid that is attracting
considerable research attention due to its broad usage as a precursor to
synthesize valuable chemical materials [101]. It is typically obtained
from the fermentation of agricultural carbohydrates, particularly glu-
cose. One important application of succinic acid is in the production of
1,4-butanediol or 1,4-butanediamine, both of which can be used as
starting materials for PU synthesis [102] (Scheme 16).
Similarly, adipic acids can be converted into diamines by initially
transforming into an intermediate referred to as adiponitrile and
thereafter into 1,6-hexamethylene diamine via a catalytic hydrogena-
tion [103] (Scheme 17).
Azelaic acid is another substance in this group. It can be used to
synthesize 1,9-nonandiamine using a similar synthetic pathway.
Polyamines can be synthesized from bio-based alcohols via catalytic
M. Ghasemlou, et al.
Scheme 17. Synthesis of 1,6-hexamethylene diamine from adipic acid.
Scheme 18. Conversion of isosorbide into the corresponding monoamine and
diamine based on Ref. [105].
amination. Ethylene glycol for example, can be catalytically obtained
from cellulose and can be exploited as a potential precursor for ami-
nation reaction [104]. Isosorbide— which is generally derived from
sorbitol via a two-fold dehydration— can be converted into corre-
sponding mono- and diamines via introduction of nitrile compounds
followed by catalytic hydrogenation [95,105] (Scheme 18).
Applying a similar strategy, Hibert et al. [85] reported the synthesis
of a series of bio-based amines from numerous bio-based alcohols via
nitrile intermediates. The authors first oxidized bio-based alcohols into
dinitrile compounds using various catalytic systems in the presence of
aqueous ammonia and O2. Afterwards, these bio-based dinitriles were
reduced into diamines under controlled hydrogenation in the presence
of Raney nickel serving as the catalyst. To synthesize fully bio-based
PHUs, the bio-based diamines were allowed to react with fatty acid-
based cyclic carbonates in mild reaction conditions. Shibata et al. [106]
recently proposed another strategy to convert sugar alcohols such as
diglycerol and D-sorbitol into their equivalent polyamines via a com-
bination of allyl-esterification and thiol-ene coupling reaction with
cysteamine hydrochloride (Scheme 19). The furfural and 5-hydro-
xymethylfurfural, which are derivatives of glucose have also been re-
ported to be suitable in synthetizing aromatic bio-based diamines,
[107] although these raw materials are available in small quantities and
may not be well-suited for industrial scale production.
6.4. Lignin derivatives
Lignin derivatives with an aromatic structure can be modified to
produce polyamines for their application in NIPU synthesis. However, it
is noteworthy to mention that because lignin depolymerization often
entails multistep harsh oxidative or reductive processes, there are very
limited synthetic routes available that directly produce amines from
lignin. However, lignin oligomers or lignin-derived monomers can be
used for this purpose [90]. Among the large variety of aromatic com-
pounds extracted from the depolymerization of lignin, vanillin and
syringaldehyde have received more attention than others for the pos-
sible conversion into bio-based amines [108]. For instance, vanillin can
participate in a reductive amination reaction and becomes converted
into its aromatic amine, vanillylamine. For this reaction, vanillin is
reacted with ammonium formate and HCl for the development of va-
nillylamine hydrochloride. The latter is then hydrolyzed using NaOH
leading to the synthesis of vanillylamine [109] (Scheme 20).
Fache et al. [17] obtained three types of vanillin-derived molecules
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European Polymer Journal 118 (2019) 668–684
via three different pathways: reduction, decarboxylation, and oxida-
tion. These molecules were then exposed to an allylation reaction be-
fore performing thiol-ene coupling reaction with cysteamine hydro-
chloride to produce three different non-aliphatic vanillin-derived
diamines (Scheme 21).
6.5. Cardanol
We explained in section 5.5 of this review that cardanol is a pro-
mising renewable resource for the synthesis of cyclic carbonate. It can
be equally used to produce of aromatic amines. The common method
for the conversion of cardanol into amines relies on the Mannich re-
action with the involvement of formaldehyde and diethylene triamine,
leading to the formation of partially bio-based phenalkamine. One of
the main drawbacks of this synthetic pathway is the use of hazardous
formaldehyde. To overcome this drawback, Darroman et al. [110] de-
veloped an alternative route to synthesize cardanol-derived aromatic
diamines by allylation of the phenol followed by a thiol-ene reaction
with cysteamine hydrochloride (Scheme 22).
Sadavarte et al. [111] chose yet another way to synthetize these
aromatic diamines. They adopted a four-step process to obtain penta-
decylbenzene-1,3-diamine starting from hydrogenated cardanol. The
phenolic hydroxyl group in cardanol was first converted into mesyl
ester by reaction with methanesulfonyl chloride. In the second step, Pd-
C catalyzed deoxygenation caused the mesyl ester to be broken with the
formation of pentadecylbenzene. The latter was sequentially subjected
to nitration and reduction reactions to produce pentadecylbenzene-1,3-
diamine which is the compound of interest for this review (Scheme 23).
Catalytic hydrogenation of cardanol yields 3-n-pentadecylphenol;
this alkyl phenol derivative is commercially available in high purity.
Attanasi et al. [112] proposed that the latter can be simply nitrated
using nitric acid resulting in the formation of a mixture of mono, di or
trinitro intermediate products. A subsequent reduction of these nitro
groups can yield the equivalent mono, di or triamines.
7. Conclusion and outlook
Polyurethanes (PUs) have been manufactured using the reaction
between isocyanates and polyols for almost half a century. The toxic
nature, moisture sensitivity and phosgene-based synthesis of iso-
cyanates have prompted researchers to seek environmentally benign
and safe processes for synthesizing PUs. As a result, numerous pathways
have emerged for synthesizing non-isocyanate polyurethanes (NIPUs).
Among these, the reaction between cyclic carbonates and polyamines
seems to show great promise in overcoming the risks associated with
synthesis of isocyanate-based PUs. The rising concerns about the
shortage of fossil-based resources combined with global awareness of
environmental problems have greatly increased the interest in utilizing
bio-based precursors for the synthesis of NIPUs. Moreover, the flex-
ibility of NIPU routes—which leaves many options to tailor green
multifunctional PUs— has further intensified using them to make sus-
tainable products. This trend has opened a new dimension of green
chemistry in the synthesis of new class of NIPUs by exploiting a wide
M. Ghasemlou, et al. European Polymer Journal 118 (2019) 668–684

Scheme 19. Synthesis of tetramine and hexamine from α,α′-diglycerol (a) and d-sorbitol (b) by the allylation and subsequent thiol-ene reactions with cysteamine
hydrochloride based on Ref. [106].

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M. Ghasemlou, et al. European Polymer Journal 118 (2019) 668–684

Scheme 20. Synthetic pathway of vanillylamine from vanillin.

range of renewable feedstocks such as vegetable oils, terpenes, lignin Scheme 22. Synthesis of amine-functionalized cardanol with allyl bromide and
derivatives, and polyols as raw starting molecules. As explained cysteamine hydrochloride based on Ref. [110].
throughout this review, artificial cyclic carbonates can be substituted
with their bio-based equivalents. Similarly, polyamines can also be
synthesized from their renewable analogous. Through this review, we
built a basis for further development of green NIPU materials with a
special focus on precursors. The synthesis of precursors of NIPUs using
bio-based and renewable sources appears to be feasible. Most im-
portantly, these precursors can bypass the need of relying on the ha-
zardous isocyanate reactants. However, there are still many challenges
before they become reality. For example, although the mechanical
performance and thermal stability of these NIPUs are comparable to
conventional PUs, they have not yet found applications in consumer
goods. Current procedures for the synthesis of bio-based precursors may
bring additional cost to the final PU product. This can become a limiting
hurdle for commercial-scale production because most consumers are
unwilling or unable to pay extra cost for the green label. The lack of
high reactivity of cyclic carbonates towards ring-opening by amine
reagents could be challenging and can indeed hamper their industrial Scheme 23. Synthesis of a cardanol-derived diamine (pentadecylbenzene-1,3-
applications. Therefore, to address these remaining challenges, to meet diamine) from hydrogenated cardanol based on Ref. [111].
customer demands and to comply with regulations, further research

Scheme 21. Three synthetic pathways for production of vanillin-derived diamines based on Ref. [17].

681
M. Ghasemlou, et al.
and development are necessary. With continued research dedicated to
the production of NIPUs using precursor compounds derived solely
from renewable sources, the future of NIPUs produced entirely from
bio-based and renewable sources appears promising.
Declaration of Competing Interest
There are no conflicts to declare
Acknowledgements
The first author would like to acknowledge and express his appre-
ciation to RMIT University, School of Science for providing scholarship
support that enabled the completion of this work.
Appendix A. Supplementary material
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.eurpolymj.2019.06.032.
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