Journal of Polymers and the Environment

https://doi.org/10.1007/s10924-020-01659-1

REVIEW

A Review of the Sustainable Approaches in the Production

of Bio‑based Polyurethanes and Their Applications in the Adhesive
Field
Adrián Tenorio‑Alfonso1 · Mª Carmen Sánchez1 · José Mª Franco1

© Springer Science+Business Media, LLC, part of Springer Nature 2020

Abstract
On account of the irreversible environmental damage caused by the utilization of non-renewable raw materials in industrial
production, since the end of the twentieth century, the interest in replacing the traditionally applied petroleum-based starting
compounds in the polyurethane production by more sustainable feedstocks has grown enormously. Such pursuit of Green
Chemistry has been fostered by the implementation of a set of national and international initiatives and stricter regulations,
especially in the field of adhesives. In this respect, the latest advances in the production of bio-based polyurethanes are
collected in this review. Thus, after a brief introduction to this subject and main tendencies towards the production of more
sustainable polyurethanes, the first section reviews the feasibility of manufacturing polyurethanes from a range of natural
platforms, including lignocellulosic biomass and vegetable oils, whether modified or in their original form, along with
some industrial wastes. Afterwards, the hitherto considered synthetic routes for the preparation of greener polyurethanes are
assessed, encompassing waterborne, radiation-curable and non-isocyanate polyurethane techniques. Finally, the last section
focuses on the research advancement on the synthesis, properties and different uses of bio-based polyurethanes specifically
implemented in the field of adhesives.

Keywords Green chemistry · Lignocellulosic materials · Vegetable oils · Bio-sourced polyurethanes · Adhesive

Towards the Green Chemistry limits [2]. Indeed, the worldwide average annual polyure-
in Polyurethane Production thane consumption has risen from 12.9 up to 16.1 Mt from
2011 to 2016, and according to the worldwide statistical
Under the stimulus of high molecular weight polyamides, study conducted by The Statistics Portal [3], a growth of
auspiciously synthesized by E.I. DuPont, Otto Bayer and 20% is envisaged until 2021.
collaborators, through the genuine discovery of the poly- The conventional industrial production of urethane poly-
condensation reaction between alcohols and isocyanate by mers deeply relies on petroleum stocks. However, as a con-
Wûrtz, succeeded in developing polyurethane fibers in 1937 sequence of the exhaustion of crude reserves, its subsequent
[1], aimed to compete with commercialized nylon-based floating price, along with the existing environmental aware-
counterparts. However, they were unaware of the rapid ness, the present paradigm in the polyurethane research has
expansion such materials would experience, representing shifted towards the exploration of new synthetic routes lead-
a milestone in the polymer chemistry. Nonetheless, it was ing to renewable bio-based products [4].
not until the recognition of their exceptional elasticity by In general, the term “bio-based products” comprises any
DuPont and ICI in 1940 when their industrial manufactur- material derived from natural and renewable resources, but it
ing commenced, which would expand towards unimaginable entails neither biodegradability nor biocompatibility. Indeed,
biodegradable polyurethanes, typically intended to tempo-
rary biomedical applications, are required to contain link-
* Adrián Tenorio‑Alfonso ages ready to degrade under biological circumstances, also
[email protected] showing biocompatible properties, i.e. easy metabolization
1
Pro2TecS‑Chemical Product and Process Technology and lacking toxicity, capable of playing their role without
Research Centre, University of Huelva, 21071 Huelva, Spain causing adverse effects in the living organism [5].

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 Journal of Polymers and the Environment

In this sense, considering polyol building blocks, enzymatic New Alternative Feedstocks: Polyols
hydrolysis of the ester bond in polyester-polyols makes them and Polyisocyanates
more appealing for the production of biodegradable polyure-
thanes [6]. Thus, polyester polyols like polycaprolactone [7], Lignocellulosic Materials and Derived Compounds
polylactic acid [8], and polyacrylic or polyglycolic acids [9, as Polyol Precursors
10] have demonstrated not to produce toxic decomposition
products. Additionally, polycarbonate polyols can also be Lignocellulose represents the most copious natural occur-
proposed as biocompatible polyurethane precursors, as it has ring biomaterial, which, together with its non-edible
been shown by Zhu et al. [11] when assessing the biostability nature and significant hydroxyl functionality, confers its
of poly(1,6-hexanediol) carbonate diol-based polyurethanes. particular appeal as a renewable platform for the polyure-
Furthermore, as shown in the investigations of Calvo-Cor- thane production [19]. Lignocellulosic materials compre-
reas et al. [12, 13], Li. et al. [14] and Basterretxea et al. [15], hend cellulose, hemicellulose and lignin, as the main com-
l-lysine and dimeryl diisocyanates exhibited suitable biocom- pounds among other minor constituents (tannins, proteins,
patible and biodegradable behaviour. ash, etc.), whose composition is not evenly distributed, but
Moreover, the renewability and biocompatibility in the pol- strongly depends on the biomass’ nature [20].
yurethane network can be raised by means of chain extenders, Due to the fact that lignin is primarily obtained as a
as can be found in the investigation of Abdollahi et al. [6], byproduct in the paper industry, the still reduced market
who conducted the prepolymer chain extension with differ- niche and its reactive and hydroxyl-groups bearing charac-
ent combinations of 1,4-butanediol and curcumin aiming to ter, lignin appears as a potential precursor for the produc-
preserve the polyurethane biocompatibility, while Kavanaugh tion of polyurethanes [21]. As a consequence of the steric
et al. [16] combined the use of biodegradable polyols (poly-ε- hindrance, lignocellulosic biomass may be submitted to
caprolactone) with a series of osteogenically active molecules different modifications to improve the accessibility of the
in pursuit of medical regeneration, evincing the ability of hydroxyl groups to further react with isocyanate moie-
β-glycerol phosphate to act as chain extender in the produc- ties [22]. The predominant chemical modifications to do
tion of cytocompatible segmented polyurethanes. Additionally, that can be classified into liquefaction and oxypropylation,
Opera et al. [17] succeeded in improving the biodegradation which will be described in the next sections. Nevertheless,
of polyurethane composites owing to the fungal susceptibil- aimed to avoid the adverse impact on the competitiveness
ity of ester group located in the vegetable oil (viz. castor oil) of the bio-based polyols emerging from the energy loss
chain extender and the cellulose filler, strongly bonded to the and the inherent economic cost associated with the imple-
urethane network through covalent bonds. mentation of such additional steps [22], some researchers
To summarize, the main focus of the current work is to have addressed the development of polyurethanes from
review the recent advances in the partial or complete replace- unmodified polysaccharides. With this aim, Araujo and
ment of non-renewable raw materials by new eco-friendly Pasa [23] dedicated their study to the direct utilization
alternatives, according to the concept of “sustainability”, of residual guaiacyl-syringyl-based lignin-containing
which in agreement with Dubé and Salehpour [18] means “the residual polysaccharide resulting from the Eucalyptus tar
ability to meet the current needs without jeopardizing the abil- distillation, so-called biopitch, in combination with differ-
ity of future generations to meet their own needs”. Neverthe- ent proportions of hydroxyl-terminated polybutadiene for
less, due to the greater difficulties in replacing non-sustainable the preparation of elastomeric polyurethanes. Addition-
isocyanates, most of the researchers have devoted their inves- ally, Griffini et al. [22] demonstrated the effectiveness of
tigations to the development of polyurethanes with improved polyurethane film preparation from fractionated softwood
renewable content considering the use of lignocellulosic bio- Kraft lignin, revealing the improved degree of sustainabil-
mass, polysaccharides and natural oils as polyol sources. In ity of such coatings through a simplified synthetic route.
the following sections the production of bio-sourced polyu- Furthermore, Gallego et al. [24, 25] extended the applica-
rethanes, not only from more renewable platforms but also tion of lignocellulosic biomass in their natural form to the
by dint of the implementation of greener synthetic routes, are achievement of bio-inspired lubricating greases, preparing
reported. NCO-terminated thickening agents through a controlled
condensation reaction of HDI not only with Kraft cellulose
pulp but also with some derivatives, such as methylcel-
lulose [26, 27] or (methyl) 2-hydroxyethyl cellulose [28].
More recently, Borrero-López et al. [29] first functional-
ized alkali Kraft lignin with a wide selection of aliphatic
and aromatic isocyanates to evaluate the curing kinetics

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Journal of Polymers and the Environment

while analyzing the evolution of the viscoelastic response of secondary reactions and to reduce to the minimum pos-
of the ensuing castor oil-based polyurethanes. Conse- sible the remaining solid content. Thus, some studies [37]
quently, the most suitable modifier from that research in intended to optimize, in terms of biomass conversion, the
terms of the ultimate viscoelastic properties, the aliphatic experimental conditions (temperature, time and catalyst con-
1,6-hexamethylene diisocyanate, was applied in further centration) to obtain liquified polyols from coffee grounds,
investigations [30, 31] as the crosslinking agent in oily accomplishing a 70% of yield at 160 °C, 80 min and sulfuric
medium in order to develop solid-state fermented wheat acid at 4% (w/w).
straw soda lignin for lubricating purposes. Despite the liquefaction modification can be conducted
through the use of a series of solvents, as Liang et al. [38]
Liquefaction showcased when evaluated the kinetics of this procedure
on different feedstocks, the most challenging issue is to
This treatment is based on the solvolysis of lignocellulosic decrease or even eliminate its dependency on petroleum
biomass at temperatures within the range of 150–250 °C, derivatives. On the other hand, as a consequence of the rapid
leading to smaller hydroxyl-bearing molecules by dint of the expansion of the biodiesel industry, in which crude glycerol
utilization of polyhydric alcohols (ethylene or polyethylene is produced as a byproduct, several studies suggest the incor-
glycol) or cyclic carbonates (ethylene carbonate) as the liq- poration of crude glycerol as solvent for the liquefaction of,
uefaction solvents, and usually an acid catalyst [32]. Besides inter alia, the solid residues of the saccharification of sun-
that, in order to prepare polyurethanes from long-chain poly- flower stalk [39] and empty fruit bunches [40], achieving a
functional alcohols, the resulting liquified units are typically yield of 59% and 47.9%, respectively, in the production of
submitted to a further transesterification producing natural bio-based polyols.
polyester polyols, as reported by Sinha and coworkers [33,
34] and Patel et al. [35], in which the glycosides resulting
from an acid liquefaction (α-D-glycoside and β-D-glycoside) Oxypropylation
with sulfuric and/or p-toluene sulfonic acids were esterified
with oils or fatty acids at low pressure and high temperatures Unlike liquefaction, when optimized, oxypropylation is a
(220–250 °C), using lithium hydroxide as catalyst (Fig. 1). chemical reaction capable of incorporating more readily
Similarly Zhou et al. [36] reported such liquefaction-trans- available hydroxyl groups, avoiding the utilization of any
esterification procedure when partially substituting PEG400 solvent while simultaneously maintaining the biomass func-
with liquified banana pseudo-stem to prepare polyurethane tionality [41]. This modification consists of a base-catalyzed
for adhesion purposes. grafting of propylene oxide onto lignocellulosic materials
This solvolytic reaction is an effective process to increase under high pressure and temperature (650–1820 kPa and
both the functionality and sustainable nature of the starting 100–200 °C) (Fig. 2). As a result of the incorporation of
polyols, notwithstanding the required optimization of the short propylene oxide chains to lignocellulosic biomass, the
reaction conditions (temperature, time, catalyst and biomass starting solid material can be converted into a viscous polyol
to solvent weight ratio) aimed to mitigate the occurrence [42].

Fig. 1  Liquefaction of cellulose with a subsequent transesterification

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 Journal of Polymers and the Environment

Fig. 2  Oxypropylation of ligno-

cellulosic biomass

As related to any chemical transformation, some side series of chemical modifications, as will be further dis-
reactions can be found yielding not only to partially oxy- cussed, some studies propose the production of “green”
propylated biomass but also polypropylene oxide homopoly- polyurethane macromolecules by direct utilization of a
mers, which, however, may take part in the chain exten- limited group of natural oils containing hydroxylated fatty
sion of the polyurethane prepolymer [42]. Bearing this fact acids, essentially castor and lesquerella oils. In this way,
in mind, and due to the high-pressure requirements, the Ferreira et al. [49] produced bioadhesives for tissue engi-
application of oxypropylation to produce bio-sourced pol- neering by direct modification of castor oil with IPDI via
yurethane may be to some extent hindered. Even so, some prepolymer method, in contrast with the straight-through
researchers have devoted their investigations to the produc- process applied by Raghunanan et al. [50] when preparing
tion of polyurethane foams prepared from oxypropylated elastomeric adhesives from castor oil and HMDI. Moreover,
cork powder [43]. Hablot et al. [51], Abdolhosseini and Givi [52] and Zhang
et al. [53] applied the one-shot formulation procedure to
Vegetable Oils as Polyol Sources synthesize elastomeric polyurethanes. Moreover, Sharma
et al. [54] reported the systematic substitution of polypropyl-
In search of the compliance of the sustainable development ene glycol by castor oil for the production of polyurethane
standards, vegetable oils have drawn the attention in the foams, proving the still need for only a partial replacement of
last decades as feasible alternatives for the partial or total petro-based polyols, given the loss in their properties when
replacement of unsustainable raw materials to produce cost- considering castor oil as the only hydroxyl group source.
effective and renewable urethane polymers [44]. The excel- This fact has also been corroborated by Septevani et al. [55]
lent properties of such natural oils, including their abundant who gradually substituted polyether polyol by a commercial
availability, non-toxicity, sustainability, easy handling and polyester polyol derived from palm kernel oil, obtaining an
structural versatility, are the driving force of their considera- appropriate foam behaviour of the ensuing polyurethane
tion as polyol sources [45]. until a critical degree of substitution of 30%, above which
Vegetable oils are mainly composed of triacylglycerides, the properties of the foam became poorer.
holding three aliphatic fatty acid chains composed of 12–22 In the following sections, the major synthetic modifica-
carbon atoms and a double-bond functionality ranging from tions affecting the functional active sites of not only veg-
0 to 3 per chain typically located at the 9th, 12th or 15th etable oils but also fatty acids (C–C double bonds and ester
C-atom [45, 46]. Each vegetable oil exhibits a characteristic groups) will be described.
fatty acid profile, which might even vary within the same
type of oil, depending on the plant variety and provenance Epoxidation
[47].
The improved hydrolytic and thermal resistances due to The formation of oxirane groups appears as one of the most
the hydrophobic character of vegetable oils are remarkable widely employed double bond modifications for the pro-
qualifications. Nevertheless, what really makes natural oils duction of polyols from vegetable oils. Epoxidation may
such a reasonable chemical platform for bio-polyurethane be performed by using either prepared or in situ generated
development is the presence of amenable unsaturations and peracids (arising from the reaction between acids and hydro-
ester groups, providing them with exceptional chemical ver- gen peroxide) and sulfuric acid as catalyst, followed by an
satility [48]. additional ring-opening process (Fig. 3a). This hydroxyla-
Even though the production of appropriately functional tion step, essentially consisting of a nucleophilic attack,
polyols from vegetable oils has been reported through a is the controversial and most engaging point in the polyol

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Journal of Polymers and the Environment

Fig. 3  Double bonds modifica-

tions: a epoxidation-hydroxy-
lation; b hydroformylation; c
ozonolysis; d air oxidation; e
thiol-ene coupling

production, since an appropriate selection of nucleophile the epoxidation conditions (75 °C, 3% ­H2SO4, ­H2O2/formic
allows for the optimization of important factors such as acid/C=C of 8:8:1) leading to an optimal epoxy number of
hydroxyl functionality, the appearance of dangling chains 7.3 in only 6.7 min of residence time [60], and afterwards,
and availability of the hydroxyl groups [56]. the hydroxylation step (75 °C, 10% H ­ 2SO4, 13 min) pro-
In this respect, the in situ oxirane ring-opening may be ducing soy-polyols with more uniform molecular weights,
performed under acid conditions with water as the reagent, characterized by a greater hydroxyl value [61], evincing the
obtaining two secondary hydroxyl groups per double bond. remarkable advantages of the microflow technology over the
Thus, Narute and Palanisamy [57] applied the epoxida- polyol production in batch.
tion and in situ ring-opening with water on cottonseed oil On the other hand, when considering acids as the hydrox-
aimed to synthesize bio-sourced polyurethane coatings ylation agents, the polyol functionality might be improved,
with an optimum NCO:OH molar ratio of 1.8. However, like for instance in the lipase-catalyzed hydroxylation of
the nucleophilic attack in this process can be conducted not epoxidized soybean oil with lactic acid performed by Miao
only by water but also by acetic acid, as shown by the study et al. [62] or in the application of castor oil fatty acids, avoid-
of Pechar et al. [58], so that the polyol functionality halves. ing the utilization of either solvent or catalyst at the expense
More recently, Mekewi et al. [59] simulated the in situ pro- of increasing the temperature (130–190 °C) [63–65]. How-
cedure by blending the epoxidized vegetable oil with deion- ever, in some instances, such as in adhesive formulations
ized water and p-toluene sulfonic acid, achieving afterwards that require gelation to ensure a suitable and safe adhesive
a partial replacement of the petrochemical polyols (50%) to application, a lower hydroxyl value with secondary func-
produce ink plasticizer polyurethanes. tional groups may be required [66]. Moreover, inorganic
As a consequence of the intrinsic constraints associated acids such as hydrochloric o hydrobromic acids can also be
to batch production, such as the unavoidable long reaction used, albeit the utilization of a polar organic solvent may be
times, side reactions and the inherent start-up and shutdown essential to overcome their incompatibility with vegetable
stages, Ji et al. developed a novel continuous microreaction oils [67].
method with improved surface to volume ratio, thus enhanc- Furthermore, alcoholysis of the oxirane ring with mono-
ing the mass and energy transfer during epoxidation and sub- functional alcohols in the presence of an acid catalyst pro-
sequent nucleophilic attack with water in order to produce vides natural polyols with secondary OH groups [68]. In
polyurethane rigid foams [60, 61]. In summary, these authors addition, given that the unsaturation density and location in
optimized the polyol production in two steps, first analyzing the fatty acid chains are the significant variables in natural

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 Journal of Polymers and the Environment

oils, Zlatanić et al. [47] analyzed the influence of hydroxyl the hydrogenation procedure on the hydroxyl functionality,
functionality (from 3 up to 5.2) and dangling chain lengths so that epoxidized soybean oil was hydrogenated by using
of polyols manufactured from different oils on the result- hydrochloric and hydrobromid acids, methanolysis and cata-
ing polyurethane, reporting the strong proportional relation lytic hydrogenation, demonstrating the improved functional-
between the glass transition temperature and the density of ity of halogen bearing polyols (up to 4.1), whereas the only
crosslinking with polyol functionality, while the impact of liquid polyol was the methoxylated one at room conditions.
the dangling chains was negligible. Finally, an alternative to the hydroxylation through a
On the other hand, the conversion with polyfunctional nucleophilic attack comprises ring-opening oligomerization
polyols enables the simultaneous incorporation of secondary and subsequent reduction of ester groups. Thus, Lligadas
and primary hydroxyl groups into the C=C linkage. In this et al. [82] reported the epoxidation of methyl oleate and
way, investigations dealing with diethylene glycol and 1,2- further oligomerization catalyzed by fluoroantimonic acid
and 1,3-propanediol as hydroxylation agents can be found ­(SbHF6), followed by a partial reduction of the carboxylate
[69, 70]. Datta and Głowińska [71–73] employed propan- functional groups with lithium aluminum hydride (­ LiAlH4)
ediols derived from glycerol resulting from the biodiesel at room temperature, aimed to incorporate primary hydroxyl
production and corn sugar fermentation processes, while groups into the polyether polyol chemical structure (Fig. 4).
Ventakesh and Viswanathan [74, 75] reported the appli- A similar reduction process was conducted by Zhang et al.
cation of castor oil-based fatty diols as the hydroxylation [64, 83] on epoxidized (soybean and linseed) and raw (cas-
agent to prepare high molecular polyols from a series of tor) oils, but at low temperatures (0 °C), thus obtaining
vegetable oils, i.e. sesame, peanut neem, jatropha and mahua hydroxyl values at least threefold higher than those reported
oils. Furthermore, Kong et al. [76] proposed an inexpensive by Lligadas et al.
combination of hydroxylation and transesterification with
1,2- and 1,3-propanediol in order to increase the polyol func- Hydroformylation
tionality and to reduce the molecular weight and viscosity
of the resulting polyurethanes, increasing their resistance Hydroformylation falls into the category of modifications
to hydrolysis and alkali attack. The polyol obtained from providing primary alcohols from natural oils or fatty acids,
the combination of those modifications succeeded in such without increasing their functionality, as only one OH group
a way that it was quickly marketed by the name of Liprol™ can be incorporated per double bond. Therefore, first, an
(Meadow Polymers, Consolidated Biofuels Ltd., Canada), intermediate aldehyde is typically produced using an inlet
which would be further used in conjunction with cellulose flow of synthesis gas (CO/H2) and a cobalt or rhodium cata-
nanocrystals to prepare polyurethane nanocomposites [77]. lyst, then conducting the followed reduction with H ­ 2 and a
Another pioneering study is that conducted by Norhisham Raney nickel catalyst (Fig. 3b). The choice of the catalyst is
et al. [78], which addresses the production of biodiesel fuel- particularly important as it will directly affect the reaction
based polyols (fatty acid methyl ester) combined with palm yield (Co-67% vs. Rh-95%). At the expense of a reduction
olein polyol to synthesize elastomeric polyurethanes with in the yield of the reaction, the utilization of cobalt-based
greater natural content and an appropriate pressure-sensitive catalysts entails some benefits, essentially their lower prices
adhesive response, using boron trifluoride diethyl ether com- and the possibility to act as hydrogenation catalysts as well,
plex ­(BF3) as the alcoholysis catalyst. though under more severe conditions [68, 84]. Further-
Catalytic hydrogenation is reckoned as another oxirane more, the type of catalyst considered in the production of
ring-opening reaction leading to secondary alcohols due the natural polyol may also influence the response of the
to the incorporation of both hydrogen atoms into the dou- resulting polyurethane, as Guo et al. reported when produc-
ble bond with the aid of a Raney nickel catalyst (Al-Ni) at ing hydroformylated soybean oil [85], obtaining bio-based
high pressures [68]. According to Petrović et al. [79], this polyurethanes whose behaviour ranged from rigid plastic to
method shows certain flexibility, since the ultimate hydroxyl hard rubber polyurethanes when using rhodium and cobalt
value of the hydrogenated polyol can be tuned by carefully catalysts, respectively.
controlling the reaction times, what inevitably influences
the properties of the resulting soybean oil-derived polyu- Ozonolysis and Hydrogenation
rethane, being possible to obtain from glass to rubber sys-
tems. Conversely, Monteavaro et al. [80] modified the polyol This oxidation procedure emerges as an alternative to pre-
functionality through different in situ hydrogenation times vious modifications, where the synthesized polyols exhibit
on epoxidized soybean oil as well, though the -OH func- dangling chains with their respective plasticizing effect [56]
tionality range (1.9–3.2) did not exceed the resulting from since ozonolysis allows for the synthesis of polyols with
the Petrovic et al. study (2.7–4.4). Furthermore, in former primary terminal hydroxyl groups, provided that vegetable
investigations, Petrovic et al. [67] assessed the influence of oils solely comprise unsaturated fatty acids. This greater

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Journal of Polymers and the Environment

Fig. 4  Oligomerization of fatty

acids followed by carboxylate
groups reduction [81]

OH availability may be translated into faster condensation from 152.4 up to 235.2 mg KOH/g was obtained, much
reactions with isocyanates thanks to the lower steric hin- closer to the theoretical 251 mg OH/g. On the other hand,
drance, despite its functionality limitation of a maximum the efficiency of canola oil ozonolysis was even higher when
of 3 hydroxyl groups per vegetable oil molecule, and the performing the ozonolysis at lower temperatures (from − 30
production of alcohols of low molecular weights [86] typi- to − 40 °C) in a blend of methylene chloride/methanol, fol-
cally removed due to their deleterious effect on the final lowed by a reduction with sodium borohydride (­ NaBH4) at
polyurethane, diminishing its microphase separation and the 10–15 °C [90]. Moreover, another variant worthwhile to
associated beneficial properties [87]. mention is the one-step ozonolysis in the presence of NaOH,
Ozonolysis comprises the formation of ozonide when ­CaCO3 or H­ 2SO4 catalysts and polyols that will interact with
treating double bond with ozone ­(O3), which subsequently the ozonide functional groups to produce polyester polyols
decomposes into aldehyde and carboxylic functional groups, (Fig. 5) [91].
giving rise to the C=C cleavage. Afterwards, the already
known hydrogenation step with Raney nickel catalyst is Oxidation with Air
performed to reduce aldehyde groups into primary alcohols
(Fig. 3c) [68, 84]. Similarly, oxidation with oxygen (­ O2) can provide plant
Nevertheless, some of the drawbacks of the ozonolysis- oil-derived polyols by the first production of hydroper-
hydrogenation of double bonds are the extreme pressures oxide (–OOH) through a UV-radiation process with thia-
and temperatures, and the requirement for toxic solvents in mine pyrophosphate in dichloromethane, followed by the
the final reduction [42], inasmuch as initial ozonolysis was reduction with ­NaBH4 in methanol at 0 °C and a catalytic
reported to be conducted in deionized water at 0 °C and the hydrogenation step in ethyl acetate (Fig. 3d). However, the
subsequent hydroxylation in tetrahydrofuran (THF) under requirement for reaction times in the order of days and the
130 °C and 350 psi of hydrogen pressure [88]. Thereupon, poorer oxidation control compared with other modifications,
Kong et al. [89] devoted one study to the enhancement of
the previous protocol via the replacement of the traditional
hazardous THF by a more environmentally friendly ethyl
acetate during the whole process, using zinc as a reagent for
the reduction of the ozonide groups to aldehydes at room
temperature. With all these improvements, along with the
reduction of temperature and pressure during hydrogenation
(70 °C and 100 psi), an increase of the hydroxyl number Fig. 5  One-step ozonolysis

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 Journal of Polymers and the Environment

such as epoxidation, have restricted the application of air- polyester polyols with a tailorable molecular weight [95].
oxidation to synthesize bio-sourced polyurethanes [68, 86]. The versatility of thiol-ene click reaction was also high-
lighted by the investigations of Alagi et al., who succeeded
Thiol‑ene Coupling in both controlling the soybean-based polyol functional-
ity [96] and accomplishing the quantitative conversion to
The last modification regarding fatty acid chain unsaturation hydroxyl of soybean and castor oils unsaturations [97] by
is the so-known thiol-ene coupling. This process, regarded sensibly adjusting the reaction time and temperature, along
as click chemistry and based on the addition of thiol link- with reagents’ concentrations. Moreover, the preparation
ages (HO-R-SH, mainly 2-mercaptoethanol) onto C=C dou- of multifunctional polyols via thiol-ene coupling incorpo-
ble bonds, leads to polyols with primary hydroxyl groups rating silane, fluorine and ethylene oxide [98] or acrylate
through an eco-friendly and highly efficient radical mecha- [99] functional groups has been recently reported, aimed
nism (Fig. 3e). This procedure may be initiated by either to improve either the coating properties or the UV-curing
UV-radiation [92] or thermal induction [93]. speed, respectively.
The appeal of this reaction comes from the possibility of
producing bio-based polyols with a wide range of functional- Transamidification and (Trans)esterification
ity through a simple, solventless, efficient and cost-competi-
tive procedure under air conditions [87], despite presenting Although the modification of fatty acid chains has been
some disadvantages such as the presence of dangling chains focused on the carbon to carbon double bonds, the produc-
and the production of some by-products [56]. However, as tion of bio-based polyols via ester functional group trans-
most of the products resulting from the side reaction have formation is also attainable, by means of transamidation and
been proved to be hydroxyl-bearing compounds, they could (trans)esterification processes.
still participate in the polycondensation reaction with reac- Amidification consists of the reaction of vegeta-
tive isocyanates. Desroches et al. [92] addressed in their ble oils with amines and a catalyst at high temperatures
study the optimization of the thiol-ene coupling conditions (100–120 °C) leading to amides and alcohols, although
(intensity of radiation, solvent and double bond contents) for diethanolamine is typically regarded as amidification agent
the photoaddition of 2-mercaptoethanol onto oleic acid, to of plant oils, alcoholamides are commonly obtained together
be further applied on rapeseed oil, thus reducing the reaction with glycerol (Fig. 6b) [68]. Moreover, if triethanolamine
time, but still obtaining byproducts. was considered as the reagent, a transesterification process
Furthermore, it is possible to obtain polyols with terminal would occur, leading to poly(ester urethane) instead of the
primary hydroxyl groups if the photochemical grafting of previous poly(urethane amide) [100]. In addition, a wide
thiols is combined with allyl esterification, as Lligadas et al. array of catalysts has been reported, ranging from metal
reported when preparing diols via thiol-ene coupling after oxides [101] to different salts, like stannous octoate [102]
esterification of oleic and 10-undecenoic acids with allyl or zinc acetate [103].
alcohol [94], and even controlling the chain length through Especially noteworthy is the progress achieved by Patil
a step-growth photopolymerization using a dithiol followed et al. [104], succeeding in the rise of polyurethane coat-
by a phototermination with 2-mercaptoethanol producing ings natural content up to 65% with fairly competitive

Fig. 6  Ester group modifica-

tions: a transesterification; b
transamidification; c direct
esterification

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Journal of Polymers and the Environment

behaviour against the petro-based counterparts, by means Other Modifications

of a further esterification of the cottonseed oil-based dieth-
anolamide with bio-sourced difunctional carboxylic acids, Although the modifications above detailed are the most
inter alia succinic, sebacic, tartaric, maleic and azelaic widely applied on vegetable oils and fatty acids, some other
acids, thus producing polyesteramide polyols as polyure- transformations have been spread to a lesser extent to pro-
thane precursors. duce polyurethane precursors, including dimerization and
Conversely, transesterification of vegetable oils com- subsequent reduction of carboxylic groups to polyols [118],
prises the reaction with multifunctional polyols, mainly self-metathesis coupling producing a diol to be used as an
glycerol, and catalyzed by enzymes and organic and inor- unsaturated chain extender [119] or even cross-metathesis
ganic catalysts at high temperatures (170–200 °C) (Fig. 6a) prior to other carbon-to-carbon double bonds modifications
[56, 105]. Nevertheless, when considering heterogeneous aimed to produced terminal hydroxyl groups [120].
catalysts, like lead oxide (PbO), greater temperatures are
required, achieving values of up to 240 °C, according to Waste Products as Polyurethane Feedstocks
the resinification of Nahar seed oil described by Karak
et al. [106–108] for the development of monoglycerides The ever-increasing worldwide population, which has
to synthesize polyurethane resins. Unlike amidification, increased in the last 60 years in 136.9 million people [121],
transesterification is a thermodynamically balanced reac- implies a huge consumption of a great variety of end-use
tion capable of modifying plant oil in a single step, which products and its corresponding agricultural and household
places it among the most appealing modifications [87]. disposal. Consequently, recycling and reutilization of waste
However, this reaction provides a mixture of the residual materials have drawn the attention in the research field in
glycerol with mono-, di- and triglycerides, so that the pursuit of “greener” processes and products.
maximum functionality is also limited, restricting the OH- In this sense, residual pine cone [122], an agricultural
source for polyurethane synthesis to mono- and diglyc- waste, has been suitably pretreated with Fenton’s reagent
eride, along with the remaining transesterification agent. to be further crosslinked with hexamethylene diisocy-
Moreover, the presence of dangling chains could only be anate in order to be applied as an effective absorbent for
advisable when flexible polyurethanes are intended to be organic water-pollutants. In addition, cardanol, a phenolic
obtained. oil obtained as a byproduct of the cashew industry, enables
Due to the low apparent thermal resistance of glycerol, the polyurethane production from a different perspective,
some studies deal with the utilization of other transesteri- despite using the above described synthetic routes, like
fication agents, such as pentaerythritol [109] or triethan- epoxidation of double bonds and further oxirane ring-open-
olamine [103], as above indicated. Furthermore, a more ing, as reported by Suresh [123] who applied afterwards
specific reaction can be conducted when dealing with non- an additional saponification step to increase the hydroxyl
hydroxyl-bearing plant oils, viz. oils interesterification, value of the oxidized cardanol. By contrast, Balgude et al.
as reported by Saravari and Praditvatanakit [110] for the [124], apart from directly using a commercial-grade epoxi-
production of urethane alkyd from interesterified jatropha/ dized cardanol, considered only the epoxy ring-opening with
castor oils. multifunctional natural acids (tartaric, citric and adipic) to
Direct carboxylic acid esterification arises as an alter- produce hydrophilically modified cardanol as the starting
native to transesterification, whether long molecular chain polyol for waterborne polyurethane coatings.
polyols are the primary target, obtaining water as a byprod- In addition, the massive production and consumption
uct instead (Fig. 6c) [68]. Therefore, the so-called fusion of of poly(ethylene terephthalate) (PET) has encouraged the
lauric [111] and ricinoleic [112] acids with ethylene glycol, development of new recycling ways to mitigate its environ-
as well as the production of polyester polyols from direct mental impact. Among other mechanisms, the depolymeri-
esterification of dicarboxylic acids with castor oil [113] have zation of PET-soft drink bottles via liquefaction with pro-
been reported to produce polyester polyurethane with adhe- pylene [125], polyethylene [126] or triethylene [127, 128]
sion properties. glycols has been reported by Cakić et al. for the prepara-
However, these three individual chemical routes cannot tion of polyurethane dispersions. In contrast with the zinc
be necessarily applied independently, as demonstrated not acetate-catalyzed liquefaction previously described by
only by the transesterification with methanol and subsequent Cakic et al., Scremin et al. [129] devised for the first time
amidification of the resulting methyl ester [114–116] but the employment of sodium metasilicate as a more accessible
also several-step modification of vegetable oils via transes- and cheaper alternative to the former alcoholysis catalyst,
terification-direct esterification [117] or transamidification- leading to similar conversion yields. Additional to the depo-
direct esterification [104] in order to produce polyester or lymerization step, a transesterification with castor oil has
poly(ester amide) diols, respectively. also been conducted, incorporating silica nanofillers [127,

13
 Journal of Polymers and the Environment

128, 130]. Moreover, Zhou et al. [131] recently verified the spite of the fact that it requires highly toxic phosgene (Fig. 8)
novel incorporation of recycled PET into both, soft and hard [4, 138].
segment domains in waterborne polyurethanes, owing to the However, the application of hazardous phosgene and the
utilization of glycolyzed oligoesters as polyols and chain associated environmental awareness, have given rise to the
extenders in the PU synthesis. seek for more eco-friendly alternatives, such as substitu-
Crude glycerol also appears as a feasible choice given tion of phosgene by other equivalents, like triphosgene to
its vast production as a secondary product in the biodiesel produce isocyanates at large scales [139], or dehydration of
industry [56], so that it has been successfully converted into carbamate resulting from the carbonylation of amines with
natural polyols by means of direct esterification with fatty ­CO2 [140], although none of them has been yet industrially
acids to prepare polyurethane adhesives for bonding wood established [141].
[132, 133], similarly to the transesterification with diethan- Even more interestingly, the increasing renewability of
olamine of tall oil obtained from Kraft pulping [100]. polyurethanes has been achieved by synthesizing isocyanates
Finally, carbon dioxide, an inexpensive and abundant from natural feedstocks, such as vegetable oils and fatty
greenhouse gas, can offer a new synthetic route in the manu- acids. Thus, Çaylı and Küsefoğlu [142] conducted the allylic
facturing of polyurethanes [134], contributing to the allevia- bromination of soybean oil, followed by its reaction with
tion of environmental pollution [135]. The synthesis of the AgNCO at room temperature in THF, leading to NCO-termi-
­CO2-based polyols consists of the fixation of C ­ O2 with the nated soybean oil, whereas Hojabri et al. [141], in an effort
aid of oxirane groups-bearing materials, using a metal cata- to reduce the steric hindrance of the present dangling chains,
lyst, leading to polycarbonate polyols (Fig. 7), which have proposed a Curtius rearrangement of diacids with sodium
served to prepare footwear polyurethane adhesives [136] or azide obtaining a linear aliphatic diisocyanate (Fig. 9a).
mussel biomimetic pH-sensitive hydrogels [137]. This process was later improved obtaining even longer
unsaturated diacids when using a 2nd generation Grubbs
Synthesis of More Sustainable Isocyanates catalyst, avoiding the occurrence of explosive intermediate
azelaic acid, to further synthesize the bio-based diisocyanate
All the renewable alternatives so far reviewed are founded (Fig. 9b) [44]. In addition, More et al. [4] efficiently synthe-
on the development of “greener” polyurethanes by generat- sized highly pure oil-based isocyanates through a several-
ing bio-based polyols, without paying attention to the other step protocol based on simple organic reactions in which
PU-major component, the isocyanates, which come from diacyl hydrazide appears as an intermediate product.
petroleum resources [42]. In the last decade, bio-sourced diisocyanates, mainly
Among other synthesis mechanisms, the conventional coming from aminoacids (l-lysine diisocyanate) and fatty
Curtius and Hoffman rearrangements, which consist of the acids (dimeryldiisocyanate), have been the focus of several
rearrangements of acyl azide or amide groups, respectively, investigations, yielding renewable polyurethanes whose
are typically employed to produce isocyanates at the labora- response appears to lack of toxicity, according to the in vivo
tory scale. Moreover, the amine phosgenation (Hetschel) is cytotoxicity analysis results reported by Calvo-Correas et al.
the main isocyanate production commercially applied, in [13].

Fig. 7  Oxirane ring carbonata-

tion

Fig. 8  Synthesis of isocyanates

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Journal of Polymers and the Environment

Fig. 9  Soybean oil-based diiso-

cyanates synthesis reported by
Hojabri et al. a [141] and b [44]

Development of new synthetic pathways be considered, including bis(hydroxymethyl)propionic

acid [148] or 2,2-dimethylbutanoic acid [149] among oth-
In accordance with the Green Chemistry tenets, the appli- ers, dimethylol propionic acid (DMPA) has been the most
cation of synthesis protocols involving “safer solvents and extensively used [150–153], even finding in the literature
reaction conditions” [18] is a further step to a sustainable simultaneous application of several emulsifiers in order to
production of PUs, as may be inferred from the recent synthesize finer WPU dispersions [154].
investigation of Boulauche et al. [143], when conducting a Furthermore, these polyurethane dispersions may be pre-
solvent-free cationic polymerization, by dint of the applica- pared by different procedures, being the prepolymer [155,
tion of a heterogeneous ecofriendly catalyst, namely magh- 156] and acetone [157–159] techniques the most extensively
nite-H+. As a consequence, the production of waterborne, reported. Briefly, in the prepolymer method, the hydrophilic
radiation-curable and non-isocyanate polyurethanes have NCO-terminated prepolymer is synthesized in a first step
emerged in response to the ever-increasing environmental from the emulsifier and the conventional polyurethane pre-
awareness. The following sections briefly describe these cursors (polyol, diisocyanate and diol chain extender). Then
synthetic routes. the carboxylic groups of the ionic emulsifier are neutralized
with amines (typically triethylamine), followed by the pre-
Waterborne Polyurethanes polymer dispersion in water. The last chain extension with
diamines terminates the preparation of waterborne polyure-
Water-based polyurethane dispersions, also known as water- thanes, as shown in Fig. 10. Conversely, the acetone process
borne polyurethanes (WPU), allow for the replacement of follows the same steps but performing the neutralization and
the traditional solvent-borne polyurethanes, thus reducing further chain extension in acetone, or other water-miscible
the environmental impact, as revealed by the comprehensive organic solvents, to ensure homogeneous conditions. This
approach of the life cycle assessment conducted by Maciel low boiling point solvent is removed through vacuum distil-
et al. [144], besides exhibiting some beneficial advantages, lation after dispersion in water (Fig. 10).
inter alia versatile structure-properties relationship and good Moreover, the significant influence of the synthetic pro-
processability and elasticity [145, 146]. cedure on the waterborne polyurethane properties has been
Waterborne polyurethanes constitute the group of polyu- corroborated by Pérez-Limiñana et al. [160], who demon-
rethane systems composed of a dispersion of binary colloidal strated the narrower particle size distribution provided by
particles in an aqueous matrix, so that, as a consequence the acetone process over the prepolymer method, due to the
of their characteristic hydrophobicity, there is the need to promotion of the prepolymer dispersion in water resulting
insert water-compatible stabilizing groups (emulsifiers) from the lower prepolymer viscosity in the presence of an
into the polyurethane matrix. These emulsifiers consist organic solvent. However, the properties of the final WPU,
of hydrophilic and amphiphilic compounds which can be such as phase separation, thermal and mechanical resistance
classified into internal and external emulsifiers [145, 147]. or the particle size, have been proved to be deeply dependent
Although a wide range of internal emulsifiers, either ionic on other reaction factors, such as the ionic content [161] or
(cationic, anionic or even zwitterionic) or non-ionic, could chain extender chemical structure [162].

13
 Journal of Polymers and the Environment

Fig. 10  Waterborne polyure-

thane synthesis via prepolymer
(solid line) and acetone (dashed
line) processes

The significant impact of the design of such sustainable antibacterial activity. To that end, in situ hybridization with
synthetic route becomes noticeable in studies as that con- silica [127] and sulfonic [166] amine chain extenders, or
ducted by Li et al. [14], revealing the preparation of polyu- diols more sensitive to hydrolysis linkages [150] like, for
rethane systems with around a 90% of renewable content, instance, those holding silver nanoparticles [167] or long ali-
owing to the combination of WPU synthesis procedure with phatic branches [151, 163], enable the customization of the
the utilization of renewable resources, namely isosorbide resulting WPUs. Indeed, as Tsen et al. pointed out [153], the
polyol and fatty acid-based isocyanate. Additionally, Zhou in situ hybridization with 2,2,3,3,4,4,4-heptafluorobutynic
et al. [131] and Cakić et al. [130], for their part, properly acid 2,2-bis-hydroxymethyl-butyl ester (HFBA) to WPUs
incorporated recycled PET bottles in the polyurethane struc- confers them impressive thromboresistance values, result-
ture via glycolysis, whereas Saetung et al. [146] used polyols ing in competitive fluorinated polyurethane dispersions to
based on natural rubber and rubber seed oil acting as the be applied as biomaterials in living organisms. Following
starting materials for renewable WPU for application in the such in situ copolymerization approach, Chen et al. [168]
footwear industry. prepared novel high viscosity waterborne polyurethane-
Waterborne polyurethanes have been mainly intended cellulose nanofibril composites for the synthesis of direct
for eco-friendly adhesive production, even though other three-dimensional printing ink, holding good shear-thinning
purposes such as gravure printing ink [151, 163], ther- properties, what enabled the production of biomedical engi-
mally responsive elastomers [164] or biomedical coatings neering scaffolds with improved mechanical behaviours and
[165] have been reported. Notwithstanding, regardless of a degradability threefold faster than a conventional PU. Con-
the application field to which these systems can be meant, versely, a simpler ex situ incorporation of modifiers includ-
there are still some shortcomings to be remedied, associ- ing silica nanoparticles [169, 170], cellulose nanocrystals
ated with the film stability in terms of mechanical, thermal [155], ferric ions [171] and thickeners [172] can be success-
and chemical resistance, or the lack of biocompatibility and fully carried out.

13
Journal of Polymers and the Environment

More interestingly, the copolymerization with acrylic apart from facilitating the control of the polymerization pro-
monomers can provide the desired properties for water- cess and improving the ultimate film properties [177].
borne polyurethanes, while simultaneously producing a This technique is particularly useful in biocompatible
controlled crosslinking process and replacing the organic adhesives and tissue engineering, where a quick curing step
solvent required to adjust the viscosity of the medium. Even is required, despite the need for oxygen inhibition in order
though some investigations have dealt with the addition of to avoid likely side reactions, quite achievable by modify-
acrylic polymer chains by radical polymerization of acrylate ing the radiation intensity and initiator concentration [178].
monomers without chemical interaction between urethane Thus, Liu et al. [165] intended to avoid attachment of micro-
and acrylate molecules [173], grafting of hydroxyl bearing organisms to WPU coatings by embedding lysozyme into
acrylate monomers (hydroxyethyl acrylate, hydroxyethyl the polyurethane backbone via photopolymerization, while
methacrylate, bisphenol-A-glycidyl dimethyl acrylate, etc.) Abdalla et al. [179] effectively prepared homogeneous bio-
as anchoring sites covalently embed into the PU backbone compatible adhesives based on polycaprolactone and 2-iso-
leads to stable WPU/acrylic hybrids, whose polymerization cyantoethylmethacrylate in just 60 s. Such UV-light sus-
step is typically accomplished with UV-radiation and a pho- ceptible isocyanates have also been applied in other studies
tosensitive compound [174] or in the presence of potassium [180, 181] pointing out that UV-induced radically polymer-
persulfate (KPS) as radical initiator [175]. Besides, Alvarez izable functional groups can be found not only in additional
et al. [176] have recently proposed a new radical polym- monomers but also in the isocyanate source.
erization methodology based on a redox initiating blend of As with the production of polyurethane dispersions in
ascorbic acid and hydrogen peroxide, allowing for conduct- water, UV polymerization technique may be combined with
ing the polymerization at 30 °C. other strategies towards sustainable production, so that it
can be supplemented with the synthesis of natural polyols
Radiation Curable Polyurethanes via fatty acid esterification [182], thiol-ene coupling of veg-
etable oils [99] or liquefaction of bagasse [183]. In addition,
Polymerization of polyurethanes with the aid of ultravio- the combination of this photo-crosslinkable technique with
let (UV) radiation has recently drawn the attention due to waterborne systems has also been reported by Wei et al.
its remarkable advantages, namely process simplicity, mild [184], and Bakhshandeh et al. [185] who produced UV-cur-
reaction conditions, fast and efficient drying process, along able polyurethane dispersions from renewable castor oil and
with the absence of volatile organic solvent in an easily con- hydroxyl-terminated polydimethylsiloxane, respectively, to
trolled curing process. The synthesis of photo-crosslinkable be applied as coatings after water evaporation. More remark-
polyurethanes requires the usage of UV-sensitive monomers, able is the dual curing polymerization proposed by Hu et al.
mainly acrylates, and a photo-initiator, together with the tra- [186] when preparing bio-based coatings from castor oil-
ditional polyurethane building blocks, leading to the pro- based polyurethane/acrylate and epoxidized cardanol glyci-
duction of polyurethane acrylate systems. Therefore, some dyl ether, so as to reduce the shrinkage previously observed
hydroxyl-containing monomers, such as 2-hydroxyethyl during radical polymerization. Not long after, Hu et al.
acrylate (HEA), 2-hydroxyethyl methacrylate (HEMA) or [187] considered the preparation of cardanyl acrylate from
2-hydroxypropyl acrylate (HPA) (Fig. 11), are typically cardanol and acryloyl chloride, in order to be considered as
considered to facilitate their grafting via polycondensation reactive diluent for the preparation of photo-crosslinkable
between their hydroxyl groups with reactive diisocyanates, polyurethanes, in an effort to further improve in more than
so that the double bonds confer their UV-light activity. The a 10% both the renewability and volumetric shrinkage of the
addition of these reactive diluents is also of great impor- resulting UV-curable polymers. Furthermore, the additional
tance, since they confer these systems a suitable viscosity, utilization of bio-based polyols has been reported as well,
such as dextran [188] or rosin [189].

Non‑isocyanate Polyurethanes

Although the vast majority of the research production has

dealt with the sustainable polyurethane synthesis by using
natural occurring building blocks, one sector of the research
field has opted for taking a further step removing the haz-
ardous isocyanate from the polyurethane production, thus
Fig. 11  Chemical structure of the most common UV sensitive meeting the current environmental regulations aimed to
acrylate monomers: a HEA; b HEMA; c HPA reduce the exposure to isocyanates [190], in such a way that

13
 Journal of Polymers and the Environment

polyurethanes thereby produced are known as non-isocy- The main disadvantage of this synthetic route is related to
anate polyurethanes (NIPU). its low reaction rate at room conditions, given that a thermal
Despite the fact that different synthetic protocols can activation may prompt side reactions [191]. Therefore, the
lead to NIPUs, as reviewed recently by Cornille et al. [191], solution that best addresses this issue is the employment of
exclusively the polyaddition between bicyclic carbonates and catalysts, since, while an increase in the number of mem-
diamines, as shown in Fig. 12, has proved to prevent the bers of cyclic carbonates has frequently proved to provoke
utilization of toxic substances (phosgene, aziridines, azides, a reactivity rise [196, 197], their synthesis requires to be
carboxamides, etc.) and the production of byproducts. Since conducted under well-defined conditions, along with the
the first patent on NIPU preparation published by Groszos application of harmful materials, especially regarding the
and Drechsel [192], this synthesis protocol has turned into manufacture of bicyclic carbonates [56].
the most relevant and used synthetic pathway for the produc- Moreover, although cyclic carbonates may be obtained
tion of bio-based polyurethanes. through transesterification and transcarbonation with
The appearance of pendant hydroxyl groups through this diols [198], the catalytic production of the most exten-
aminolysis reaction, whose primary or secondary character sively utilized 5-membered cyclic carbonate via ­C O 2
heavily depends on the synthetic path followed (Fig. 12), is fixation into oxirane groups seems to be a much more
the reason why this group of polyurethanes is also known as appealing method to pursue an improved renewable con-
polyhydroxyurethanes (PHU). The improved hydrophilicity tent, while mitigating the environmental impact of this
entails stronger cohesive forces, apart from enhanced ther- greenhouse gas [199]. Hence, the synthesis of bicyclic
mal and chemical resistance owing to the establishment of carbonate from carbonation of bisphenol S-based diglyci-
inter- and intra-hydrogen bonds, which, in turn, gives them dyl ether, as described by Kim et al. [200], offers a yield
the chance to act as reactive polyols in further chemical of 74%, similar to the 76% reported by Cornille et al.,
modifications. whose polyfunctional cyclic carbonates conferred quanti-
The reaction mechanism of this process has been ana- tative conversion with diamines in the presence of a thio-
lyzed from different standpoints, so that, according to Tom- urea catalyst, leading to non-isocyanate polyurethane with
ita et al. [193], this reaction is controlled by differences in appropriate foam [201] and adhesion [202] performances.
electron densities giving rise to the appearance or breaking Moreover, Arvin et al. [203] recently prepared NIPUs
of chemical linkages, while to Zabalov et al. [194] it is based from carbonate sucrose soyate synthesized through ­CO2
on a single- or several-step procedure in which a second fixation on epoxidized sucrose soyate under supercriti-
amine molecule acts as catalyst. Anyhow, it was disclosed cal conditions, optimizing the solvent resistances of the
the second-order character of this reaction [193], besides the ensuing polymer coatings when using a dual Lewis acid/
fact that primary amines and polar solvents seem to promote Lewis base pair catalyst and conducting a 1 week cur-
the addition reaction [195]. ing procedure at room temperature. On account of such a

Fig. 12  Non-isocyanate polyu-

rethane synthesis

13
Journal of Polymers and the Environment

high pressure requirement associated to the C­ O2 fixation,

Wang et al. [204] promoted the production of NIPUs by
conducting a sustainable synthesis protocol under milder
and safer reaction conditions for the preparation of those
cyclic carbonates comprising a first O-chloro alcohol
resin synthesis from phthalic anhydride and pentaerythri-
tol, and its subsequent reaction with sodium bicarbonate,
leading to polyfunctional cyclic carbonates.
Even more sustainable production of NIPUs deals
with obtaining bio-based cyclocarbonates by means of
a lipase B-catalyzed esterification of Sapium sebiferum
oil-derived dimer acid with glycerol carbonate [205],
or applying an easily scalable catalytic procedure from
levulinic acid biomass-derived diphenolic acid, leading
to renewable WPU coatings [206]. On the other hand,
Thébault et al. [207] reported the preparation of PHUs
with aminated and carbonated mimosa tannin extract,
achieving a bio-sourced content above 70%. By contrast,
Tryznowski et al. [196] attained a 79% yield in the syn-
thesis of five-membered cyclic carbonate from diglyc-
erol to further produce non-isocyanate polyurethanes
via one-step protocol at high temperatures. Further on,
the wettability of these NIPUs was subjected to a deeper Fig. 13  Non-isocyanate poly(ester urethane) synthesis [214]
investigation [208], revealing that the low hydropho-
bicity of polyhydroxyurethanes may have a detrimental
effect on their performance under high moisture condi- Bio‑polyurethanes in the Adhesion Field
tions. Besides, these systems typically exhibit reduced
hardness and glass transition temperatures, giving rise to Fundamentals and General Concepts
inefficient chain mobility [205]. Although Cornille et al.
[201] were capable of increasing the movement of the Since their inception, polyurethanes have become wide-
molecular chains with the utilization of a blowing agent, spread in the adhesive field, being applied on an extensive
that methodology applies only for foams. array of surfaces (glass, wood, plastics, ceramics, etc.).
Therefore, other methodologies, essentially hybridiza- Thus, starting with the urethane prepolymers during the
tion, have been considered. Thus, in an attempt to replace fifties, followed by the waterborne polyurethanes patented
traditionally isocyanate-based polyurethane adhesives, by DuPont [215] and ending with the most recent pressure
Leitsch et al. [209] claimed to report the pioneering pro- sensitive and hot melt adhesion techniques, polyurethane
duction of PU/PHU hybrids first conducting a conven- adhesives have carved out a well-established market niche.
tional NCO-OH condensation, followed by chain exten- Adhesion can be defined as the phenomenon of join-
sion with diamines, thanks to the previously grafted ing two substrates, so that it is not an exclusive property
1,2-carbonate glycerol. Although, according to Leitsch of adhesives but, in general terms, also of coatings, paints,
et al., the presence of free isocyanates is avoided dur- varnishes, etc., in other words, whenever two solids are put
ing the adhesive application, they still participate in the together [216]. Therefore, adhesion is the result of a sev-
early stages of the synthesis. In this sense, the prepara- eral-step process in which the adhesive flows and wets the
tion of PHU hybrids with epoxy [210, 211], polyhedral surface, establishing certain physicochemical interactions in
oligomeric silsesquioxane [212] and amide [213] groups the adhesive mass (cohesion) and with the substrate (adhe-
appears to provide a safer way to tailor the PHU proper- sion), including Van der Waals and dipole forces, along with
ties while preventing the use of isocyanates. More inter- stronger hydrogen and covalent bonds. Hence, a suitable
estingly, Wang et al. [214] completely averted pendant wettability, thus promoting an intimate adhesive-substrate
hydroxyl groups in NIPU’s chemical structure by the contact, is an important factor to take into consideration,
reaction between diamines and monocyclic carbonates, which can be achieved whether the intermolecular forces of
and further esterification with dicarboxylic acids, as the adhesive are weaker than the corresponding interaction
shown in Fig. 13. with the adhesion surface, meaning surface energy lower
than the corresponding to the adhesion substrate [2].

13
 Journal of Polymers and the Environment

Additionally, the performance of an adhesive is not only Table 1  Polyurethane adhesives classifications [2]
determined by its properties, such as rheological behaviour Components One component Two
or surface free energy, but also by the adhesion surface char- Physical State compo-
acteristics (pH, functional groups, roughness, presence of nents
debris or extractives) and curing conditions (temperature,
Liquid like Solvent-borne TPS TS
humidity, etc.). As a consequence, some investigations have
Water-borne TPS TS
revealed the relevant influence of parameters such as the
Solvent-free TS TS
relative humidity [217], artificial aging [218] and substrate
Solid like Hot melt TP
modifications to improve the adhesive wettability [219] on
Reactive hot melt TS
the ultimate properties developed by the adhesive joints.
Powder TPS
The already discussed heavy reliance on industrial pro-
duction of crude oil, also concerning the adhesive field, TP thermoplastic, TS thermosetting, TPS thermoplastic or thermoset-
has been the driving force for the removal of toxic vola- ting
tile organic compounds (VOC) from adhesive formulations
traditionally used as carrier fluids [220]. Nonetheless, the reactive, consist of NCO-terminated prepolymers, in which
well-known efficient wettability, hydrogen bonding and the reaction with proton donor groups on the substrate and/or
ability to establish chemical interactions associated with with atmospheric humidity (moisture curable polyurethanes)
polyurethanes place them in a favorable position to suitably is the driving force for curing, whereas those containing a
satisfy the requirements for the production of bioadhesives. carrier, like in two-component PUs, curing comprises the
Additionally, bearing in mind the progress made in the coalescence of precipitated particles owing the removal of
manufacturing of bio-sourced polyurethanes, as described the carrier fluid. Moreover, hot melt PU adhesives are solid
in preceding sections, these “greener” adhesives seem to be typically melted, thus acquiring appropriate wettability,
increasingly meeting the definition of “bio-based adhesive” leading to the adhesive bond by cooling from the molten
coined by Pizzi [221], which states that “bio-based adhe- state, although on some occasions combined with moisture
sives include those materials of natural, non-mineral, ori- reactions (reactive hot melt adhesives) [2].
gin which can be used as such or after small modifications As reflected by extensive research production on moisture
to reproduce the behaviour and performance of synthetic curable adhesives [224–227], such type of one component
resins”. polyurethanes has been widely applied. Notwithstanding,
as stated above, the main obstacle of the consequent cur-
Latest Advances in Bio‑based Polyurethane ing step is the production of ­CO2, which may diminish the
Adhesives adhesion performance as a result of the appearance of bub-
bles or pores. In this regard, some studies have avoided the
As reviewed throughout the previous sections, the widely carbon dioxide production by synthesizing silane-modified
flexible composition of polyurethanes adhesives has made PU, releasing ethanol instead of ­CO2 as a result of the cur-
them such versatile materials that they can be applied in ing reaction with environmental humidity [228], while Yuan
many areas, such as in automotive [222], footwear [173], et al. [229] reported the implementation of oxazolidines as
woodworking [223], etc. In general, as a consequence of latent curing agent, since their hydrolysis leads to alkano-
such extensive array of polyurethane adhesives, several lamines as intermediate products, further reacting with
classifications can be found on the basis of different cri- free isocyanate groups (Fig. 14). The ketones, produced
teria, whether physical state (solid or liquid), number of as byproducts, are easily volatilized. With this modifica-
components to blend to promote the adhesion (single or two tion, these authors succeeded in raising the shear strength
components), curing mechanism (thermosetting or thermo- of single-component polyurethanes eight times, while
plastic) or carrier (solvent-borne, water-borne or solvent- attaining 20-fold greater adhesion forces via the addition
free). These classifications meeting different approaches are of ­CaCO3 as a filler at 23% of the content. Filler incorpora-
summarized in Table 1. tion allowed them to prepare smoother adhesive surfaces
Two-component polyurethanes represent those adhesives with reduced pores content as a consequence of the reinforc-
traditionally produced whose components are delivered in ing water absorption effect of ­CaCO3 particles. Therefore,
separate compartments given their commonly high reaction these authors successfully produced more environmentally-
rate. In these systems, whether solvent- or water-based, the friendly polyurethane adhesives, in a broader sense than the
curing process is mainly occasioned by carrier release after one associated with the definition of “bio-based adhesives”
urethane linkages formation, while solvent-free polyure- abovementioned [221]. Indeed, as previously stated, accord-
thanes yield adhesive joints exclusively due to NCO-OH ing to the Green Chemistry principles [18], the “sustainabil-
reaction. Conversely, one-component adhesives, when ity” of adhesives lies not only in their provenance, i.e. their

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Journal of Polymers and the Environment

Fig. 14  Latent curing mecha-

nism of oxazolidines [229]

chemical constituents, but also in all aspects associated to that, Norazwani et al. [233] assessed the modification of
their synthesis and application, such as the reduction of the aluminum alloy by either alkaline etching or warm water
­CO2 release related to the adhesive end-use. followed by silanization. The improved polyurethane adhe-
Furthermore, the great versatility of the urethane poly- sive wettability resulting from greater surface roughness
mer network has unleashed a myriad of investigations [112, achieved through either case was especially noticeable in
113, 133, 230, 231] dealing with judicious variations in the the significant contact angle reduction (20–30°) and the
NCO:OH molar ratio in order to optimize the PU adhesion development of shear strengths three times higher than that
response. Even though some researchers achieved optimal shown by the untreated aluminum surface.
properties at higher NCO:OH ratios [232, 233], most of Moreover, given the natural compatibility between iso-
them reported a generalized value of 1.3 to obtain more cyanate and hydroxyl bearing compounds, polyurethane
appropriate adhesion performance, giving rise to not only adhesives have been extensively applied for bonding wood
more interesting type of failure, i.e. substrate [113], but also [113, 223, 232]. However, on this substrate the adhesive
to improved lap-shear strengths, as described by Cui et al. mobility into the substrate porous is strongly influenced by
[132, 133] who developed PU adhesives with shear strengths wood moisture, owing to the side reaction occurring between
of around 36 MPa, fairly competitive with the 29-37.7 MPa NCO groups with water (free or bound) instead of with sub-
shown by commercial benchmarks based on petrochemical strate reacting sites. Therefore, Bastani et al. [234] thermally
raw materials. Cui and coworkers succeeded in synthesiz- modified Scots wood pine to control its moisture content,
ing fast-curing adhesives from crude-glycerol, whose cur- while Lavalette et al. [235] revealed the greater influence
ing times have proven to be below 1 h, even shorter than of moisture content on the ultimate shear strength than the
those accomplished by PU adhesives based on castor [112] amount of one-component polyurethane adhesive in the pro-
or canola [220] oils. duction of green-glued plywood. Hence, the considerable
On the other hand, the adjustment of adhesion properties influence of water contact is apparent, although it can also
of polyurethanes has also been addressed by changing other be extended to curing and storage steps as shown by Chat-
parameters, such as polyol hydroxyl value [133] or chemical topadhyay et al. [236] or Asahara et al. [217] when analyzing
structure of chain extenders [162]. Particularly significant is the curing kinetics under moisture conditions. Because of
Somani’s investigation [112], which revealed the superior the critical importance of correctly understanding the adhe-
properties of aromatic isocyanates over their analogous ali- sive aging, Huacuja-Sánchez et al. [237] have studied the
phatic, leading to castor oil-based aromatic polyurethanes long-term adhesion performance of crosslinked PU adhe-
with lap-shear strengths around seven times greater. Over- sives by conducting different maturation conditions, namely
all, larger polyol functionalities promote greater crosslinking conditioning under 90% of relative humidity at 60 °C and
densities, resulting in improved glass transition temperature immersion in water at different temperatures. The plasticiz-
­(Tg), chemical and hydrolysis resistance [113, 133]. ing effect of water, more pronounced at greater temperatures,
With the aim to design high-quality joint adhesives, was proved to undermine the shear modulus in a 40% and
as above stated, the characteristics of the substrates to ­Tg in 16.7 °C due to the substitution of free urethane and
be bonded deserve attention as well. Indeed, the applica- inter-urethane hydrogen bonding by hydrogen bridging with
tion of mechanical pretreatment on the adhesion surfaces, water molecules. Similarly, Raghunanan et al. [50] submit-
mainly polishing with sandpaper to increase the adhesive ted castor oil-based PU adhesives to different controlled
penetration, is generally acknowledged [231]. Besides relative humidities, pointing out that greater environmental

13
 Journal of Polymers and the Environment

moisture allowed to achieve an improved mechanical resist- also been applied to synthesize PU adhesives, thus improv-
ance, owing to the stronger hydrogen bridging associated to ing their renewability due to the utilization of sustainable
a larger urea content. materials, such as C ­ O2 [134, 136] or sucrose [245], while
In order to enhance the behaviour of polyurethane adhe- at the same time avoiding the utilization of isocyanates dur-
sives, among other properties adhesion strength, durability ing their synthesis. This technique also promotes the adhe-
and thermomechanical resistance, the addition of modifiers sion to the substrates via secondary interactions (van der
has been proposed. Accordingly, Arán-Aís et al. [238] added Waals forces, hydrogen bonding, etc.) due to the presence of
rosin acid to the polyurethane-urea formulation as an inter- hydroxyl groups in their chemical structure, outperforming
nal tackifier to bestow a proper immediate adhesion to PVC. not only the previous solvent-borne but also WPU adhesive
Malik and Kaur [105] reported the preparation of nanocom- dispersions [246, 247].
posites with the addition of titanium dioxide ­(TiO2) in castor Finally, bearing in mind the likely reaction between free
oil-based PU adhesives, entailing remarkable enhancements isocyanates with amine groups located in the proteins, the
in adhesion strength and chemical resistance with only a 3% polyurethane adhesive field has also spread to the biomedi-
wt of nanoparticles, while the addition of a more moderate cal area, requiring quick curing process and biocompatible
content of 2.5% wt of organically modified nanosilicas into building blocks to be applied as bioadhesives in living tis-
hyperbranched polyurethane obtained from Mesua ferrea L. sues [49, 227, 248]. In response to the growing need for
seed oil [239] almost doubled the lap shear strength results the rapid curing process, photo-crosslinkable technique
on wood (from 6.5 up to 10.8 MPa) also raising tensile emerges to satisfy such requirements [180], enabling the
strength in 10 MPa. For their part, Li et al. [171] achieved a reduction of the curing times until one minute as Abdalla
substantial increase of 330% in the shear strength of WPU et al. [179] pointed out, obtaining morphologically homo-
adhesives when adding a 25% w/w of ferric nitrate, used as geneous and biocompatible photo-crosslinkable biomedi-
a complexing agent in contrast with the neat WPU. cal polyurethane adhesives from polycaprolactone-diol and
In an effort to further increase the sustainability of poly- 2-isocyanatoethylmethacrylate.
urethane adhesives, petrochemical derivatives traditionally
used in the PU production have been substituted by more
eco-friendly alternatives, such as polyols. For that matter, Concluding Remarks
Tenorio-Alfonso et al. [240, 241] succeeding in completely
replacing the hydroxyl-bearing building block with cellu- Given the emerging environmental concern prevailing in the
lose acetate and unmodified castor oil, preparing bio-sourced industrial production of polyurethanes and the awareness of
polyurethane adhesives whose shear, stripping and flexural the use of non-renewable raw materials, the recent trends
resistances equated or even exceeded those found on a wide framed within the actions intended to reduce the detrimental
assortment of commercial benchmarks [242]. Conversely, effects attributable to traditional petroleum-based polyure-
Raghunanan et al. [50, 243] implemented more benign reac- thanes have been reviewed, with a special focus on adhe-
tion conditions (at room temperature and in the absence of sives, which are also generally associated with the release
heating or inert atmosphere protection) to functionalize raw of toxic solvents during curing. Therefore, the viability of
castor oil with hexamethylene diisocyanate, intended for preparing polyurethanes from various natural feedstocks has
bio-adhesive applications. Hence, Raghunanan et al. [50] been amply demonstrated. Indeed, among others, lignocel-
highlighted the advanced adhesion strengths exhibited by lulosic biomass, primarily composed of hemicellulose, cel-
the thus synthesized bio-adhesives on wood when cured at lulose and lignin, has been proven effective in increasing
high humidity environments, given the promoted hydrogen the renewability of polyurethanes, due to their significant
bond content arising from the larger number urea linkages hydroxyl content, thereupon implemented as elastomers,
in the PU structure. adhesives, coatings, lubricants, etc. On the other hand, veg-
It can also be found the implementation of natural poly- etable oils have emerged as promising polyol precursors.
ols, such as bio-based aliphatic poly(1,3-propylene dicar- For that purpose, given their scant reactivity, most inves-
boxylate) diols [244], those resulting from liquefaction of tigations have encompassed a series of chemical modifica-
polysaccharides [32, 34, 231] or from the modification of tions (epoxidation, hydroformylation, trans-amidification,
vegetable oils (predominantly epoxidation with further esterification, etc.) in order to confer hydroxyl functionality
oxirane ring-opening [66, 78] or transesterification [126, upon these plant oils, even though some natural oils already
128, 129]), thus designing polyurethane adhesives with exhibit a certain hydroxyl character (lesquerella or castor
fairly competitive or even superior adhesion properties than oils), which allows them to be implemented without further
commercial benchmarks. functionalization, even achieving a complete replacement of
Furthermore, the production of polyhydroxyurethanes the petrochemical polyols while maintaining their ultimate
through the already detailed non-isocyanate pathway has properties, when combining castor oil and lignocellulosic

13
Journal of Polymers and the Environment

materials for adhesion purposes. Although the application towards the synthesis of thermoplastic polyurethanes. Eur
of controlled environmental moisture has proved to opti- Polym J 49:823–833
5. Cherng JY, Hou TY, Shih MF, Talsma H, Hennink WE (2013)
mize the adhesion properties of vegetable oil-based PUs, Polyurethane-based drug delivery systems. Int J Pharm
some other techniques, such as hybridization or addition 450:145–162
of fillers seem to lead to even twofold lap shear strengths 6. Abdollahi MF, Zandi M, Shokrollahi P, Ehsani M (2015) Syn-
on wood. Moreover, pursuant to environmental protection, thesis and characterization of curcumin segmented polyure-
thane with induced antiplatelet activity. J Polym Res 22:1–10
the preparation of polyurethane adhesives from wastes has 7. Kupka V, Vojtova L, Fohlerova Z, Jancar J (2016) Solvent free
demonstrated to yield bio-adhesives which not only exhibit synthesis and structural evaluation of polyurethane films based
competitive adhesion strengths but also improved curing on poly (ethylene glycol) and poly (caprolactone). Express
response, fitting to the fast curing adhesive requirements. Polym Lett 10:479–492. https​: //doi.org/10.3144/expre​s spol​
ymlet​t.2016.46
Likewise, the production of bio-sourced isocyanates from 8. Rezayan AH, Firoozi N, Kheirjou S, Tabatabaei Rezaei SJ,
vegetable oils and fatty acids to be implemented in the con- Nabid MR (2017) Synthesis and characterization of biodegrad-
ventional polycondensation reaction has been reported as able semi-interpenetrating polymer networks based on star-
well. Additionally, milder manufacturing conditions and shaped copolymers of varepsilon-caprolactone and lactide. Iran
J Pharm Res 16:63–73
more sustainable synthetic routes have been proposed to suc- 9. Su S, Gu J, Lee H, Yu S, Wu C, Suen M (2016) Effects of
cessfully substitute such traditional protocol, including the an aromatic fluoro-diol and polycaprolactone on the prop-
preparation of waterborne polyurethane dispersions, remov- erties of the resultant polyurethanes. Adv Polym Technol
ing the utilization of the previous solvents as the dispers- 37(4):1142–1152
10. Wu C, Tsou C, Tseng Y, Lee H, Suen M, Gu J, Tsou C, Chiu S
ing agent, thus achieving an increase in the shear strength (2016) Preparation and characterization of biodegradable poly-
larger than a 300% when including just a 25% of ferric ions. urethanes composites filled with silver nanoparticles-decorated
Besides, the radiation-induced curing process has allowed graphene. J Polym Res 23:263
the production of biocompatible polyurethane adhesives 11. Zhu R, Wang Y, Zhang Z, Ma D, Wang X (2016) Synthesis of
polycarbonate urethane elastomers and effects of the chemical
from acrylate monomers in the absence of volatile organic structures on their thermal, mechanical and biocompatibility
compounds and through a 1 min-length reaction procedure. properties. Heliyon 2:e00125
On the other hand, the synthesis of non-isocyanate polyu- 12. Calvo-Correas T, Martin MD, Retegi A, Gabilondo N, Cor-
rethane adhesives by means of the polyaddition of cyclic cuera MA, Eceiza A (2016) Synthesis and characterization of
polyurethanes with high renewable carbon content and tailored
carbonates and diamines has also allowed not only the pro- properties. ACS Sustain Chem Eng 4:5684–5692. https​://doi.
motion of the adhesion performance, owing to the additional org/10.1021/acssu​schem​eng.6b015​78
hydroxyl groups, but also the fixation of environmental ­CO2 13. Calvo-Correas T, Santamaria-Echart A, Saralegi A, Martin L,
to become part of those cyclic carbonates while mitigat- Valea Á, Corcuera MA, Eceiza A (2015) Thermally-responsive
biopolyurethanes from a biobased diisocyanate. Eur Polym J
ing the environmental impact of this greenhouse gas, even 70:173–185. https​://doi.org/10.1016/j.eurpo​lymj.2015.07.022
though NIPUs with a bio-sourced content up to 70% have 14. Li Y, Noordover BA, van Benthem RA, Koning CE (2014)
been obtained when employing aminated and carbonated Reactivity and regio-selectivity of renewable building blocks
mimosa tannin extract. for the synthesis of water-dispersible polyurethane prepoly-
mers. ACS Sustain Chem Eng 2:788–797
15. Basterretxea A, Haga Y, Sanchez-Sanchez A, Isik M, Irusta L,
Tanaka M, Fukushima K, Sardon H (2016) Biocompatibility
Funding This work is part of two research projects (CTQ2014– and hemocompatibility evaluation of polyether urethanes syn-
56038-C3-1R and TEP-1499) sponsored by MINECO-FEDER and thesized using DBU organocatalyst. Eur Polym J 84:750–758
Junta de Andalucía programmes, respectively. One of the authors 16. Kavanaugh TE, Clark AY, Chan-Chan LH, Ramírez-Saldaña
(Adrián Tenorio-Alfonso) has also received a Ph.D. Research Grant M, Vargas-Coronado RF, Cervantes-Uc JM, Hernández-
from “Ministerio de Educación” (FPU13/01114). The authors grate- Sánchez F, García AJ, Cauich-Rodríguez JV (2016) Human
fully acknowledge the financial support. mesenchymal stem cell behavior on segmented polyurethanes
prepared with biologically active chain extenders. J Mater Sci
Mater Med 2:71–77
17. Oprea S, Potolinca VO, Gradinariu P, Joga A, Oprea V (2016)
Synthesis, properties, and fungal degradation of castor-oil-
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