polymers

Article
Synthesis of Nonisocyanate Poly(hydroxy)urethanes from
Bis(cyclic carbonates) and Polyamines
Marc Martínez de Sarasa Buchaca 1 , Felipe de la Cruz-Martínez 1 , Enrique Francés-Poveda 1 ,
Juan Fernández-Baeza 1 , Luis F. Sánchez-Barba 2 , Andrés Garcés 2 , José A. Castro-Osma 3, *
and Agustín Lara-Sánchez 1, *

1 Departamento de Química Inorgánica, Orgánica y Bioquímica-Centro de Innovación en Química

Avanzada (ORFEO-CINQA), Facultad de Ciencias y Tecnologías Químicas, Universidad de Castilla-La
Mancha, 13071 Ciudad Real, Spain; marc.martinezsarasa@uclm.es (M.M.d.S.B.);
felipe.cruz@uclm.es (F.d.l.C.-M.); enrique.frances@uclm.es (E.F.-P.); juan.fbaeza@uclm.es (J.F.-B.)
2 Departamento de Biología y Geología, Física y Química Inorgánica, Universidad Rey Juan Carlos,
28933 Móstoles, Spain; luisfernando.sanchezbarba@urjc.es (L.F.S.-B.); andres.garces@urjc.es (A.G.)
3 Departamento de Química Inorgánica, Orgánica y Bioquímica-Centro de Innovación en Química
Avanzada (ORFEO-CINQA), Facultad de Farmacia, Universidad de Castilla-La Mancha,
02071 Albacete, Spain
* Correspondence: joseantonio.castro@uclm.es (J.A.C.-O.); agustin.lara@uclm.es (A.L.-S.)

Abstract: Nonisocyanate polyurethane materials with pending alcohol groups in the polymeric chain
were synthesized by polyaddition reaction of bis(cyclic carbonates) onto diamines. For the platform
Citation: Martínez de Sarasa molecule, 1,4-butanediol bis(glycidyl ether carbonate) (BGBC, 1) was used. The polyaddition reaction
Buchaca, M.; de la Cruz-Martínez, F.; of 1 onto a wide range of diamines with different electronic and physical properties was explored.
Francés-Poveda, E.; Fernández-Baeza, J.; All PHUs were obtained quantitatively after 16 h at 80 ◦ C temperature in MeCN as solvent. The
Sánchez-Barba, L.F.; Garcés, A.; low nucleophilicity of L-lysine has proven unable to ring-open the cyclic carbonate and, thus, no
Castro-Osma, J.A.; Lara-Sánchez, A.
reaction occurred. The addition of DBU or TBD as the catalyst was tested and allows the obtention
Synthesis of Nonisocyanate
of the desired PHU. However, the presence of strong bases also led to the formation of polyurea
Poly(hydroxy)urethanes from
fragments in the new PHU. The different poly(hydroxyurethane) materials were characterized using
Bis(cyclic carbonates) and
a wide range of spectroscopic techniques such as NMR, IR, MALDI-ToF, and using GPC studies. The
Polyamines. Polymers 2022, 14, 2719.
https://doi.org/10.3390/
thermal properties of the NIPUs were investigated by DSC and TGA analyses. Moreover, reactions
polym14132719 employing different monomer ratios were performed, obtaining novel hydroxycarbamate compounds.
Finally, sequential and one-pot experiments were also carried out to synthesize the PHUs polymers
Academic Editors: Arantxa Eceiza
in one-step reaction.
Mendiguren, Lorena Ugarte
and Tamara Calvo-Correas
Keywords: non-isocyanate polyurethanes (NIPUs); poly(hydroxyurethanes) (PHUs); CO2 ; polyaddition
Received: 3 June 2022 reaction; cyclic carbonates
Accepted: 29 June 2022
Published: 2 July 2022

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1. Introduction
In the last 50 years, a compelling growth of interest has emerged within the scientific
community and plastic industry for the production of polyurethane (PU) materials due to
their versatility and wide range of applications. Thanks to their physical properties such as
hardness, elongation, strength, abrasion resistance, light weight, etc., they have been widely
used in biomedical, building and construction, automotive, textiles, adhesives, packaging,
and several other industries [1–7]. Traditionally, these materials have been prepared by the
polyaddition reaction of a diol (or polyol) onto a diisocyanate (or poly isocyanate), and
this method is still currently in use in industries [8]. However, isocyanate reagents are
hazardous for the environment and their production often requires the use of phosgene,
which is highly toxic for humans [9]. Therefore, alternative pathways for PU synthesis
involving greener intermediates and processes have become more and more attractive
for industrial and academic research. In this context, the synthesis of nonisocyanate

Polymers 2022, 14, 2719. https://doi.org/10.3390/polym14132719 https://www.mdpi.com/journal/polymers

Polymers 2022, 14, x FOR PEER REVIEW 2 of 17
Polymers 2022, 14, 2719 2 of 17

between a biscarbamate
polyurethanes and a diol
can be achieved [6,10–13],
by the the copolymerization
transurethanization of azidirines
polycondensation and COa2
between
[14–16], and the polyaddition reaction of bis(cyclic carbonates) and diamines (Scheme 1)
biscarbamate and a diol [6,10–13], the copolymerization of azidirines and CO2 [14–16], and
[17–19].
the polyaddition reaction of bis(cyclic carbonates) and diamines (Scheme 1) [17–19].

O O
(a) HO OH + R R R
R O N N O
H H
diol activated
biscarbamate
O
H R
(b) N N O
+ CO2 H
n

aziridine
NIPU
O O

(c) O O O O R R = different
+ H2N NH2 substituents
R
bis(cyclic carbonate) diamine
Scheme 1. Synthesis of nonisocyanate polyurethanes by: (a) transurethanization
transurethanization reaction;
reaction; (b)
(b) cou-
cou-
pling of azidirines and CO ; and (c) polyaddition reaction of bis(cyclic carbonates) and diamines.
pling of azidirines and CO2 ; and (c) polyaddition reaction of bis(cyclic carbonates) and diamines.
2

Amongst them,
Amongst them,most
mostattention
attentionhas hasbeen
beengiven
giventotothe
the polyaddition
polyaddition reaction
reaction of of bis(cy-
bis(cyclic
carbonates) and and
clic carbonates) diamines sincesince
diamines cycliccyclic
carbonates have gained
carbonates much much
have gained interest from many
interest from
research groupsgroups
many research and industry due to due
and industry theirtoapplications as solvents
their applications [20,21], [20,21],
as solvents electrolytes for
electro-
batteries [22,23], and
lytes for batteries precursors
[22,23], for the synthesis
and precursors of polymers
for the synthesis and fine chemicals
of polymers [24]. This
and fine chemicals
route exhibits
[24]. This routeseveral advantages
exhibits such as the such
several advantages use ofasCOthe2 as a sustainable
use of CO2 as aCsustainable
1 feedstock C to1
synthesize
feedstock to thesynthesize
cyclic carbonate, which
the cyclic has beenwhich
carbonate, seen of
hasvital
beenenvironmental
seen of vitalimportance
environmentaland
as a synthetic
importance challenge
and duringchallenge
as a synthetic the last few yearsthe
during [25–30].
last fewFurthermore, the Furthermore,
years [25–30]. ring-opening
reaction with diamines generates linear poly(hydroxyurethane)s,
the ring-opening reaction with diamines generates linear poly(hydroxyurethane)s, with pending primary
with
or secondary alcohol groups within the main polymeric chain,
pending primary or secondary alcohol groups within the main polymeric chain, whichwhich gives the polymer
specific
gives the properties
polymer such as better
specific adhesion,
properties such thermal
as betterstability,
adhesion, and chemical
thermal resistance
stability, andto non-
chem-
polar solvents (Scheme
ical resistance 2) [31].
to nonpolar In addition,
solvents the reactive
(Scheme 2) [31]. hydroxyl groups
In addition, theenable thehydroxyl
reactive polymer
to undergo
groups postfunctionalization
enable the polymer to undergo reactions with chemical and biological
postfunctionalization reactions functionalities
with chemical [32].
and
As reported in the literature, the secondary alcohols moieties
biological functionalities [32]. As reported in the literature, the secondary are mainly generated
alcoholsduring
moie-
the
ties polymerization
are mainly generatedprocess with respect
during to their primary
the polymerization counterparts
process [32–34].
with respect to their primary
Since the pioneer
counterparts [32–34]. work of this synthetic route for the NIPUs in 1957 [35], several
reviews about the synthesis of polyurethanes have been reported by different research
groups [6,10,17–19,31,36]. In general, the ring-opening reaction of the cyclic carbonate
by the amine takes place without the use of a catalyst. However, the reaction rate can
be accelerated through activation of the monomers by using either weak Lewis acid or
oxophilic additives to increase the electrophilicity of the cyclic carbonate group or by the
addition of basic additives to increase the nucleophilicity of the amine or even deprotonate
it [37,38]. Generally, the polyaddition of cyclic carbonates onto diamines is carried out
in polar aprotic solvents such as dimethylformamide (DMF), dimethylsulfoxide (DMSO),
N,N-dimethylacetamide (DMAc), etc., due to the better solubility of the starting materi-
als [32,33,39]. The temperature also has an influence on the outcome of the polyaddition
reaction [40,41]. Thus, higher yields and reaction rates were obtained when the reaction
temperature was increased, which was explained by the decrease of the viscosity in the
reaction mixture [41].
Polymers 2022, 14, 2719 3 of 17
Polymers 2022, 14, x FOR PEER REVIEW 3 of 17

Scheme 2. Synthesis
Scheme 2. Synthesis of
of poly(hydroxyurethane)s
poly(hydroxyurethane)s by
by polyaddition
polyaddition reaction
reaction of
of bis(cyclic
bis(cyclic carbonates)
carbonates)
and diamines.
and diamines.

Since
In thisthe pioneer
paper, work of the
we reported thissynthesis
syntheticof route for the
different NIPUs
NIPUs in 1957 by
materials [35], several re-
polyaddition
views
reaction about
of COthe
2 synthesis
-based of
cyclic polyurethanes
carbonate, have been
1,4-butanediol reported
bis(glycidyl by different
ether research1
carbonate)
groups [6,10,17–19,31,36]. In general, the ring-opening reaction
(BGBC), with a wide range of commercial diamines to afford the corresponding NIPUs of the cyclic carbonate by
the amine takes place without the use of a catalyst. However, the
in quantitative yields, including a crosslinked one, which showed enhanced thermal reaction rate can be ac-
celerated through
properties. activation
The obtained of the
PHUs monomers
were by using
characterized by either
NMR,weak Lewis acid or
IR, MALDI-ToF, andoxoph-
GPC
ilic additives
studies. to increase
In addition, the the electrophilicity
synthesis of the
of different cyclic carbonate
carbamates group or
was designed by by the addi-
varying the
tion
ratioofofbasic additives Finally,
the substrates. to increase the nucleophilicity
one-pot of the amine were
and sequential experiments or even
alsodeprotonate
performed to it
[37,38].
obtain the Generally, the polyaddition
corresponding PHU materials.of cyclic carbonates onto diamines is carried out in
polar aprotic solvents such as dimethylformamide (DMF), dimethylsulfoxide (DMSO),
2. Experimental Details (DMAc), etc., due to the better solubility of the starting materials
N,N-dimethylacetamide
2.1. Materials
[32,33,39]. Theand Methods also has an influence on the outcome of the polyaddition re-
temperature
action All[40,41]. Thus, higher
manipulations yields andunder
were performed reaction rates were
nitrogen, using obtained when the
standard Schlenk reaction
techniques.
1temperature
H and 13 C NMR was increased,
spectra werewhich was explained
recorded by theAscend
on a Bruker decrease of the viscosity
TM-500/400 in the
spectrome-
ters (Bruker
reaction Corporation,
mixture [41]. Billerica, MA, USA) and referenced to the residual deuterated
solvent. Gelpaper,
In this permeation chromatography
we reported the synthesis (GPC) measurements
of different were performed
NIPUs materials on a Wa-
by polyaddition
ters 1515 of
reaction model (Waterscyclic
CO2-based Corporation,
carbonate, Milford, CT, USA),bis(glycidyl
1,4-butanediol equipped with etherthree different
carbonate) 1
columns:with
(BGBC), 1× aPSSwideGRAM
rangeprecolumn
of commercial 10 µm 8 × 50tomm,
diamines 1×the
afford PSScorresponding
GRAM column 10 µm
NIPUs in
30 Å 8 × 300 yields,
quantitative mm, and 1× PSS aGRAM
including column
crosslinked 10 µm
one, which1000 Å 8 × 300
showed mm, and
enhanced a refractive
thermal prop-
index The
erties. detector (Waters
obtained PHUs 2414).
were The GPC column
characterized was eluted
by NMR, using DMAc
IR, MALDI-ToF, and asGPCsolvent
studies.at
25 ◦ C at 1 mL·min−1 and calibrated using eight monodisperse polystyrene standards in
In addition, the synthesis of different carbamates was designed by varying the ratio of the
the range ofFinally,
substrates. 580–50000 Da. and
one-pot TGAsequential
analysis was performed
experiments on also
were a TAperformed
instruments TGA-Q50
to obtain the
(TA instruments,
corresponding PHU New Castle, DE, USA). The heating rate for the sample was 10 ◦ C/min,
materials.
and the nitrogen flow rate was 60 mL/min. DSC curves were obtained under N2 atmo-
sphere
2. on a TA instruments
Experimental Details DSC-Q20 (TA instruments, New Castle, DE, USA). Samples
were weighed into aluminum crucibles with 5 mg of sample and subjected to two heat-
2.1. Materials and Methods
ing cycles at a heating rate of 10 ◦ C/min. The MALDI-ToF spectra were acquired using
All manipulations
a Bruker Autoflex II TOF/TOFwere performed
spectrometerunder nitrogen,
(Bruker using standard
Corporation, Schlenk
Billerica, MA, USA) tech-
niques. 1H and 13C NMR spectra were recorded on a Bruker Ascend TM-500/400 spectrom-
using dithranol (1,8,9-trihydroxyanthracene) as matrix material and NaOAc as additive.
eters (Bruker Corporation,
Commercially Billerica,
available chemicals MA,used
were USA) asand referenced to the residual deuterated
received.
solvent. Gel permeation chromatography (GPC) measurements were performed on a Wa-
ters 1515 model (Waters Corporation, Milford, CT, USA), equipped with three different
columns: 1× PSS GRAM precolumn 10 µm 8 × 50 mm, 1× PSS GRAM column 10 µm 30 Å
Polymers 2022, 14, 2719 4 of 17

2.2. Materials and Reagents

Solvents, deuterated solvents, and all other reagents were purchased from common
commercial sources and used as received.

2.3. General Procedure for the Synthesis of 1,4-Butanediol bis(glycidyl ether carbonate) 1
The 1,4-butanediol bis-glycidyl ether (BGBE) (50.00 g, 0.25 mol) and the bifunctional
organocatalyst (0.99 g, 2.47 mmol) were placed in a 500 mL stainless steel reactor with
a magnetic stirrer bar. The reaction mixture was heated to 80 ◦ C, then pressurised to
10 bar of carbon dioxide pressure and stirred for 2 h. The mixture was purified by flash
chromatography using a solvent system of first hexane, then hexane:EtOAc (9:1), then
hexane:EtOAc (3:1), then EtOAc to achieve the pure cyclic carbonate as a white solid in 90%
yield (65.31 g, 0.22 mol).

2.4. General Procedure for the Synthesis of Poly(hydroxyurethane)s 1a-e

In a 10 mL Schlenk flask equipped with a small stir bar, BGBC 1 (0.25 g, 0.86 mmol), the
corresponding diamine (0.86 mmol), and MeCN (2 mL) were added. The reaction mixture
was then warmed up at 80 ◦ C and left stirring for 16 h. After that time, the solvent was
removed in vacuo and the residue was washed with methanol. The mixture was filtered,
and the solvent was dried in vacuo to afford the corresponding poly(hydroxyurethane) as
a rubbery material or a solid depending on the diamine used in 80–95% yield.

2.5. Synthesis of Poly(hydroxyurethane) 1f

The synthesis of PHU 1f was carried out in a similar manner to PHUs 1a–e, using BGBC
(1) (0.25 g, 0.86 mmol), L-lysine (0.13 g, 0.86 mmol), and 1,5,7-Triazabicyclo[4.4.0]dec-5-ene
(TBD) (0.12 g, 0.86 mmol) or 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) (0.13 g, 0.86 mmol),
and 1f material was obtained as a white-yellowish solid in 93% yield after the appropriate
work-up procedure.

2.6. General Procedure for the Synthesis of Hydroxycarbamates 2 and 3

In a 10 mL Schlenck equipped with a small stir bar, 1,4-butanediol bis(glycidyl ether
carbonate) 1 (0.25 g, 0.86 mmol), 1,4-diaminobutane (43 µL, 0.43 mmol and 0.13 mL,
1.72 mmol for 2 and 3 respectively), and MeCN (2 mL) were added. The reaction mixture
was then warmed up at 80 ◦ C and left stirring for 16 h. After that time, the solvent was
removed in vacuo, extracted with MeOH, and filtered off. Removal of the solvent under
vacuum afforded the corresponding hydroxycarbamate as a white solid in 95% yield.

2.7. General Procedure for the One-Pot Synthesis of Poly(hydroxyurethane)s 1a,c,d

The 1,4-butanediol bis-glycidyl ether (BGBE) (0.17 g, 0.86 mmol), bifunctional organocat-
alyst (3.44 mg, 8.6 µmol) and the corresponding diamine) (0.86 mmol), and MeCN (2 mL)
were placed in a 50 mL stainless steel reactor with a magnetic stirrer bar. The reaction
mixture was then warmed up at 80 ◦ C, then pressurised to 10 bar of carbon dioxide pres-
sure, and left stirring for 16 h. After that time, CO2 was released, the solvent was removed
in vacuo and the residue was washed with methanol. The mixture was filtered, and the
solvent was dried in vacuo to afford a rubbery mixture composed of the corresponding
poly(hydroxyurethane) and polyaminoalcohol was obtained.

2.8. General Procedure for the Sequential Synthesis of Poly(hydroxyurethane)s 1a,c,d

The 1,4-butanediol bis-glycidyl ether (BGBE) (0.17 g, 0.86 mmol) and bifunctional
organocatalyst (3.44 mg, 8.6 µmol) were placed in a 50 mL stainless steel reactor with a
magnetic stirrer bar. The reaction mixture was then warmed up at 80 ◦ C, then pressurised
to 10 bar of carbon dioxide pressure, and left stirring for 2 h. After that time, CO2 was
released, MeCN (2 mL) and the corresponding diamine (0.86 mmol) were added, and the
reaction mixture was stirred for 16 h. Then, the solvent was removed in vacuo and the
residue was washed with methanol. The mixture was filtered, and the solvent was dried
 ganocatalyst (3.44 mg, 8.6 µmol) were placed in a 50 mL stainless steel reactor with a mag-
netic stirrer bar. The reaction mixture was then warmed up at 80 °C, then pressurised to
10 bar of carbon dioxide pressure, and left stirring for 2 h. After that time, CO2 was re-
leased, MeCN (2 mL) and the corresponding diamine (0.86 mmol) were added, and the
Polymers 2022, 14, 2719 reaction mixture was stirred for 16 h. Then, the solvent was removed in vacuo 5 ofand
17 the
residue was washed with methanol. The mixture was filtered, and the solvent was dried
in vacuo to afford the corresponding poly(hydroxyurethane) 1a, 1d and 1e as rubbery
materials
in vacuointo85–90% yield.
afford the corresponding poly(hydroxyurethane) 1a, 1d and 1e as rubbery
materials in 85–90% yield.
3. Results and Discussion
3. Results and Discussion
Initially, the multigram scale preparation of 1,4-butanediol bis(glycidyl ether car-
Initially, the multigram scale preparation of 1,4-butanediol bis(glycidyl ether carbon-
bonate) (1) from the commercially available 1,4-butanediol bis-glycidyl ether and CO2 was
ate) (1) from the commercially available 1,4-butanediol bis-glycidyl ether and CO2 was
carried using
carried using1 1mol%
mol% ofof the hydroxy-containingimidazole
the hydroxy-containing imidazole organocatalyst
organocatalyst designed
designed by by
ourour
group
group [42]
[42]atat10
10bar
bar of
of CO and 80
CO22 and 80◦°C for2 2h hunder
C for under solvent-free
solvent-free conditions
conditions affording
affording
compound
compound 1 1inin90%
90%yield
yield (Scheme 3).
(Scheme 3).

Scheme 3. Synthesis
Scheme 3. Synthesisofof1,4-butanediol bis(glycidylether
1,4-butanediol bis(glycidyl ether carbonate)
carbonate) (1). (1).

Bis(cycliccarbonate)
Bis(cyclic carbonate) (1)
(1) was
was used
usedalong
alongwith
with 1,4-diaminobutane
1,4-diaminobutane (BDA) in a 1:1
(BDA) in amolar
1:1 molar
ratio to optimize the reaction conditions to synthesize the different
ratio to optimize the reaction conditions to synthesize the different NIPUs (Scheme NIPUs (Scheme 4). 4).
Firstly, the solvent effect on the polyaddition process was investigated (Table 1, entries
Firstly, the solvent effect on the polyaddition process was investigated (Table 1, entries 1–
1–4). As can be seen, all solvents afforded the formation of the desired PHU quantitatively.
4). As can be seen, all solvents afforded the formation of the desired PHU quantitatively.
However, MeCN was chosen as the optimal solvent to perform this reaction due to its
However, MeCN
high polarity was chosen
to increase as the optimal
the solubility solvent
of the starting to perform
materials and itsthis reaction
easy due to its
accessibility.
high polarity to increase the solubility of the starting materials and its easy
Then, the effect of the reaction temperature was studied (Table 1, entries 5–9). As expected, accessibility.
Then,
the the effect ofdecreased
conversion the reaction temperature
as the temperaturewas wasstudied (Table
decreased. 1, entriesof
Polyaddition 5–9).
BGBC As(1)
expected,
to
the conversion decreased as the temperature was decreased. Polyaddition of BGBCh (1) to
BDA at room temperature afforded the corresponding PHU in 67% conversion after 16
BDA of reaction
at room(Table 1, entry 7).
temperature This factthe
afforded hascorresponding
been previouslyPHU observed
in 67%for this process. after
conversion This 16 h
is probably due to two factors. First, the low reactivity between five members
of reaction (Table 1, entry 7). This fact has been previously observed for this process. This of cyclic
carbonates and diamines, and, second, due to monomer diffusion during polymerization.
is probably due to two factors. First, the low reactivity between five members of cyclic
This is an important phenomenon in which are involved the hydrogen bonds created
carbonates and diamines, and, second, due to monomer diffusion during polymerization.
with carbamate groups. The increase of the temperature allows to decrease the viscosity,
Thisandis an important
to increase thephenomenon
mobility, and in thuswhich are involved of
the advancement thethe
hydrogen
reaction bonds
and thecreated
molar with
carbamate groups. The increase of the temperature allows to decrease the viscosity, and
masses [17,36,43,44].
to increase
Oncethethemobility, and thus for
optimal conditions thetheadvancement
polyadditionof ofthe
BGBCreaction
(1) andandBDA the molar
were masses
deter-
◦
[17,36,43,44].
mined (80 C and MeCN as solvent for 16 h), several PHUs were prepared using a wide
range of commercial diamines (Scheme 5). The results are shown in Table 2. All PHUs were
obtained quantitatively after 16 h (Table 2, entries 1–6), except when L-lysine was used, in
which case, no reaction was observed (Table 2, entry 7). This result can be explained based
on the low nucleophilicity of L-lysine, which is not able to ring-open the cyclic carbonate,
and no polyaddition occurred. Since previous works confirmed that the presence of strong
bases catalyzed the process [45], the addition of DBU or TBD as catalyst was tested. The
addition of a catalyst resulted in the obtention of the desired PHU (Table 2, entries 8 and 9).
However, the presence of strong bases also led to the formation of polyurea fragments
(Figures 1 and S35), as has been previously reported in similar reactions [38].
Polymers 2022, 14, x2719
Polymers FOR PEER REVIEW 6 6ofof 17
17

Scheme
Scheme 4.
4. Synthesis
Synthesis of
of PHU
PHU 1a.
1a.

Table
Table 1.
1. Optimization
Optimization of
of reaction
reaction conditions
conditions for
for the
the polyaddition
polyaddition of
of BGBC
BGBC 11and
and1,4-diaminobutane.
1,4-diaminobutane.

EntryEntry Solvent
Solvent Time
Time(h)(h) TT(°C)
(◦ C) Conversion (%)1 1
Conversion (%)
1 1 DMFDMF 1616 80
80
100
100
2 2 MEKMEK 1616 80
80 100
100
3 3 EtOAcEtOAc 1616 80
80 100
4 4 MeCN MeCN 1616 80
80 100
100
5 MeCN 16 60 93
5 MeCN 16 60 93
6 MeCN 16 40 83
Polymers 2022, 14, x FOR PEER REVIEW 6 7 MeCN MeCN 1616 40
r.t 83
67 7 of 17
7
1 Determined MeCN
by NMR. 16 r.t 67
1 Determined by NMR.

Once the optimal conditions for the polyaddition of BGBC (1) and BDA were deter-
mined (80 °C and MeCN as solvent for 16 h), several PHUs were prepared using a wide
range of commercial diamines (Scheme 5). The results are shown in Table 2. All PHUs
were obtained quantitatively after 16 h (Table 2, entries 1–6), except when L-lysine was
used, in which case, no reaction was observed (Table 2, entry 7). This result can be ex-
plained based on the low nucleophilicity of L-lysine, which is not able to ring-open the
cyclic carbonate, and no polyaddition occurred. Since previous works confirmed that the
presence of strong bases catalyzed the process [45], the addition of DBU or TBD as catalyst
was tested. The addition of a catalyst resulted in the obtention of the desired PHU (Table
2, entries 8 and 9). However, the presence of strong bases also led to the formation of
polyurea fragments (Figure 1 and S35), as has been previously reported in similar reac-
tions [38].

Scheme
Scheme 5.
5. Synthesis
Synthesis of
of poly(hydroxyurethane)s 1a-f.
poly(hydroxyurethane)s 1a-f.

The synthesis of a crosslinked PHU was achieved by the reaction of BGBC (1) with
tris(2-aminoethyl)amine in a 3:2 molar ratio (Table 2, entry 6). The higher Tg value ob-
tained by differential scanning calorimetry for polymer 1e suggested the formation of a
crosslinked PHU. This high glass transition temperature was attributed to the increased
rigidity of the resulting polymer (Table 3, entry 6).
 Polymers 2022, 14, 2719 7 of 17

Table 2. GPC data for selected PHUs 1 .

Entry Diamine (PHU) Conversion (%) 2 Primary OH: Secondary OH Mn, exp 3 PDI 3
Polymers 2022, 14, x FOR PEER REVIEW 8 of 17
1 1,4-diaminobutane (1a) 100 32:68 14500 2.2
2 Isophorone diamine (1b) 100 36:64 13250 1.5
1,3-cyclohexanebis
3 100 36:64 17800 1.6
(methanamine)
at 2.96 ppm; (1c)1.37 ppm and 3.39 ppm; 1.51 ppm were assigned to the methylene protons of
4 m-Xylene diamine (1d) 100 38:62 9050 2.2
the alkyl groups of the diamine and the BGBC (1), respectively. As has been previously
5 tris(2-aminoethyl)amine (1e) 100 28:72 17200 2.1
64 mentioned, it is
tris(2-aminoethyl)amine known that 100
(1e) both primary and secondary
- hydroxyl groups can - be formed -
7 in the PHU
L-lysine (1f) backbone depending 0 on the ring-opening- pathway of the cyclic- carbonate -
85 moiety.(1f)
L-lysine In Figure 2, two signals
88 are observed at 4.89 and
- 4.75 ppm, corresponding
39200 to the 2.1
96 formation
L-lysine (1f) of the secondary and
90 primary hydroxyl groups,
- respectively. Following
40325 previ- 2.2
ously reported
1 Reactionsresults [32–34],
were carried out atthe
80 ◦PHUs synthesized
C in MeCN in this work
for 16 h. 2 Determined exhibited
by NMR. a primary:sec-
3 Determined by GPC. 4 0.66 eq.
5 6
ondaryofOH ratio ranging from
tris(2-aminoethyl)amine used.28:72 toof38:62
1 eq. DBU (Table
was used. 2, entries 1–5).was used.
1 eq. of TBD

Figure Figure 1. IR spectra

1. IR spectra for (a)forBGBC
(a) BGBC
andand PHUs
PHUs (b)(b)
1c1c and(c)
and (c)1f.
1f.

The synthesis of a crosslinked PHU was achieved by the reaction of BGBC (1) with
tris(2-aminoethyl)amine in a 3:2 molar ratio (Table 2, entry 6). The higher Tg value obtained
by differential scanning calorimetry for polymer 1e suggested the formation of a crosslinked
Polymers 2022, 14, 2719 8 of 17

PHU. This high glass transition temperature was attributed to the increased rigidity of the
resulting polymer (Table 3, entry 6).

Table 3. DSC and TGA analyses for selected PHUs.

Entry Diamine (PHU) T g (◦ C) 1 T d, 5% (◦ C) 2

1 1,4-diaminobutane (1a) 11 252
2 Isophorone diamine (1b) 22 272
3 1,3-cyclohexanebis(methylamine) (1c) 22 263
4 m-Xylene diamine (1d) 22 231
5 tris(2-aminoethyl)amine (1e) −3 229
63 tris(2-aminoethyl)amine (1e) 43 261
7 L-lysine (1f) −13 128
1 Determined by differential scanning calorimetry. 2 Determined by thermogravimetric analysis. 3 0.66 eq. of
tris(2-aminoethyl)amine used.

The chemical structures of the PHUs were characterized by 1 H-NMR and 13 C-{1 H}-
NMR (Figure 2 and Supplementary Information), diffusion ordered spectroscopy (DOSY)
NMR (Figure S35) and IR spectroscopy (Figure 1 and Supplementary Information), MALDI-
ToF analysis (Figure 3 and Supplementary Information), and gel permeation chromatogra-
phy (GPC) (See Supplementary Information). Figure 1 shows the FT-IR spectra of BGBC (1)
and PHUs (1c) and (1f). Bis(glycidyl ether carbonate) (1) exhibited two characteristic bands
at 1781 and 1050 cm−1 corresponding to the cyclic carbonate groups (Figure 1a). However,
those bands disappeared in the PHUs IR spectra, and two new bands were observed at
1695 cm−1 and 1538 cm−1 , and 1699 cm−1 and 1537 cm−1 for PHUs (1c) and (1f), respec-
tively, confirming the formation of urethane groups (Figure 1b,c, respectively). In addition,
another band at 1646 cm−1 was observed for PHU (1f), which was assigned to the C=O
stretching vibration of the urea group, indicating the formation of polyurethane-polyurea
chains (Figure 1c) [38]. Analysis of the 1 H-NMR spectra of the generated polymers also
confirmed the formation of the urethane moieties. Characteristic peaks at 7.11 ppm and
6.74 ppm were assigned to the protons of the urethane groups, confirming the urethane
structure of the final product (Figure 2). The pair of resonances at 2.96 ppm; 1.37 ppm and
3.39 ppm; 1.51 ppm were assigned to the methylene protons of the alkyl groups of the
diamine and the BGBC (1), respectively. As has been previously mentioned, it is known
that both primary and secondary hydroxyl groups can be formed in the PHU backbone
depending on the ring-opening pathway of the cyclic carbonate moiety. In Figure 2, two
signals are observed at 4.89 and 4.75 ppm, corresponding to the formation of the secondary
and primary hydroxyl groups, respectively. Following previously reported results [32–34],
the PHUs synthesized in this work exhibited a primary:secondary OH ratio ranging from
28:72 to 38:62 (Table 2, entries 1–5).
MALDI-ToF mass spectrometry was also used to determine the end groups of the
obtained PHUs. As an example, the MALDI-ToF spectrum for PHU 1b (Figure 3) shows
a major series of peaks with an m/z interval of 460 mass units, indicating a controlled
alternating microstructure, which is in good agreement with a polymeric chain with one
isophorone diamine group in one end and a protonated urethane group in the other end.
Polyhydroxyurethanes 1a–e exhibited molecular weights between 9050 and 17,800 g mol−1
with moderate polydispersity ranging from 1.5 to 2.2 (Table 2). This was attributed to the
fact that no catalyst was used during the polymerization process. Thus, there is not a good
control over the polyaddition reaction and multiple chains with different molecular weights
can be generated; hence, the PDI values obtained. On the other hand, molecular weight
increased notably for PHU 1f, since DBU or TBD were added to the polyaddition process,
with values of 39,200 g mol−1 and 40,325 g mol−1 , respectively (Table 2, entries 8 and 9).
 Polymers
Polymers 2022,2022, 14, x FOR PEER REVIEW
14, 2719 9 of917
of 17

Polymers 2022, 14, x FOR PEER REVIEW 10 of 17

Figure
2. 2.1 H-NMR
1 H-NMRspectrum
spectrum for
for poly(hydroxyurethane)
poly(hydroxyurethane) 1a
1aininDMSO-d6.
DMSO-d
Figure 6.

MALDI-ToF mass spectrometry was also used to determine the end groups of the
obtained PHUs. As an example, the MALDI-ToF spectrum for PHU 1b (Figure 3) shows a
major series of peaks with an m/z interval of 460 mass units, indicating a controlled alter-
nating microstructure, which is in good agreement with a polymeric chain with one iso-
phorone diamine group in one end and a protonated urethane group in the other end.

Figure 3. MALDI-TOF spectrum for PHU 1b.

Polyhydroxyurethanes 1a–e exhibited molecular weights between 9050 and 17,800 g

mol−1 with moderate polydispersity ranging from 1.5 to 2.2 (Table 2). This was attributed
to the fact that no catalyst was used during the polymerization process. Thus, there is not
a good control over the polyaddition reaction and multiple chains with different molecu-
lar weights can be generated; hence, the PDI values obtained. On the other hand, molec-
 [46–48]. Thus, PHUs derived from rigid amines such as isophorone diamine (Table 3, en-
try 2), 1,3-cyclohexanebis(methylamine) (Table 3, entry 3), or m-xylene diamine (Table 3,
entry 4) exhibited higher Tg values than PHUs derived from aliphatic diamines such as
BDA (Table 3, entry 1), tris(2-aminoethyl)amine (Table 3, entry 5), or L-lysine (Table 3,
Polymers 2022, 14, 2719 10 of 17
entry 7). On the other hand, the crosslinked PHU derived from tris(2-aminoethyl)amine
1e exhibited the highest Tg (Table 3, entry 6).

Table 3.Thermal
DSC andproperties of thefor
TGA analyses NIPUs were
selected investigated by DSC and TGA analyses (Table 3).
PHUs.
TGA showed that all PHUs were stable in the range of temperatures from 0 ◦ C to 270 ◦ C
Entry
(Table 3), except Diamine
for the PHU(PHU) Tg (°C)(Table
(1f) derived from L-lysine
1
3, entryTd,7),5%which
(°C) 2 was
1
found to be stable between 0 ◦ C and
1,4-diaminobutane (1a)128 ◦ C. DSC thermograms
11 252
(Figure 4) revealed that
2 glass temperature
the Isophorone Tgdiamine (1b) ranged from −22
of the PHUs 13 ◦ C to 43 ◦ C (Table 2723, entries
1–7),
3 depending on the chemical structure
1,3-cyclohexanebis(methylamine) of the diamines
(1c) 22 used. Most studies 263 agreed
that
4 higher molecular
m-Xylene flexibility
diaminebetween
(1d) the hydroxyurethane
22 groups led to231 lower Tg of
PHUs [46–48]. Thus, PHUs derived from rigid amines such as isophorone diamine (Table 3,
5 tris(2-aminoethyl)amine (1e) −3 229
entry 2), 1,3-cyclohexanebis(methylamine) (Table 3, entry 3), or m-xylene diamine (Table 3,
6 3 tris(2-aminoethyl)amine (1e) 43 261
entry 4) exhibited higher Tg values than PHUs derived from aliphatic diamines such as
7 L-lysine (1f) −13 128
BDA (Table 3, entry 1), tris(2-aminoethyl)amine (Table 3, entry 5), or L-lysine (Table 3,
1Determined
entry 7). On bythe
differential
other hand,scanning calorimetry.
the crosslinked PHUDetermined
2 by tris(2-aminoethyl)amine
derived from thermogravimetric analysis.
1e
3

0.66 eq. of tris(2-aminoethyl)amine used.

exhibited the highest T (Table 3, entry 6).
g

−1

PHU 1a
Heat Flow (W/g)

−2 PHU 1d

PHU 1c

−3 PHU 1e
crosslinked
PHU 1b

−4
0 50 100 150 200 250
T (°C)
Figure 4. 4.
Figure DSC thermograms
DSC thermogramsfor
forselected
selectedpoly(hydroxyurethanes) PHUs.
poly(hydroxyurethanes) PHUs.

TheThe effectofofthe
effect the[diamine]/[BGBC]
[diamine]/[BGBC]ratio ratioonon the
the polyaddition
polyaddition reaction
reactionofof11onto
onto1,4-
1,4-
diaminobutane was also investigated (Scheme 6). Thus, when 0.5 eq. of 1,4-diaminobutane
diaminobutane was also investigated (Scheme 6). Thus, when 0.5 eq. of 1,4-diaminobutane
was used (1:2 ratio [diamine]/[BGBC]), a hydroxycarbamate with two cyclic carbonate
was used (1:2 ratio [diamine]/[BGBC]), a hydroxycarbamate with two cyclic carbonate
ending groups was obtained (2). On the other hand, when 2 eq. of diamine was added
ending groups was obtained (2). On the other hand, when 2 eq. of diamine was added (2:1
(2:1 ratio [diamine]/[BGBC]), a hydroxycarbamate with two amine ending groups was
ratio [diamine]/[BGBC]), a hydroxycarbamate with two amine ending groups was ob-
obtained (3). The structures for compounds 2 and 3 were confirmed by NMR and IR
tained (3). The and
spectroscopy structures
MALDI-ToFfor compounds
analysis. The2 and
1 H-NMR3 were confirmed
spectrum by NMR and
for compound IR spec-
2 exhibited
troscopy and MALDI-ToF analysis. The 1H-NMR spectrum for compound 2 exhibited res-
resonances at 4.92 ppm, 4.52 ppm, and 4.27 ppm which confirmed the presence of cyclic
onances at 4.92
carbonate ppm,
groups, 4.52 as
as well ppm, andat4.27
a signal 7.24 ppm
ppm, which confirmed
confirming the presence
the formation of cyclic
of the urethane
moieties (Figure S38). Additionally, the IR spectrum exhibited two bands at 1787 cm−1
and 1048 cm−1 , which correspond to the cyclic carbonate groups, as well as two bands at
1692 cm−1 and 1525 cm−1 , assigned to the urethane groups generated (Figure S40). The
MALDI-ToF spectrum showed single peak with a m/z of 691 mass units, which is in good
agreement with the molecular weight of hydroxycarbamate 2 and Na+ (Figure S41).
 carbonate groups, as well as a signal at 7.24 ppm, confirming the formation of the urethane
moieties
carbonate(Figure S38).
groups, Additionally,
as well the7.24
as a signal at IR ppm,
spectrum exhibited
confirming two bandsofatthe
the formation 1787 cm−1 and
urethane
1048 cm ,(Figure
moieties−1 which S38).
correspond to the the
Additionally, cyclic carbonateexhibited
IR spectrum groups, two
as well as at
bands two1787bands
cm−1atand1692
cm
1048and
−1 cm−11525 cm correspond
, which−1, assigned toto the urethane groupsgroups,
cyclic carbonate generated (Figure
as well S40).
as two bandsTheatMALDI-
1692
ToF
cm−1spectrum
and 1525 showed singleto
cm−1, assigned peak with a m/z
the urethane of 691
groups mass units,
generated (Figurewhich is The
S40). in good
MALDI-agree-
Polymers 2022, 14, 2719 11 of 17
ToF spectrum
ment showed single
with the molecular weightpeakof with a m/z of 691 mass
hydroxycarbamate units,
2 and Nawhich
+ is in
(Figure good agree-
S41).
ment with the molecular weight of hydroxycarbamate 2 and Na+ (Figure S41).

Scheme
Scheme6.6.Synthesis
Synthesisof
of poly(hydroxyurethane)s 1a–f.
poly(hydroxyurethane)s 1a–f.
Scheme 6. Synthesis of poly(hydroxyurethane)s 1a–f.
The
Theresults
The resultsobtained
results obtainedfor
obtained forthe reaction
thereaction ofof
reactionof BGBC
BGBC
BGBC (1)
(1) with
with
(1) different
different
with diamines
diamines
different support
support
diamines thethe
support
general
general mechanism
mechanism
the general mechanismproposed
proposed thethe
for for
proposed the polymerization
polymerization
polymerization process
process byby
process polyaddition
polyaddition
by reaction
reaction
polyaddition reactionof of
bis(cyclic
bis(cycliccarbonates)
carbonates) and
and diamines
diamines [36,49].
[36,49]. Thus,
Thus, aa three-step
three-step reaction
reaction involving
involving
of bis(cyclic carbonates) and diamines [36,49]. Thus, a three-step reaction involving a a a tetra-
tetra-
hedral
hedralintermediate
intermediate
tetrahedral was
was proposed
intermediate proposed
was proposed(Figure
(Figure 5). 5).
5).
(Figure

Figure 5. General mechanism proposed for the polymerization process by polyaddition reaction of
bis(cyclic
Figure carbonates) and diamines.
Figure5.5.General
Generalmechanism
mechanism proposed for the
proposed for thepolymerization
polymerizationprocess
processbyby polyaddition
polyaddition reaction
reaction of of
bis(cyclic
bis(cycliccarbonates)
carbonates) and diamines.
and diamines.
After the successful multistep synthesis of PHUs 1a–f, their direct synthesis from
BGBE, COthe
After
After 2, and a diamine in a one-pot process was investigated (Scheme 7). For that
thesuccessful
successful multistep synthesis
synthesis of
ofPHUs
PHUs1a–f,
1a–f,their
theirdirect
direct synthesis
synthesis from
from
BGBE,CO
BGBE, CO2,2 ,and
andaa diamine
diamine in a one-pot
one-potprocess
processwaswasinvestigated
investigated (Scheme
(Scheme7). 7).
ForFor
that
that
purpose, BDA, 1,3-cyclohexanebis(methylamine), and m-xylene diamines were used as
starting materials. In all cases, full conversion of BGBE to BGBC (1) and subsequent
polyaddition onto the corresponding diamine to generate the corresponding NIPU was
achieved when the reaction was carried out at 80 ◦ C and 10 bar of CO2 for 16 h using
acetonitrile as solvent (Scheme 7). Additionally, to polymer 1a, 1c, and 1d, the formation
of crosslinked poly(aminoalcohols) from bis-epoxides and diamines was observed, these
 purpose, BDA, 1,3-cyclohexanebis(methylamine), and m-xylene diamines were used as
starting materials. In all cases, full conversion of BGBE to BGBC (1) and subsequent poly-
addition onto the corresponding diamine to generate the corresponding NIPU was
Polymers 2022, 14, 2719 achieved when the reaction was carried out at 80 °C and 10 bar of CO2 for 16 h 12 of 17
using
acetonitrile as solvent (Scheme 7). Additionally, to polymer 1a, 1c, and 1d, the formation
of crosslinked poly(aminoalcohols) from bis-epoxides and diamines was observed, these
polymers
polymers were
werepreviously
previouslyreported
reported [50,51]. Moreover,
[50,51]. a white
Moreover, precipitate
a white was also
precipitate was obtained
also ob-
and was
tained andidentified as the corresponding
was identified carbamate
as the corresponding salt fromsalt
carbamate thefrom
diamine and CO2and
the diamine reaction
CO2
(Scheme 7) [52]. 7) [52].
reaction (Scheme

Scheme 7. One-pot synthesis of poly(hydroxyurethane)s 1a,c,d.

Scheme 7. One-pot synthesis of poly(hydroxyurethane)s 1a,c,d.

IR analysis
IR analysis of the resulting
of the resulting mixture
mixture confirmed
confirmed the presence of
the presence of poly(aminoalcohol),
poly(aminoalcohol),
carbamate salt and poly(hydroxyurethane). Figure 6 shows the comparison ofof
carbamate salt and poly(hydroxyurethane). Figure 6 shows the comparison the
the IRIR spec-
spectra
traaof
of a blank
blank sample
sample containing
containing 1,4-diaminobutane
1,4-diaminobutane and BGBE
and BGBE (Figure(Figure 6a), 1,4-diamino-
6a), 1,4-diaminobutane
butane
and COand
2 CO
(Figure 2 (Figure
6b), and 6b),
the and the
one-pot one-pot
reaction reaction
mixture mixture
(Figure (Figure
6c). As 6c).
canAs becan be ob-
observed
served
from from 5,
Figure Figure 5, the one-pot
the one-pot reaction reaction
mixture mixture
(Figure(Figure 6c) shows
6c) shows a sharpa sharp
band at band
3315atcm −1
3315
cm−1 corresponding
corresponding to theto the stretching
stretching frequency
frequency of the amino-end
of the amino-end group fromgroup thefrom the carba-
carbamate salt
mate salt as well as bands −
at1 1555 cm −1 and− 11326 cm −1 which correspond to the N−H bend-
as well as bands at 1555 cm and 1326 cm which correspond to the N−H bending and C-
ingstretching
N and C-Nfrequencies
stretchingoffrequencies
the amine group.of theSimilarly,
amine group. Similarly,
the presence the presence of
of poly(aminoalcohol)
poly(aminoalcohol)
was confirmed by thewas confirmed
presence of twoby at 1108 cmof−1two
the presence
peaks andpeaks
1454 cmat −1108
1 corresponding
cm−1 and 1454 to
cm C-O
the −1 corresponding
stretching and to O-H
the C-O stretching
bending from the and O-H bending
alcohol group. The from the alcohol
obtention of thegroup. The
PHU was
obtention of
confirmed bythe
thePHU was confirmed
presence of a band at by1699 cm−1 corresponding
the presence of a band at 1699to thecmurethane
−1 corresponding
moiety.
to theFinally,
urethane in moiety.
an effort to minimize the formation of the carbamate salt and the poly
(aminoalcohol),
Finally, in an a effort
sequential one-potthe
to minimize method
formationwasof developed
the carbamatefor thesaltsynthesis of PHUs
and the poly(ami-
1a,c,d (Scheme
noalcohol), 8). Therefore,
a sequential one-pot bis(cyclic
method carbonate)
was developedBGBC for (1) the
wassynthesis
preparedoffrom PHUs BGBE as
1a,c,d
shown
(Scheme in8).
Scheme 3. The
Therefore, subsequent
bis(cyclic addition
carbonate) of a solution
BGBC of the diamine
(1) was prepared from BGBEin MeCN to the
as shown
reaction
in Scheme mixture
3. The afforded
subsequent theaddition
formation of of the corresponding
a solution of the diamine PHUs.in MeCN to the reaction
mixture afforded the formation of the corresponding PHUs.
 (methylamine) diamine H H
O O O N N
O R
O O
OH 1a, c, d n

Scheme 8. Sequential synthesis of poly(hydroxyurethane)s 1a,c,d.

Polymers 2022, 14, 2719 13 of 17

Polymers 2022, 14, x FOR PEER REVIEW 14 of 17

Figure 6. IR spectra for (a) 1,4-diaminobutane + BGDE reaction, (b) 1,4-diaminobutane + CO2 reaction,
and (c) one pot synthesis of PHU 1a.

Bu
N
O
OH I
O N O
Bu O
O O
O O O
O 10 bar CO2, 80 ºC, 2h O
BGDC (1)
O
NH2

R
H2N NH2 H2N NH2
H2N (CH)4 NH2 NH 2
R=

a BDA c 1,3-Ciclohexanebis d m-Xylene

(methylamine) diamine OH
H H
O O O N N
O R
O O
OH 1a, c, d n

Scheme
Scheme 8.
8. Sequential
Sequential synthesis
synthesis of
of poly(hydroxyurethane)s
poly(hydroxyurethane)s 1a,c,d.
1a,c,d.
Polymers 2022, 14, 2719 14 of 17

4. Conclusions
Herein, we reported the synthesis of different nonisocyanate polyurethanes via the
polyaddition reaction of bis(butanediol glycidyl ether)carbonate (1) with different diamines
under mild reaction conditions. All PHUs were obtained quantitatively after 16 h at 80 ◦ C
temperature in MeCN as solvent. The low nucleophilicity of L-lysine has proven unable
to ring-open the cyclic carbonate and no polyaddition occurred. The addition of DBU or
TBD as a catalyst was tested and allows the obtention of the desired PHU. However, the
presence of strong bases also led to the formation of polyurea fragments in the new PHU.
All polymers were thoroughly characterized by different spectroscopic techniques and
their thermal properties were also investigated by DSC and TGA. As expected, crosslinked
PHU (1e) exhibits the highest glass transition temperature of 43 ◦ C due to its higher
rigidity. Under the optimized reaction conditions, molecular weights of the synthesized
poly(hydroxyurethane)s showed values up to 18.7 kg mol−1 and 40.1 kg mol−1 for PHU
(1f), when an external base was used as catalyst. In addition, the use of different cyclic
carbonate/diamines ratios was explored, which allowed the preparation of hydroxycar-
bamates 2 and 3 quantitatively. One-pot experiments led to the formation of different
compounds where CO2 carbamate salt and poly(aminoalcohol) products were identified as
byproducts. Thus, a sequential one-pot reaction, combining the synthesis of BGBC (1) and
subsequent polymerization, afforded the formation of the corresponding NIPUs without
further purification of the carbonate intermediate.

Supplementary Materials: The following are available online at https://www.mdpi.com/article/

10.3390/polym14132719/s1, Figure S1. 1 H NMR spectrum of PHU 1a in DMSO-d6 . Figure S2.
C13 {1 H} NMR spectrum of PHU 1a in DMSO-d6 . Figure S3. IR spectrum of PHU 1a. Figure S4. DSC
thermogram of PHU 1a. Figure S5. TGA thermogram of PHU 1a. Figure S6. 1 H NMR spectrum of
PHU 1b in DMSO-d6 . Figure S7. C13 {1 H} NMR spectrum of PHU 1b in DMSO-d6 . Figure S8. IR
spectrum of PHU 1b. Figure S9. MALDI-ToF spectrum of PHU 1b. Figure S10. DSC thermogram
of PHU 1b. Figure S11. TGA thermogram of PHU 1b. Figure S12. 1 H NMR spectrum of PHU 1c in
DMSO-d6 . Figure S13. C13 {1 H} NMR spectrum of PHU 1c in DMSO-d6 . Figure S14. IR spectrum of
PHU 1c. Figure S15. DSC thermogram of PHU 1c. Figure S16. TGA thermogram of PHU 1c. Figure
S17. 1 H NMR spectrum of PHU 1d in DMSO-d6 . Figure S18. C13 {1 H} NMR spectrum of PHU 1d in
DMSO-d6 . Figure S19. IR spectrum of PHU 1d. Figure S20. GPC trace of PHU 1d. Figure S21. DSC
thermogram of PHU 1d. Figure S22. TGA thermogram of PHU 1d. Figure S23. 1 H NMR spectrum
of PHU 1e in DMSO-d6 . Figure S24. C13 {1 H} NMR spectrum of PHU 1e in DMSO-d6 . Figure S25.
IR spectrum of PHU 1e. Figure S26. DSC thermogram of PHU 1e. Figure S27. TGA thermogram of
PHU 1e. Figure S28. IR spectrum of PHU 1e crosslinked. Figure S29. DSC thermogram of PHU 1e
crosslinked. Figure S30. TGA thermogram of PHU 1e crosslinked. Figure S31. 1 H NMR spectrum
of PHU 1f in DMSO-d6 . Figure S32. C13 {1 H} NMR spectrum of PHU 1f in DMSO-d6 . Figure S33.
IR spectrum of PHU 1f. Figure S34. GPC trace of PHU 1f. Figure S35. DOSY spectrum of PHU
1f. Figure S36. DSC thermogram of PHU 1f. Figure S37. TGA thermogram of PHU 1f. Figure
S38. 1 H NMR spectrum of hydroxycarbamate 2 in DMSO-d6 . Figure S39. C13 {1 H} NMR spectrum
of hydroxycarbamate 2 in DMSO-d6 . Figure S40. IR spectrum of hydroxycarbamate 2. Figure S41.
MALDI-ToF spectrum of hydroxycarbamate 2. Figure S42. 1 H NMR spectrum of hydroxycarbamate
3 in DMSO-d6 . Figure S43. C13 {1 H} NMR spectrum of hydroxycarbamate 3 in DMSO-d6 . Figure S44.
IR spectrum of hydroxycarbamate 3. Figure S45. MALDI-ToF spectrum of hydroxycarbamate 3.
Author Contributions: Conceptualization, J.A.C.-O. and A.L.-S.; methodology, F.d.l.C.-M., M.M.d.S.B.,
L.F.S.-B. and A.G.; formal analysis, F.d.l.C.-M., M.M.d.S.B. and J.A.C.-O.; investigation, F.d.l.C.-M.
and M.M.d.S.B.; resources, J.F.-B., E.F.-P. and A.L.-S.; data curation, E.F.-P., J.A.C.-O. and A.L.-S.;
writing—original draft preparation, J.A.C.-O.; writing—review and editing, F.d.l.C.-M., J.F.-B.,
L.F.S.-B., J.A.C.-O. and A.L.-S.; supervision, J.A.C.-O. and A.L.-S.; funding acquisition, A.L.-S. All
authors have read and agreed to the published version of the manuscript.
Polymers 2022, 14, 2719 15 of 17

Funding: We gratefully acknowledge the financial support; grant PID2020-117788RB-I00 funded

by MCIN/AEI/10.13039/501100011033, grant CTQ2017-84131-R funded by MCIN/AEI/10.13039/
501100011033 and, as appropriate, by “ERDF A way of making Europe”, by the “European Union”,
grant RED2018-102387-T funded by MCIN/AEI/10.13039/501100011033, and grant 2021-GRIN-31240
funded by Universidad de Castilla-La Mancha. Marc Martínez de Sarasa Buchaca acknowledges the
Universidad de Castilla-La Mancha (UCLM) for the PhD Fellowship. Felipe de la Cruz-Martínez
acknowledges the Ministerio de Educación, Cultura y Deporte (MECD) for the FPU Fellowship.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Conflicts of Interest: The authors declare no conflict of interest.

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