Synthesis of aminophosphonate polyols and polyurethane foams with

improved fire retardant properties


Ana M. Borreguero, María M. Velencoso, Juan F. Rodríguez, Angel Serrano, M. José Carrero,
María J. Ramos
Department of Chemical Engineering, Institute of Chemical and Environmental Technology, University of Castilla-La Mancha, Avd.
Camilo José Cela 1A, 13005 Ciudad Real, Spain
Correspondence to: M. J. Ramos (E-mail: mariajesus.ramos@uclm.es)

ABSTRACT: Aminophosphonated polyols with flame retardant properties are synthesized by ring opening polymerization using diethyl-
N,N-bis(2-hydroxyethyl) aminomethyl phosphonate (Fyrol-6) as initiator. The influence of the catalyst type and its concentration on
the polymerization rate are studied. The catalyst system formed by potassium methoxide (MeOK) in DMSO as a solvent presents the
highest polymerization rate and allows reducing the polydispersity. The thermal resistance of the synthesized polyols is confirmed by
the char residues formation. Finally, PU foams are synthesized containing up to a 50 pph of PFyCs[1:1], preserving good cellular struc-
ture up to a 25 pph content and improving the fire resistance by increasing the char residue from 7.79 to 22.13 wt % and decreasing the
PHRR and the smoke production according to TGA and cone calorimeter tests, respectively. © 2019 Wiley Periodicals, Inc. J. Appl. Polym.
Sci. 2019, 136, 47780.

KEYWORDS: fire retardant; foam; fyrol; polyether polyol; polyurethane

Received 4 September 2018; accepted 10 March 2019

DOI: 10.1002/app.47780

INTRODUCTION polymers when phosphorous and nitrogen compounds are used

Polyurethane (PU) foams are three-dimensional crosslinked
structures with unique structural and mechanical properties that
make them proper for building insulation applications, domestic
mattresses, cushions, sealants, and so forth.1,2 However, they are
also readily flammable unless treated due to their low thermo-
oxidative properties. To solve this drawback, the main alternative
has usually been the incorporation of different types of flame
retardant additives such as phosphorus compounds,3 bromine
compounds,4 inorganic salts,5 expandable graphite,4,6 hollow glass
microspheres or glass fibers.7 However, new routes are being
explored since the direct additives incorporation commonly pre-
sents poor compatibility, leaching, and can cause a reduction in
the mechanical properties of the obtained PU.8–11 The new routes
to overcome these problems are focused on the covalent union of
the flame retardant agents to the structure of the polyurethanes
for instance by including them in the initiators molecule,12 in the
monomers13,14 or linking them to the polyurethane backbone by
different covalent bonds.15–18
Nowadays, phosphorous compounds stand out as flame retardant
for polyurethane foams.17 These compounds are able to form a
char layer that prevents the oxygen and heat to reach the rest of
the material, extinguishing the combustion. Besides, it is well
known that there is a synergetic effect on the flame retardancy of
together.11,15,17
The diethyl-N,N-bis(2-hydroxyethyl) aminomethyl phosphonate,
commercially known as Fyrol-6, agrees with the conditions
pointed out as beneficial for the behavior of flame retardant: is a
reactive compound that can be covalently joined to the polyure-
thane backbone and contains both, nitrogen and phosphorous
compounds.19 Besides, Fyrol-6 is a liquid, which can help to use
it in polymerization processes, avoiding the necessity of solvents
that can negatively affect the process and that have to be
removed during the polymer purification. Thus, Fyrol-6 has been
studied as a reactive flame retardant in different polymers11,20–22
and applied in rigid polyurethane foams but never as polyol initi-
ator. However, it could be especially useful as an initiator in syn-
thesis of polyether polyols due to its nature, a diol.
In this work, aminophosphonated polyols are synthesized by ring
opening polymerization using Fyrol-6 as an initiator in order to
improve the flame retardant properties of conventional polyols.
The selection of Fyrol-6 was done in base of all the previously
mentioned advantages and the fact of having hydroxyl groups,
which react with propylene oxide. The influence of the type of
catalyst and the molar ratio catalyst to initiator were studied, ana-
lyzing the influence on the polymerization rate and on the main
characteristics of the synthesized polyols (composition, molecular

© 2019 Wiley Periodicals, Inc.

47780 (1 of 10) J. APPL. POLYM. SCI. 2019, DOI: 10.1002/APP.47780

ARTICLE WILEYONLINELIBRARY.COM/APP
weight, and polydispersity). Finally, the flame retardant proper-
ties of the polyols and PU foams containing them were deter-
mined by cone calorimeter.
EXPERIMENTAL
Materials
The following materials were used as received in the produc-
tion of the functionalized polyols: Propylene oxide (100%,
Praxair) as monomer, Diethyl bis(2-hydroxyethyl) amino-
methyl phosphonate (also called as Fyrol-6, 85–95%, ICL
Industrial) as initiator; CsOH (99%, Chemetall GmbH), KOH
(85%, Panreac), NaOH (98%, Panreac), and potassium
methoxide (MeOK) (≥ 90%, Sigma-Aldrich) as catalysts. Distil-
late water was used to dissolve the corresponding catalysts in
the case of the metal hydroxides: CsOH, KOH, or NaOH.
DMSO (98%, Sigma-Aldrich) was used as solvent for the case
of using MeOK. For the PU foams synthesis, commercial polyol
Alcupol R-4520 (hydroxyl number, 455 mg KOH g−1; average
MW, 555 g mol−1), silicone Tegostab B8404 as a silicone sur-
factant, and amine Tegoamin ZE1, as amine catalyst, from
Evonik, isocyanate (MDI) from POLIURETANOS AISMAR
S.A. and deionized water as blowing agent were used.
Polyols Synthesis Procedure
The synthesis of polyols initiated with Fyrol-6 was carried out
according to Scheme 1. The preparation of the different initiator
solutions and the polymerization reactions were carried out in a
2 L jacketed glass reactor (Büchi, Uster, Switzerland), with digital
control of stirring rate, temperature, and pressure. The vacuum
was controlled using a Divatronic DT (Köln, Germany) digital
vacuum indicator–controller, acting on a solenoid valve. To pre-
pare the different initiator solutions, Fyrol-6 was added to the
Scheme 1. Synthesis of aminophosphonate polyether polyol.
47780 (2 of 10)
reactor together with the catalysts, which were added in water
solution (50 wt %) for the case of CsOH, KOH, or NaOH and in
DMSO for the case of MeOK, in order to facilitate the miscibility
between the initiator and the catalysts. This initiator solution was
pressurized with nitrogen to achieve an inert atmosphere and
heated to 120 C. When the temperature was reached, the mixture
was stirred under high vacuum for 3 hours to ensure that the ini-
tiator solution was free of water (<0.2% water). Subsequently,
propylene oxide (PO) was fed into the reactor so that the pres-
sure in the reactor was 3 bar (0.3 MPa). The amount of added
PO was 146.5 g per 10 g of Fyrol-6. During the PO addition, the
monomer consumption rate was calculated by the measurement
of the remaining monomer in the feed at different times. Once
the addition of monomers was finished, a certain post-synthesis
time was needed. Finally, to eliminate residual monomers, high
vacuum (40 mbar) was applied for 2 hours.
The terminology used to identify samples is PFyX(), where PFy
indicates that the polyols are initiated with Fyrol-6, X will be the
cation of the used catalyst for the hydroxides and MeOK for the
methoxide, () will include the molar proportion between the cata-
lyst and the hydroxyl groups of the initiator.
Polyurethane Foams Synthesis
One of the polyols, PFyCs(1:1), was next used as a reagent in the
synthesis of PU foams in order to check the feasibility of using
these functionalized polyols as PU foams raw material. PU foams
were synthesized by weighting and mixing the desired masses of
the PFyCs(1:1) and a commercial polyol (Alcupol R-4520), sili-
cone Tegostab B8404, deionized water and amine Tegoamin ZE1,
and further stirring the mixture during 1 minute at 1000 rpm.
Then, the adequate quantity of isocyanate (MDI) was added to
the mixture, and the resulting solution was stirred for just
J. APPL. POLYM. SCI. 2019, DOI: 10.1002/APP.47780
ARTICLE WILEYONLINELIBRARY.COM/APP
5 seconds at 2000 rpm, moment at which the foam started to
grow up. Finally, the obtained foams were cured at room temper-
ature. Table I shows the foam synthesis recipe in parts per hun-
dred (pph) of polyol.
Characterization Techniques
Gel Permeation Chromatography (GPC) was used to determine
the molecular weight distribution of the polyols. Measurements
were performed with a Viscotek chromatograph with two col-
umns (Styragel HR2 and Styragel HR0.5) at 35 C with a flow of
1 mL
min−1 and THF as eluent. The calibration curves for GPC
analysis were obtained with poly(ethylene glycol) standards (from
waters).
Infrared spectra (FT-IR) were recorded on a Varian 640-IR FT-
IR spectrophotometer using KBr disks. 1H NMR spectra were
measured with a Varian Gemini FT-400 spectrometer using
CDCl3 as solvent.
Thermogravimetric analysis (TGA) was performed with a TA
instruments SDT Q600 Simultaneous DSC-TGA from room tem-
perature to 600 C at a heating rate of 10 C
min−1 under nitrogen
atmosphere.
Synthesized PU foams were depicted by the scanning electron
microscope (SEM, Quanta, FEI Company), using a large field
detector (LFD) with and accelerating voltage of 10 kV and with
magnification x 100. The samples were cut with a razor blade
and then analyzed.
The cone calorimetry experiments were carried out following the
procedure defined in ISO5660, on 12 mm thick 31 × 31 mm2
plaques. The cone data obtained are reproducible to within
10%, when measured at a heat flux of 35 kW m−2.
RESULTS AND DISCUSSION
Synthesis and Characterization of the Polyols
The influence of the cation of different metal hydroxides on the
synthesis of aminophosphonated polyols was studied, considering
the influence on the polymerization rate, the molecular weight
and polydispersity of the polyols. For this study, the ratio
between the catalyst and the initiator was maintained at 1:1.
Figure 1 compares the polymerization rates in form of PO con-
sumption with time. It can be observed that the PO consumption
in the polymerization catalyzed by CsOH presented a linear rela-
tionship without the induction period observed for the same cata-
lyst with other initiators, probably due to the good solubility of
the Fyrol-6 in the reaction media.12,14 When using catalysts KOH
and NaOH, induction periods with slow reactivity but of just few
Table I. Content of Raw Materials for PU Foams Synthesis
Material Content (pph)
Polyol (Alcupol R-4520 + PFyCs(1:1)) 100
Water 2.50
Silicone 1.51
Amine 2.50
MDI 100
47780 (3 of 10)
25
PFyCs(1:1)
PFyK(1:1)
20
PFyNa(1:1)
PO Consumption (g)
15
10
5 Propagation
Induction period
0
0 25 50 75 100 125 150 175 200
Time (min)
Figure 1. PO consumption with time depending on the catalyst for a molar
ratio catalyst to initiator of 1:1.
minutes (under 40 min in both cases) were observed. These ini-
tial induction periods are quite lower than those observed for
other initiators such as the glycerol phosphate calcium salt
hydrate or the glycerol phosphate disodium salt,12,14,23 and other
catalysts (such as multimetal cyanide or double cyanide
catalysts).24–26 This fact can be attributed to the time required for
the Fyrol deprotonation, probably due to it is a liquid instead of
a solid. In a previous work, it was observed that when using glyc-
erol phosphate disodium salt as initiator, the addition of that ini-
tiator partially deprotonated, reduced the induction period.
Once to overcome the initial induction period, the polymeriza-
tion reactions with these catalysts present linear relationships
between the PO consumption and time. Attending to the slope of
these curves, the CsOH promoted the highest polymerization rate
with a value of PO consumption of 0.61 g
min−1, while the values
for the KOH and the NaOH are 0.29 and 0.10 g
min−1, respec-
tively. The difference in the polymerization rate can be attributed
to the ionic radius (IR) of the catalyst cation, which are 1.67,
1.33, and 0.97 Å for Cs+, K+, and Na+, respectively.27 Thus, it can
be observed that the activity of the catalyst follows the same ten-
dency that the ionic radius order of their cations: irCs > irK >
irNa. This is so because the highest the ionic radius, the larger
the separation of the ion pair, improving the insertion of the
monomer into the polymer chain.28
In order to achieve a deep knowledge of the synthesized polyols,
FT-IR analysis was performed. Figure 2 shows the FT-IR spectra
of the synthesized polyols and of the initiator Fyrol-6. All the FT-
IR spectra of the synthesized polyols presented the typical func-
tional groups of a polyalcohol with the absorption bands of the
hydroxyl groups at 3460 cm−1 and with the corresponding signal
of C-O groups around 1080 cm−1.29 Besides, in the spectra region
between 2850 and 2990 cm−1 appeared the absorption bands due
to stretching vibrations of CH bonds of the aliphatic carbons of
the polyol chain and, in the region from 1370 and 1450 cm−1, it
can be observed the signal assigned to the bending vibrations of
methylene groups.30
J. APPL. POLYM. SCI. 2019, DOI: 10.1002/APP.47780
ARTICLE WILEYONLINELIBRARY.COM/APP

PFy Cs(1:1) PFy Na(1:1)

Transmittance (a.u.)

Transmittance (a.u.)
3460
C-OH 1645
C=O

930
P-OR

1014
P=O
2990-2850 1370-1450
1080
C-H CH2, CH3
C-O
4000 3500 3000 2500 2000 1500 1000 500 4000 3500 3000 2500 2000 1500 1000 500
Wavenumber (cm-1) Wavenumber (cm-1)

PFy K(1:1) Fyrol-6

Transmittance (a.u.)

Transmittance (a.u.)

930
P-OR
1014
P=O
4000 3500 3000 2500 2000 1500 1000 500 4000 3000 2000 1000
Wavenumber (cm-1) Wavenumber (cm-1)
Figure 2. IR spectra of the synthesized polyols with the different catalysts and the initiator Fyrol-6.

Additionally to the typical polyol signals, there are absorption different reasons: secondary reactions such as the transfer one
bands at 1014 and 930 cm−1 due to the presence of P O and and the presence of an impurity in the commercial Fyrol-6 that
P OR bonds, respectively, which can also be appreciated in the can initiate some chains of lower molecular weight. In order to
Fyrol-6 spectra.15 Therefore, the incorporation of the phospho-
rous in the polyol chain was confirmed and, thus, Fyrol-6 has
properly acted as an initiator with all the catalyst assayed. PFyCs(1:1)
The molecular weight and polydispersity of the synthesized poly- PFyK(1:1)
ols were obtained from GPC analysis (Figure 3). All the polyols PFyNa(1:1)
peaks were quite wide, indicating a high polydispersity index.
Intensity (a.u.)

The calculated values of the molecular weights of the main distri-

bution of the synthesized polyols and their polydispersity indexes
(PI) are shown in Table II. As expected, PFyK(1:1) and PFyNa
(1:1) had similar molecular weights of their main distributions,
being slightly higher the one from the polyol synthesized with
PFyK(1:1). In the same way, PFyCs(1:1) had a higher molecular
weight. Therefore, the molecular weight seems to follow a similar
tendency than the reaction rates. This seems to indicate that the
higher the polymerization rate, the higher the kinetic of the main
reaction, which leads to high molecular weights.28 On the other 10 11 12 13 14 15 16
hand, the polydispersity index is high in all the cases, due to the Elution Volume (ml)
broaden chain distribution. This can be attributed to two Figure 3. GPC analysis of the synthesized polyols with the different catalysts.

47780 (4 of 10) J. APPL. POLYM. SCI. 2019, DOI: 10.1002/APP.47780

ARTICLE WILEYONLINELIBRARY.COM/APP
Table II. Molecular Weight and Polydispersity of the Synthesized Polyols
Polyol Mw (g
mol−1)
PFyCs(1:1) 6000
PFyK(1:1) 4000
PFyNa(1:1) 3250
see clearly the different chains distributions of PFyCs(1:1), its
spectrum was deconvoluted (Figure 4). Figure 4 shows that
PFyCs(1:1) is composed of three chain distributions with two
main ones (A1 and A2), that correspond to the polyol chains that
grow initiated by the Fyrol-6 and its impurity component. A1
distribution has a molecular weight of 6072 g
mol−1, which was
assigned to the polyether polyol chain, while A2 distribution
molecular weight is just 3390 g
mol−1. Besides, there is a third
distribution of less importance (just corresponding to the 21% of
the area), which is formed by small oligomers formed due to sec-
ondary reactions. The hypothesis that the presence of an impu-
rity in the commercial Fyrol-6 causes the second peak that
appears in the PFyCs(1:1) GPC is supported by the two different
molecular weight distributions observed in GPC analyses of the
commercial Fyrol-6. Figure 5 shows the deconvolution of the
main distributions observed in the GPC results of the commercial
Fyrol-6 used in this work. The commercial product presents a
main distribution corresponding to a molecular weight of
255 g
mol−1, which corresponds to the structure known as Fyrol
(253.23 g
mol−1). Additionally, the spectrum deconvolution
shows a second distribution of less contribution (about a 20% of
the area) with lower molecular weight, around 170 g
mol−1. Con-
sidering the molecular weight of the second distribution, the
impurity that acts as a secondary initiator could be the diethyl-
(aminomethyl)-phosphonate. This compound presents a molecu-
lar weight of 167.14 g
mol−1 and a similar structure than Fyrol-6
but with an amino group (Scheme 2).
1
H NMR analysis of the commercial Fyrol-6 was performed in
order to confirm the presence of the diethyl-(aminomethyl)-
phosphonate as impurity (Figure 6). As can be seen in Figure 6,
PFy Cs(1:1)
A1
A2
A3
Intensity (a.u.)
10 11 12 13 14 15
Elution Volume (ml)
Figure 4. Deconvolution of GPC spectrum of PFyCs(1:1).
Commercial Fyrol-6
Main distribution (Fyrol)
PI Secondary distribution (Impurities)
2.03
1.48
Intensity (a.u.)
2.13
16.0 16.4 16.8 17.2 17.6 18.0
Elution Volume
Figure 5. Deconvolution of GPC spectrum of Fyrol-6 commercial product.
the 1H NMR presents a peak at 8.05 ppm corresponding to the –
NH2 group, supporting the hypothesis of the presence of diethyl-
(aminomethyl)-phosphonate as impurity. Amines have been
previously used as initiators in anionic polymerization of epox-
ides, thus, the diethyl-(aminomethyl)-phosphonate can be con-
sidered as initiator of polyol chains in our system.31,32 Besides,
the initiation with amines promotes many side reactions, the
hydrogen of amino groups usually causes transfer and termina-
tion reaction,31 which agrees with the presence of the commented
polyol secondary molecular weight distributions.
The use of CsOH as a catalyst allowed obtaining the highest reac-
tion rate without induction period but the obtained polyols pres-
ented a high polydispersity index. In order to reduce the polyols
polydispersity and see the effect on the rest of polyols properties,
the catalyst to initiator ratio was modified. This ratio was
reduced, studying the cases 1:2 and 1:5, in addition to the 1:1
previously assayed. The reaction rate in form of PO consumption
with time is shown in Figure 7 just for the cases of ratios 1:1 and
1:2, since the ratio 1:5 did not allow to obtain the polyol. As
expected, the reduction of the catalyst proportion reduced the
polymerization rate since the slope of the evolution of PO con-
sumption with time decreased from 0.61 to 0.28 g
min−1. More-
over, a significant induction period of about 180 minutes
appeared, as occurred for the cases of using KOH and NaOH as
catalyst. The ratio 1 to 5, did not allow to obtain the polyol
16
Scheme 2. Structure of the possible impurity presented in commercial
Fyrol-6.
47780 (5 of 10) J. APPL. POLYM. SCI. 2019, DOI: 10.1002/APP.47780
ARTICLE WILEYONLINELIBRARY.COM/APP

OH
d
O
e a
b
P N OH
O
a c
O

O
f
P NH2
O
O e
d
b c

Figure 8. GPC spectrum of PFyCs(1:2).

8 7 6 5 4 3
δ (ppm)
1
Figure 6. H NMR analysis of the commercial Fyrol-6.
synthesis, at least not in a reasonable time, compared to the other
two assayed ratios.
According to the results shown by the use of the other catalyst
(which presented lower consumption rates), the lower consump-
tion rate should be translated in a reduction of the final molecu-
lar weight and should also affect the polydispersity index. GPC
analysis of PFyCs(1:2) was performed in order to determine its
molecular weight and the polydispersity index (Figure 8).
According to the GPC results as shown in Figure 8, polyol PFyCs
(1:2) presented again two main distributions with a PI value of
2.05 and a molecular weight of the main distribution of
4019 g
mol−1. Thus, as expected, the use of a lower proportion of
catalyst reduced the molecular weight, but there was no improve-
ment on the polyol polydispersity. The two main distributions
30
PFy Cs(1:1)
PFy Cs(1:2)
25
PO Consumption (g)
2 1
seems to follow the same behavior than those obtained for polyol
PFyCs(1:1) and grow using as initiator Fyrol-6 and its impurity.
Thus, the polydispersity was practically the same (2.03 and 2.05
for ratio 1:1 and 1:2, respectively) and, thus, the reduction of the
growth of the polyol using the impurity as initiator was not
achieved by changing the catalyst ratio when using CsOH as
catalyst.
The polydispersity can be increased by the presence of water, since
it can promote secondary reactions, affect to the activation of the
initiators and to the catalyst activity. In the studied catalyst, there
is water due to the fact that it is the solvent for their solutions but
also because it is formed during the initiator deprotonation pro-
cess. Once the initiator is deprotonated, a dehydration step is car-
ried out before the monomer addition. However, water moieties
can remain in the system promoting high polydispersity indexes in
the polyols. In order to reduce the polyols PIs, a system free of
water making use of potassium methoxide (MeOK) as catalyst and
dimethyl sulfoxide (DMSO) as solvent was used. The expected
advantages of this system are the absence of water, and a conse-
quent reduction of the secondary reactions, and the increase of the
reaction rate, since the DMSO favors the catalyst ions separation
and, thus, the monomer insertion.33
A solution of 20% of MeOK in DMSO was used as catalyst sys-

20
tem in the ratios 1:1, 1:2, and 1:5 with respect to the Fyrol-6. The
polymerization rates in form of PO consumption with time for
15 the cases of catalyst to initiator 1:1 and 1:2, PFyMtK(1:1) and
PFyMtK(1:2), respectively, are shown in Figure 9. As for the case
of using CsOH as catalyst, the ratio 1:5 did not allow to obtain
10
the desired polyol.
As expected, the higher the catalyst concentration, the faster the
5 PO consumption, with a slope of the PO consumption with
respect to the time of 3.04 and 1.75 g
min−1, for the PFyMtK
0 (1:1) and PFyMtK(1:2), respectively. It is remarkable that this cat-
0 50 100 150 200 250 alyst system promotes reaction rates much faster than the studied
Time (min) metal hydroxides in water, being the values of PO grams con-
Figure 7. PO consumption with time depending on the molar ratio catalyst sumption
min−1, a 398% higher than for the CsOH, which was
to initiator when using CsOH as a catalyst. the best case of the studied metal hydroxides.

47780 (6 of 10) J. APPL. POLYM. SCI. 2019, DOI: 10.1002/APP.47780

ARTICLE WILEYONLINELIBRARY.COM/APP

35 suitable than the use of metal hydroxides in water for the poly-
merization of propylene oxides using Fyrol-6 as initiator.
30 PFyMtK(1:1)
Thermal Resistance Properties of the Synthesized Polyols
PFyMtK(1:2)
25 The thermal resistance is evaluated by the amount of char residue
PO Consumption (g)

formation, which corresponds to the phosphorous presence.

20
15
10
5 sized with metal hydroxides and water. This way, the influence
0 tested. The thermal degradation and the char residue were stud-
0 10 20 30
Time (min)
Figure 9. PO consumption with time depending on the molar ratio catalyst
to initiator when using MeOK in DMSO as catalyst system.
The synthesized polyols were characterized by means of GPC
analyses (Figure 10) obtaining Mw of 2840 and 3546 g
mol−1
and PI values of 2.55 and 1.87 for the PFyMtK(1:1) and PFyMtK
(1:2), respectively.
As can be seen in Figure 10, both polyols synthesized with the
system MeOK in DMSO presented wide molecular weight distri-
butions with the difference that for lower ratios of catalyst, there
are two different peaks instead of a wider one. It seems to indi-
cate that the lower reaction rate promotes a more controlled
growth of the monomer over the main components of commer-
cial Fyrol-6, as was observed for the same catalyst ratio of the
system of CsOH in water. The main difference found in the
obtained polyols when using MeOK in DMSO is the fact that the
polydispersity index is improved with the reduction of the cata-
lyst proportion, which was the aim of this part of the work.
Therefore, due to the increase of the polymerization rate and the
reduction of the PI, the use of MeOK in DMSO seems to be more
Besides, the nitrogen content is proportional to the phosphorous
one. For this propose, thermogravimetric analyses (TGA) of pure
Fyrol-6, PFyMtK(1:2), and PFyCs(1:1) polyols were assayed.
PFyMtK(1:2) was chosen, since it presented better polydispersity
index and high polymerization rate and PFyCs(1:1) because of its
good polymerization rate compared to the rest of polyols synthe-
on the thermal behavior of the two studied catalytic systems is
40 50 ied by TGA (Figure 11).
Figure 11 shows that pure Fyrol-6 exhibits a first degradation
step starting at 130 C, with a maximum peak temperature at
210 C, and a second graduated weight loss step starting at 250 C
until the end of the analysis, where the remaining 21 wt % of the
compound corresponds with the char residue. On the contrary,
both polyols present an only backward degradation step that
starts at higher temperature, around 300 C with a maximum
peak at 375 C [Figure 11(b)], degradation temperature in the
range of those obtained for similar polyols.14 The main fact is
that both polyols present important char residues, with values of
5.6 and 4.0 wt% for the PFyCs(1:1) and PFyMtK(1:2), respec-
tively. This indicates the incorporation of the phosphorous in
both polyols in similar percentages and even higher than those of
other polyols found in literature.13,14,23,34 The higher char residue
of PFyCs(1:1) can be attributed to the observed presence of oligo-
mers that incorporate higher phosphorous content per chain,
since they have higher proportion of initiator per mass of polyol.
Functionalized PU Foams
Different percentages from 0 to 50 pph of the synthesized PFyCs
(1:1) were used as replacement for a commercial polyol used for
rigid polyurethane synthesis. PFyCs(1:1) was selected for the
foams synthesis, since it presented the highest char residue and,

(a) (b) 2.5

100
PFyMtK(1:1)
PFyMtK(1:2) 2.0
80
PFyCs(1:1)
Deriv. Weight (%/C)

PFyMtK(1:2)
1.5 Fyrol-6
Intensity (a.u.)

60
Weight (%)

1.0
40

0.5

20
PFyCs(1:1)
PFyMtK(1:2)
Fyrol-6 0.0

0
0 100 200 300 400 500 600 0 100 200 300 400 500 600
10 11 12 13 14 15 16 Temperature (C) Temperature (C)
Elution volume (ml) Figure 11. (a) TG curves. (b) DTG curves of Fyrol-6, PFyCs(1:1), and
Figure 10. GPC analysis of PFyMtK(1:1) and PFyMtK(1:2) polyols. PFyMtK(1:2) polyols.

47780 (7 of 10) J. APPL. POLYM. SCI. 2019, DOI: 10.1002/APP.47780

ARTICLE WILEYONLINELIBRARY.COM/APP
Figure 12. SEM analysis of PU foams with different PFyCs(1:1) contents: (a) 0.0 pph, (b) 5.0 pph, (c) 10.0 pph, (d) 25.0 pph, and (e) 50.0 pph.
thus, potential higher flame retardant properties. Figure 12 shows
the cell structure of the pure PU foam and of those containing
the different PFyCs(1:1) contents.
As can be seen in Figure 12, the foams containing up to a 25.0
pph of PFyCs(1:1) exhibited polyhedral closed-cell structures
with pentagonal or hexagonal faces containing nodes formed by
the junction of four struts. The cell disruption for the foam con-
taining the 50 pph of the PFyCs(1:1) maybe just due to the fact
that we are using a recipe that is optimized for the commercial
polyol and is known that unadjusted foam formulation can mod-
ify the nucleation rate and the final cell size.35 The average value
of the cell sizes and their standard deviation for the synthesized
foams are shown in Figure 13.
47780 (8 of 10)
As can be seen, the average cell size does not change significantly,
with a value <300 μm in all cases. However, it is worthy to point
out that the cell homogeneity was good up to a PFyCs(1:1) con-
tent of 10 pph (with standard deviations < 45.0 μm), while for
the case of the 25 pph it increased, with a standard deviation up
to a value of 118.9 μm. As indicated before, the structure of the
foam containing a 50 pph of PFyCs(1:1) was very disrupted, in
fact, the cell size study showed a high heterogeneity with cells
sizes between 200 μm and more than 1.0 mm.
On the other hand, to investigate the improvement in the ther-
mal resistance of the foams depending on the polyol content,
thermogravimetric analyses were performed. The thermal resis-
tance of polymer is directly related to the char formation during
J. APPL. POLYM. SCI. 2019, DOI: 10.1002/APP.47780
ARTICLE WILEYONLINELIBRARY.COM/APP

450 Table III. Combustion Data of Foams with Different PFyCs(1:1) Contents

375 PHRR THR TSR

Foam (kW m−2) (MJ m−2) TSP (m2) (m2 m −3)

300 0 pph 109  18 1.8  0.3 0.40  0.08 44  10

Cell Size (μm)

25 pph 49  1 0.8  0.1 0.18  0.04 21  5

225
the combustion process,36–38 and the char percentage measured
150 by TGA is accepted by an indirect way of measuring this prop-
erty.39,40 Figure 14 compares the TG analyses of foams with the
polyols contents from 0.0 to 25.0 pph. As commented before, the
75
foam with a 50.0 pph presented a deteriorated cell structure and
it was not used for this study.
0
0 5 10 25 As expected, the higher the polyol content, the higher the char
PFyCs(1:1) Content (pph) yield, passing from 7.79 to 22.13 wt% for the cases of 0.0 pph
Figure 13. Cell size of foams with different PFyCs(1:1) contents. and 25 pph of PFyCs(1:1), respectively. This means a char resi-
due increase of a 184%.
100 In order to evaluate the PU foams fire resistance, the cone calo-
rimeter provides a wealth of information on the combustion
behavior under ventilated conditions. Figure 15 shows the heat
80 PFyCs(1:1) Content (pph) release rate (HRR) curves of foams with the polyols contents
0.0 from 0.0 to 25.0 pph. Table III summarizes the detailed results
5.0
on the peak heat release rate (PHRR), the total heat release
Weight (%)

60 10.0
(THR), the total smoke production (TSP), and the total smoke
25.0
release (TSR). The HRR curve seems nearly the same but the
main different is in the PHRR. The PHRR of the foam with
40
25 pph was lower of that for the foam with 0 pph, which shows
clearly a charring behavior. The lower the value of PHRR, the
lower the maximum temperature and flame spread rate of the
20
tested sample. In addition, the introduction of 25 pph of polyol
decreased the THR value (Table III). The lower the value of
0 THR, the smaller the fire load of the tested sample, which means
0 100 200 300 400 500 600 700 that the sample with PFyCs(1:1) will promote a faster extinction
Temperature (ºC) of fire. According to the smoke production (TSP and TSR), the
presence of polyol (25 pph) reduced the quantity of smoke that
Figure 14. TGA results of foams with PFyCs(1:1) contents from 0 to
the fire produces. Thus, the use of the synthesized polyols using
25 pph.
Fyrol as initiator allows to obtain PU foams that, in a fire situa-
tion, produce more char and less flammable volatile products,
obtaining a good flame retardant material.

CONCLUSIONS
Polyols with flame retardant properties were synthesized by using
the aminophosphonated molecule Fyrol-6 as an initiator. The
polymerization rates depend on the catalyst system and on the
ratio of catalyst to initiator. The catalyst system formed by the
potassium methoxide in DMSO as solvent present the highest
polymerization rate (up to 398% higher than for the best case of
the metal hydroxides studied). CsOH as catalyst presented the
highest reaction rate. The polydispersity index was high in all
the cases, what can be attributed to secondary reactions such as
the transfer reaction and the presence of an impurity in the com-
mercial Fyrol-6 that can initiate some chains of lower molecular
weight. The reduction of the catalyst ratio in the case of the cata-
Figure 15. The HRR curves of foams with PFyCs(1:1) contents from 0 to lyst system of potassium methoxide in DMSO was able to reduce
25 pph. a 33% the polydispersity, while keeping high polymerization

47780 (9 of 10) J. APPL. POLYM. SCI. 2019, DOI: 10.1002/APP.47780

ARTICLE WILEYONLINELIBRARY.COM/APP
rates. This system also presented a reduction of an 8.8% respect
to the PI of polyols synthesized with metal hydroxides for catalyst
to initiator ratios of 1:2. The thermal resistance properties of the
synthesized polyols were confirmed by the TGA results, which
shows a char residue of 5.6 and 4.0 wt% for the PFyCs(1:1) and
PFyMtK(1:2), respectively. Finally, PU foams were synthesized
containing up to a 50 pph of PFyCs(1:1), preserving the good cel-
lular structure up to a 25 pph content and improving the thermal
resistance properties by increasing the char residue formation
from 7.79 to 22.13 wt%. Results obtained in cone calorimeter
confirmed that PU foam with a 25 pph content of PFyCs(1:1)
decreased the PHRR, THR, and the smoke production, which
confirmed the behavior as flame retardant.
REFERENCES
1. Hirschler, M. Polym. Adv. Technol. 2008, 19, 521.
2. Serrano, A.; Borreguero, A.; Garrido, I.; Rodriguez, J.;
Carmona, M. Appl. Therm. Eng. 2016, 103, 226.
3. Xu, W.; Wang, G.; Zheng, X. Polym. Degrad. Stab. 2015,
111, 142.
4. Ye, L.; Meng, X.; Liu, X.; Tang, J.; Li, Z. J. Appl. Polym. Sci.
2009, 111, 2372.
5. Lindholm, J.; Brink, A.; Wilen, C.; Hupa, M. J. Appl. Polym.
Sci. 2012, 123, 1793.
6. Liu, C. H.; Lin, C. Y.; Chen, J. L.; Lai, N. C.; Yang, C. M.;
Chen, J. M.; Lu, K. T. J. Catal. 2016, 336, 49.
7. Cheng, J.; Shi, B.; Zhou, F.; Chen, X. J. Appl. Polym. Sci.
2014, 131, 40253.
8. Chang, T.; Shen, W.; Chiu, Y.; Ho, S. Polym. Degrad. Stab.
1995, 49, 353.
9. El Khatib, W.; Youssef, B.; Bunel, C.; Mortaigne, B. Polym.
Int. 2003, 52, 146.
10. Grancharov, G.; Mitova, V.; Shenkov, S.; Topliyska, A.;
Gitsov, I.; Troev, K. J. Appl. Polym. Sci. 2007, 105, 302.
11. Devedjiev, I.; Ganev, V.; Borisov, G. Eur. Polym. J. 1989,
25, 1027.
12. Velencoso, M. M.; Gutierrez, C.; Ramos, M. J.; García-
Martínez, J. C.; De Lucas, A.; Rodriguez, J. F. J. Macromol.
Sci., Part A: Pure Appl. Chem. 2011, 48, 569.
13. Zhang, Q.; Chen, F.; Ma, L.; Zhou, X. J. Appl. Polym. Sci.
2014, 131, 40422.
14. Velencoso, M. M.; Ramos, M. J.; Serrano, A.; de Lucas, A.;
Rodríguez, J. F. Polym. Int. 2015, 64, 1706.
15. Ding, H.; Wang, J.; Wang, C.; Chu, F. Polym. Degrad. Stab.
2016, 124, 43.
47780 (10 of 10)
16. Borreguero, A. M.; Sharma, P.; Spiteri, C.;
Velencoso, M. M.; Carmona, M. S.; Moses, J. E.;
Rodríguez, J. F. React. Funct. Polym. 2013, 73, 1207.
17. Yuan, Y.; Yang, H.; Yu, B.; Shi, Y.; Wang, W.; Song, L.;
Hu, Y.; Zhang, Y. Indus. Eng. Chem. Res. 2016, 55, 10813.
18. Yang, R.; Hu, W.; Xu, L.; Song, Y.; Li, J. Polym. Degrad.
Stab. 2015, 122, 102.
19. Yin, X.; Luo, Y.; Zhang, J. Indus. Eng. Chem. Res. 2017, 56, 1791.
20. Sivriev, C.; Zabski, L.; Borissov, G. Eur. Polym. J. 1992, 28, 9.
21. Sivriev, C.; Zabski, L. Eur. Polym. J. 1994, 30, 509.
22. Alcon, M.; Ribera, G.; Galia, M.; Cadiz, V. J. Polym. Sci.
Part A-Polym. Chem. 2005, 43, 3510.
23. Velencoso, M. M.; Ramos, M. J.; Garcia-Martinez, J. C.; De
Lucas, A.; Rodriguez, J. F. J. Macromol. Sci., Part A: Pure
Appl. Chem. 2013, 50, 905.
24. Lee, S. H.; Byun, S. H.; Baek, S. T.; Seo, H. S.; Park, D. W.;
Ha, C. S.; Kim, I. Catalysis Today. 2008, 132, 170.
25. Lee, S.; Baek, S. T.; Anas, K.; Ha, C. S.; Park, D. W.;
Lee, J. W.; Kim, I. Polymer. 2007, 48, 4361.
26. Zhang, J.; Liu, Q.; Ren, H.; Zhang, N.; Li, P.; Yang, K.
J. Mol. Struct. 2017, 1148, 421.
27. Ahrens, L. H. Geochim. Cosmochim. Acta. 1952, 2, 155.
28. de Lucas, A.; Rodríguez, L.; Pérez-Collado, M.; Sánchez, P.;
Rodríguez, J. F. Polym. Int. 2002, 51, 1066.
29. Simon, D.; Borreguero, A. M.; de Lucas, A.; Rodriguez, J. F.
Polym. Degrad. Stab. 2015, 121, 126.
30. Simón, D.; de Lucas, A.; Rodríguez, J. F.; Borreguero, A. M.
Polym. Degrad. Stab. 2016, 133, 119.
31. Brocas, A. L.; Mantzaridis, C.; Tunc, D.; Carlotti, S. Prog.
Polym. Sci. 2013, 38, 845.
32. Simon, D.; Maria Borreguero, A.; de Lucas, A.; Molero, C.;
Francisco Rodriguez, J. J. Mater. Cycles Waste Manage.
2014, 16, 525.
33. Baskaran, D.; Muller, A. Prog. Polym. Sci. 2007, 32, 173.
34. De Espinosa, L.; Meier, M.; Ronda, J.; Galia, M.; Cadiz, V.
J. Polym. Sci. Part A-Polym. Chem. 2010, 48, 1649.
35. Borreguero, A. M.; Valverde, J. L.; Rodriguez, J. F.; Barber, A. H.;
Cubillo, J. J.; Carmona, M. Chem. Eng. J. 2011, 166, 384.
36. Lyon, R. Polym. Degrad. Stab. 1998, 61, 201.
37. Lyon, R.; Takemori, M.; Safronava, N.; Stoliarov, S.;
Walters, R. Polymer. 2009, 50, 2608.
38. Tarakcilar, A. J. Appl. Polym. Sci. 2011, 120, 2095.
39. Chattopadhyay, D.; Webster, D. Prog. Polym. Sci. 2009, 34, 1068.
40. Mequanint, K.; Sanderson, R.; Pasch, H. Polym. Degrad.
Stab. 2002, 77, 121.
J. APPL. POLYM. SCI. 2019, DOI: 10.1002/APP.47780