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Research Article

pubs.acs.org/journal/ascecg

Rigid Polyurethane Foam Fabrication Using Medium Chain

Glycerides of Coconut Oil and Plastics from End-of-Life Vehicles
Aleksandra Paruzel,† Sławomir Michałowski,‡ Jiří Hodan,† Pavel Horák,† Aleksander Prociak,*,‡
and Hynek Beneš*,†
†
Institute of Macromolecular Chemistry AS CR, v.v.i., Heyrovsky Sq. 2, 162 06 Prague 6, Czech Republic
‡
Cracow University of Technology, Department of Chemistry and Technology of Polymers, Warszawska 24, 31-155 Cracow, Poland
*
S Supporting Information

ABSTRACT: Polycarbonate and polyurethane scraps from end-of-

life vehicles were converted into liquid recycled polyols with hydroxyl
number around 300 mgKOH·g−1 by using medium chain glycerides
of coconut oil. The obtained polyols were used for preparation of
low-density rigid polyurethane foams. It was found that up to 50 wt %
of the virgin petrochemical polyol can be replaced by the recycled
polyols without any negative effect on the foaming process. The
obtained foams exhibited the apparent density of 40−44 kg·m−3, the
homogeneous cellular structure with a high content of closed cells
(>91 vol %) and the beneficially low value of lambda coefficient (∼23
mW·m−1·K−1). The exceptionally high compressive strength (>350
kPa in parallel to foam rise direction) of the rigid PUR foams with 50
wt % of recycled polyol derived from polycarbonate scrap resulted probably from the unique structure of recycled polyol
combining rigid aromatic segments together with flexible coconut oil glyceride units. In conclusion, this approach utilizing the
renewable coconut oil-derived reagent provides a sustainable recycling solution for two major plastics from automotive waste.
KEYWORDS: Polyurethane, Polycarbonate, Rigid foam, Vegetable oil, Chemical recycling, Degradation, Renewable resource,
Microwave irradiation

■ INTRODUCTION
The global automotive plastics consumption is expected to
grow from 7.1 million tons in 2012 to 11.3 million tons by
2018.1 Polypropylene (PP) leads consumption by 36%
followed by polyurethanes (PUR) (17%), acrylonitrile−
butadiene−styrene copolymer (ABS) (12%), composites
(11%), high-density polyethylene (HDPE) (10%), polycar-
bonates (PC) (7%), and poly(methyl methacrylate) (PMMA)
(7%).1 End-of-life vehicles (ELVs) thus present one of the main
sources of different plastic wastes. Some of them such as
polyolefins (including HDPE, PP) can be relatively easily
reprocessed, while the others, such as PUR, must be subjected
to chemical recycling (e.g., glycolysis, hydrolysis, etc.) in order
to be converted into low molecular weight products with
functional groups capable of further reacting.2 However, the
chemical recycling methods might be also useful for thermo-
plastic waste treatment, especially when additives, admixtures,
or other impurities initiate undesirable polymer degradation
during reprocessing, which deteriorates mechanical properties
of recycled products. A typical example might be a PC scrap of
automotive headlamps containing siloxane coatings and/or
metallic paints making its reprocessing without unwanted PC
degradation difficult. On the other hand, both PUR and PC
wastes might be easily dismantled from ELVs and sorted out
from other thermoplastics (PE, PP, etc.), which enables their
recovery via chemical recycling.
Various methods of chemical recycling for PUR wastes have
been broadly explored during the last three decades and were
the subject of several reviews.3−5 Despite the numerous
chemical recycling techniques that have been developed for
PUR, only a few studies investigated potential applications of
recovered products (recycled polyols) to prepare novel PUR
materials,6−9 especially rigid PUR foams.10−13 The rigid PUR
foams, because of their excellent properties such as low density
and thermal conductivity, high strength-to-weight ratio, low
moisture absorption, etc., are widely used as thermal insulations
in building construction and refrigeration, cushioning and
insulating materials in automotive industry, or in packaging.14
The addition of recycled polyols into rigid PUR foam
formulation must be well balanced since it often increases the
viscosity of the polyol stream and leads to failure of foam
properties. Prociak et al. found that the glycolysis product
might replace a virgin polyol of rigid PUR foam formulation in
the amount not exceeding 30 wt % due to processing limits
connected to too high a viscosity of the recycled polyols.15 The
Received: April 18, 2017
Revised: May 15, 2017
Published: May 19, 2017

© 2017 American Chemical Society 6237 DOI: 10.1021/acssuschemeng.7b01197

ACS Sustainable Chem. Eng. 2017, 5, 6237−6246
ACS Sustainable Chemistry & Engineering
glycolysis product addition often causes an undesirable increase
of foam density, which can be slightly adjusted using density
modifiers such as starch.16 Zhu et al. reported the preparation
of rigid PUR foams meeting industrial requirements only when
the content of glycolysis product in the polyol mixture was
below 10 wt %.17 Lee et al. used the reaction of butyl glycidyl
ether with amines to convert aromatic amines presented in the
glycolysis product to polyols.18 This modification allowed
increasing the content of recycled polyol (up to 30 wt % in a
polyol mixture) in rigid PUR foams with no deterioration of
their physical properties. The novel types of recycled polyols
derived from oleochemical (rapeseed oil and fish oil based)
polyols enabled 100% replacement of virgin polyols, but only
high-density rigid PUR foams19 or semirigid PUR foams20 were
obtained.
Contrary to widely explored chemical recycling methods of
PUR producing recycled polyols, only a few examples of PC
glycolysis yielding polyol products, namely bis-hydroxylalkyl
ethers of bisphenol A (BPA), have been mentioned in the
literature.21−23 Lin et al. applied the produced bis-hydroxyalkyl
ethers of BPA for preparation of PUR elastomers.21 No further
application for polyols produced during PC chemolysis has
been described yet in the literature.
Generally, the higher content of recycled polyols, prepared
by the conventional glycolysis, in rigid PUR foams resulted in a
too brittle foam structure due to a high content of aromatic
segments in the PUR network interconnected via short glycol-
derived linkages. It was found that this drawback might be
eliminated when rapeseed, castor, and fish oil-based polyols,
bearing hydroxyl groups on glyceride units, were used for
polymer decomposition instead of short glycols.19,20,24−26
However, these polyols contained mainly long chain glycerides
acting as soft segments of PUR networks producing semirigid
PUR foams. In one of a last study, Beneš et al. used a waste
fraction from the soap industry composed uniquely of medium
chain triglycerides of coconut oil (CCO) for synthesis of a
biobased reagent for PC degradation.26 The reagent was
prepared by transesterification of CCO with glycerol from
biodiesel production. The obtained transesterified CCO
(TCCO) is thus 100% renewable-based, prepared only from
byproducts and was already proven to be an efficient reagent
for solvolysis of PC technological scraps.26
In this paper, TCCO was used for microwave-accelerated
decompositions of two postconsumer wastes (PUR and PC)
coming from ELVs. The PUR and PC wastes were converted
by TCCO into two types of recycled polyols, both composed
uniquely of renewable and recycled components. The obtained
polyols were analyzed and tested for preparation of low-density
rigid PUR foams applicable as thermal insulations. The
influence of recycled polyols’ additions on the foaming process
as well as on the morphology and properties of final PUR foams
were investigated in details.
■
EXPERIMENTAL SECTION
Transesterification of Medium Chain Glycerides of Coconut
Oil. CCO, the byproduct from soap industry composed of >99%
triglycerides of caprylic (C8:0) and capric (C10:0) acids, was kindly
received from Environ Ltd. (Czech Republic) and transesterified using
glycerol (99.5%, Preol, Czech Republic), the byproduct from biodiesel
production, according to the procedure previously described.26 The
prepared transesterified product (TCCO) exhibited the hydroxyl
number of 560 mgKOH·g−1 and the number-average functionality of
2.15. TCCO was used as the reagent for conversions of PUR and PC
wastes into recycled polyols.
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Preparation of Recycled Polyol from Polyurethane Waste.
The postconsumer waste of semirigid PUR foam from ELVs was first
pressed and cut to small pieces (ca. 1 × 1 × 1 cm3). Next, the PUR
waste (150 g) and TCCO (165 g) were placed into a 2500 mL three-
neck flask equipped with nitrogen inlet, reflux, and mechanical stirrer.
The reaction mixture was heated in a multimode microwave reactor
(Romill, Ltd., Czech Republic, f = 2.45 GHz, maximum power of 1000
W). The temperature was controlled using a shielded Pt100-
thermometer inserted directly into the reaction medium. After ca. 30
min of microwave heating with the constant power of 400 W, the
temperature of reaction mixture reached 210 °C. Then, the
temperature was kept constant at 210 °C for further ca. 15 min.
The reaction was complete when no PUR oligomers were found in the
mixture, which was checked using size exclusion chromatography
(SEC). The product was cooled, and the solid impurities were filtered
off. The obtained product, recycled PUR polyol (RPUP), was a brown
liquid.
Preparation of recycled polyol from polycarbonate waste.
The granulated postconsumer PC waste from ELV (800 g) and
TCCO (800 g) were placed into a 2500 mL three-neck flask equipped
with nitrogen inlet, reflux and mechanical stirrer. The reaction mixture
was heated in the same microwave reactor with the same temperature
control as described above for the PUR waste decomposition. After ca.
40 min of microwave heating with the constant power of 500 W, the
temperature of such reaction mixture reached 215 °C. Then, the
temperature was kept constant at 215 °C, and within ca. 40 min the
reaction was complete since no PC oligomers were found in the
mixture (verified by SEC). The product was cooled, and the solid
impurities were filtered off. The obtained product, recycled PC polyol
(RPCP) was a pale yellow liquid.
Characterization of the Recycled Polyols. The SEC of the
recycled polyols was performed on a Modular GPC system equipped
with a refractive index detector RIDK-102 (Laboratorni pristroje
Praha, Czech Republic) and an UV−vis photometric detector LCD
2084 (ECOM, Czech Republic) operated at λ= 254 nm, and a set of
two columns PLgel 10E3 and 50 Å, 10 μm particle size, 300 mm × 7.5
mm (Polymer Laboratories, UK) was used. Chromatographic data
were collected and treated using Clarity software (Data-Apex, Czech
Republic). Tetrahydrofuran and toluene were used as a mobile phase
and a flow marker (retention time of toluene was 17.72 min) at a flow
rate of 1 mL/min, respectively. Polystyrene standards with weight-
average molecular weights (Mw) of 500, 1000, 3000, and 10 000 were
used for calibration.
FTIR spectra were measured using the attenuated total reflectance
(ATR) technique on a Spectrum 100T FTIR spectrometer
(PerkinElmer, USA) with a DTSG detector fitted with a Universal
ATR accessory with a diamond/ZnSe crystal. All spectra were
recorded in the range 650−4000 cm−1 at 16 scans per spectrum at
4 cm−1 resolution.
The viscosity of recycled polyols was measured using a Bohlin
Gemini HR nano- rheometer (Malvern Instruments) with cone/plate
geometry (40 mm diameter, 4°angle, 0.15 mm gap) at a temperature
of 25 °C in the range of shear rates 0.001−100 s−1.
The hydroxyl number and acid number of recycled polyols were
determined according to ISO 2554:1974 and ASTM D 4662-93,
respectively, using a titrator SCHOTT TITRONIC universal
(SCHOTT-GERÄ TE GmbH).
The water content in recycled polyols was determined using the
Karl Fischer titration method according to ISO 760.
Number-average functionality of recycled polyols ( f n, OH) was
calculated from the determined hydroxyl number (OH) and number-
average molar mass (Mn) using the following eq (eq 1):
fn,OH = OH·M n /56100 (1)
Mn was determined from SEC calibrated on polystyrene standards.
Foam Formulation. Rigid polyurethane foams were prepared
using a commercial virgin polyol Rokopol 551 (oxypropylenated
sorbitol, PCC Rokita, Poland), which was partially replaced by the
recycled polyols (RPUP or RPCP). Polymeric diphenylmethane-4,4′-
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ACS Sustainable Chemistry & Engineering Research Article

Table 1. Optimized Rigid PUR Foam Formulations (Parts by Weight)

component 0% 10% RPUP 10% RPCP 30% RPUP 30% RPCP 50% RPUP 50% RPCP
virgin polyol 100 90 90 70 70 50 50
RPUP 10 30 50
RPCP 10 30 50
water 1 1 1 1 1 1 1
catalyst 1.5 1.15 1.15 0.8 0.8 0.45 0.45
surfactant 1.5 1.5 1.5 1.5 1.5 1.5 1.5
n-pentane 12 12 12 12 12 12 12
PMDI 130 127 126 123 118 118 110

Scheme 1. Reaction of TCCO with PUR and PC Wastes

diisocyanate (PMDI, Ekopur B) with 31% content of NCO groups
was kindly provided by Minova Ekochem, Poland. The NCO index of
110 was applied in the case of all prepared foams. N,N,N′,N″,N″-
Pentamethyldiethylenetriamine (Polycat 9, Air Products) as the
catalyst and Niax Silicone L-6900 (Momentive Performance Materials)
as the silicone surfactant were used.
Typically, all components (except PMDI) were well homogenized
in a 0.5 dm3 plastic cup and then PMDI was quickly added and mixed
for 10 s at 2000 rpm. The first series of water-blown rigid PUR foams
were prepared in 0.5 dm3 cups in order to optimize the content of
catalyst. The next series of rigid PUR foams using the optimized
formulations with n-pentane (Lach-Ner, Czech Republic) as the
physical blowing agent were prepared in 5 dm3 open mold. The
optimized rigid PUR foam formulations are given in Table 1. All foams
were conditioned for 24 h at room temperature.
Foaming Parameters. During the PUR foam preparation, the
following parameters were observed and characterized: cream time, the
time when the polyol and isocyanate mixture begins to change from
the liquid state to a creamy and starts expansion subsequently; gel
time, the time the foam start to stiffen; free rise time, the time at which
a freely rising foam stopped expanding; and tack-free time, when the
surface of foam stopped being sticky.
Additionally, the foaming process was analyzed using a FOAMAT
device (Messtechnik, Germany) that allows the determination of
characteristic parameters, such as foam rise height, reaction temper-
ature, and dielectric polarization during foaming.
Scanning electron microscope (SEM) Vega Plus TS 5135 (Tescan,
Czech Republic) was used for observing the morphology of PUR
foams. The micrographs were done using a secondary electron imaging
(SEM/SE) at 30 kV. The samples were broken in liquid nitrogen. The
samples were fixed on a metallic support with carbon adhesive tape
and sputtered with Pt (vacuum sputter coater, SCD 050, Balzers,
Lichtenstein).
A compression test was performed according to ISO 844. The
specimens (50 mm-side cubes) were cut from blocks of PUR foam.
The tests were performed at room temperature in parallel or
perpendicularly to foam rise at the speed of 5 mm·min−1 using an
Instron 6025/5800R tester (Instron, UK). The compressive stress at
10% deformation or the compressive strength reached at lower
deformations was evaluated.
Dynamic mechanical and thermal analysis (DMTA) was conducted
on an ARES-G2 rheometer (TA Instruments, USA). The temperature
dependence of the complex shear modulus of rectangular samples
(dimension: 20 × 10 × 3 mm3) was measured by oscillatory shear
deformation in the temperature range of 25−250 °C at a temperature
ramp rate of 3 °C·min−1 with 0.2% strain and 1 Hz frequency. The
temperature of main (alfa) transition (Tα) was evaluated as the
maximum of tan δ peak. The typical precision of the measurements
was Tα ± 2 °C.
Thermogravimetric analysis (TGA) was performed on a Pyris 1
TGA thermogravimetric analyzer (PerkinElmer, USA). The samples
were heated at a rate of 10 °C·min−1 from 30 to 800 °C under
nitrogen atmosphere.

Foam Properties. Free rise (apparent) density was determined
according to ISO 845. Closed cells content (%) was determined
according to ISO 4590.
The thermal conductivity factors were determined using a Laser
Comp heat flow instrument Fox 200. The measurements were made at
an average temperature of 10 °C (temperature of the cold plate was 0
°C and that of the warm plate was 20 °C).
Water absorption was measured according to ISO 2896.
Dimensional stability was measured according to ISO 2796 in dry
conditions at 70 °C. The samples were measured to an accuracy of
0.01 mm as it is shown in Figure S1.
6239
■
RESULTS AND DISCUSSION
Characteristics of Prepared Recycled Polyols. The
decomposition of PUR and PC wastes took place according to
Scheme 1. The PUR waste of the semirigid foam used in car
interiors was based on aromatic isocyanate (PMDI) and
polyether polyol(s). The PC waste of car headlights was BPA-
based PC containing siloxane top coating (0.2 wt %), which
was removed from the recycled PC polyol by filtration.
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SEC records of both recycled polyols (not shown here)
displayed no presence of high molecular weight oligomers
giving thus evidence of completeness of polymer degradation.
The physical-chemical properties of the recycled polyols are
summarized in Table 2.
Table 2. Properties of RPUP and RPCP Recycled Polyols
Prepared from PUR and PC Waste, Respectively
name RPUP RPCP
hydroxyl number [mgKOH·g−1] 333 270
viscosity at 25 °C [mPa·s] 9500 3500
water content [wt %] 0.1 0.01
acid number [mgKOH·g−1] 1.1 1.2
Mw [g·mol−1] 1322 438
Mw/Mn 2.22 1.16
f n, OH 3.5 1.8
renewable/recycled content [wt %] 52/48 50/50
The higher TCCO/polymer weight ratio used for the
preparation of RPUP resulted in its slightly higher hydroxyl
number compared to the respective value of RPCP. The
different viscosities of both recycled polyols were primary
connected to their different molecular weights. The average
molecular weight (Mw) of the more viscous RPUP was 3 times
higher than the Mw of RPCP (Table 2). Moreover, the broad
molecular weight distribution (the high Mw/Mn ratio) of RPUP
originated from the presence of a large variety of branched and
linear compounds with rigid aromatic as well as flexible
aliphatic segments. During the decomposition of chemically
cross-linked PUR waste by means of TCCO, an original
(aliphatic) polyol with a functionality of ≥3 (an unknown
structure, here expressed as HO−R1(OH)−OH, see Scheme 1)
and a mixture of aromatic (carbamate) polyols and amines were
formed. The FTIR spectrum of RPUP (Figure S2) confirmed
the presence of NH and OH groups, carbamate, and ester
linkages as well as aromatic structures and aliphatic chains. The
resulting RPUP was thus composed of various compounds
differing in chemical structure (aliphatic vs aromatic), func-
tional group (aliphatic OH and aromatic NH2), functionality,
and supramolecular structure (branched vs linear). Therefore,
RPUP had broad molecular weight distribution and its
determined average number functionality ( f n, OH = 3.5) was
quite high (Table 2).
Contrary to that, the linear PC was predominantly converted
by the reaction with TCCO into diols (BPA and BPA end-
capped with one monoglyceride unit through carbonate bond),
triols (BPA end-capped with one glycerol unit through
Figure 1. Effect of (a) RPUP and (b) RPCP addition on PUR foaming parameters.
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carbonate group or BPA end-capped with one monoglyceride
and one glycerol units through carbonate groups) considering
monoglycerides and glycerol as the main components of
TCCO.26 FTIR spectrum of RPCP (Figure S2) revealed the
presence of aromatic and aliphatic structures, phenolic and
alcoholic OH groups as well as glyceride and carbonate
linkages. The detailed analysis of RPCP components was
previously performed26 and therefore is not mentioned in this
paper. The determined average number functionality of RPCP
( f n, OH = 1.8, Table 2) was lowered due to the presence of OH-
monofunctional (e.g., BPA end-capped with one diglyceride
unit through carbonate group) and OH-free (e.g., BPA end-
capped with two diglyceride units through carbonate groups)
compounds in RPCP. The low functionality together with the
presence of mostly linear aromatic structures caused the
narrower molecular weight distribution of RPCP as well as its
lower average molecular weight and viscosity compared to
RPUP (Table 2).
Renewable and recycled contents in RPUP and RPCP were
calculated (Table 2). Both polyols were composed uniquely of
the renewable (derived from TCCO) and the recycled
(originated from PUR or PC wastes) raw materials with
approximately equal proportion.
Foaming Parameters of Rigid Polyurethane Foams.
Rigid PUR foams were produced under the reaction of a polyol
with a slight excess of PMDI (molar NCO/OH ratio of 1.10) in
the presence of several additives (catalyst, blowing agent,
stabilizer, and surfactant). The amount of PMDI was varied for
each PUR foam formulation as a function of polyol hydroxyl
number, keeping the NCO/OH ratio constant.
The first series of PUR foams were prepared with the
constant amount of catalyst (Polycat 9) and different content of
the recycled polyols (RPUP and RPCP) using only water as a
chemical blowing agent (Figure 1).
The additions of both recycled polyols significantly
accelerated the foaming process. Cream time was only slightly
influenced by the content of recycled polyols. Gel, rise, and
tack-free times became apparently shorter with the increasing
content of RPUP (Figure 1a) due the presence of aromatic
amines, which accelerated foaming process.11,19,27
The accelerated foaming was also observed for the
formulations with RPCP (Figure 1b) due to the presence of
low molecular weight components (BPA and free glycerol),
which enhanced the reaction with isocyanates.28−30 Moreover,
both recycled polyols contained traces of DBTL catalyst
coming from the synthesis of TCCO,26 which might also
accelerate the PUR foaming process.
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Figure 2. Temperature and dielectric polarization changes of PUR systems modified with (a,c) RPUP and (b,d) RPCP during the foaming process.

Figure 3. Microphotographs of cell structure of the prepared rigid PUR foams containing no recycled polyol (a, e), 50 wt % of RPUP (b, f), 50 wt %
of RPCP (c, g), and 75 wt % of RPCP (d, h); in parallel (a−d) and perpendicularly (e−h) to foam rise directions.

Table 3. Average Cell Diameter (d), Apparent Density (ρ), Closed Cell Content, Water Absorption, and Thermal Conductivity
(λ coefficient) of Rigid PUR Foams Containing Various Amounts of RPUP and RPCP Recycled Polyols
recycled polyol content [wt %] da [μm] db [μm] ρ [kg·m−3] closed cell content [vol %] water absorption [vol %] λ coefficient [mW·m−1·K−1]
0 430 ± 118 387 ± 85 41.1 ± 1.3 88.8 ± 1.2 0.43 ± 0.01 24.3 ± 0.2
RPUP:
10 322 ± 102 269 ± 77 41.5 ± 1.5 90.1 ± 0.1 0.43 ± 0.00 23.6 ± 0.1
30 254 ± 84 258 ± 71 41.8 ± 0.4 91.6 ± 1.1 0.34 ± 0.01 23.3 ± 0.1
50 222 ± 59 243 ± 62 42.4 ± 1.1 91.3 ± 1.0 0.35 ± 0.02 23.4 ± 0.3
RPCP:
10 347 ± 100 329 ± 60 39.8 ± 0.9 89.9 ± 0.6 0.40 ± 0.03 23.9 ± 0.2
30 387 ± 109 280 ± 65 42.5 ± 0.7 91.1 ± 0.4 0.34 ± 0.01 23.0 ± 0.2
50 216 ± 61 260 ± 80 43.9 ± 2.0 90.6 ± 0.5 0.35 ± 0.01 22.8 ± 0.1
75 261 ± 127 73 ± 23 48.0 ± 1.6 n.d. n.d. n.d.
a
In parallel to foam rise direction. bPerpendicularly to foam rise direction, n.d. = not determined.

Consequently, the PUR formulations had to be optimized by
decreasing the content of catalyst (Table 1). The foaming
parameters of optimized PUR formulations containing various
amounts of the RPUP and RPCP and n-pentane as a physical
co-blowing agent were investigated using the foam qualification
6241
system FOAMAT. The effect of type and amount of recycled
polyols in the PUR formulations on temperature and dielectric
polarization during foaming are shown in Figure 2.
The increase of both recycled polyols content caused a
decrease of reaction mixture temperature (Figure 2a,b). The
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Figure 4. Compressive strength (normalized to the density of 40 kg·m−3) of rigid PUR foams containing (a) RPUP and (b) RPCP.
higher content of recycled polyols (30 and 50 wt %) caused a
fast temperature increase in the beginning of foaming (up to ca.
100 s) indicating the larger reaction heat release and the higher
extent of isocyanate−polyol reaction. The temperature profiles
corresponded well to the dielectric polarization evolution,
which reflected the progress in chemical reactions between OH
and NCO groups.31 The PUR cross-linking reaction ultimately
suppressed all dipole mobility during foaming.32 The decrease
of dielectric polarization thus reflected the PUR cross-linking
reaction progress. The faster decrease of dielectric polarization
was observed at the highest content of recycled polyols (50 wt
% replacement of petrochemical polyol) indicating the faster
foaming kinetics (Figure 2c,d). However, the incorporation of
both recycled polyols did not bring any important changes of
PUR system reactivity. From this point of view, all PUR
formulations were successfully optimized by decreasing of the
catalyst content.
Structure of Rigid Polyurethane Foams. The PUR
formulations were adjusted by the amount of the chemical
(water) and physical (n-pentane) blowing agents in order to
receive the rigid PUR foams with unified apparent density of ca.
40 kg·m−3, as common for PUR thermal insulation materials in
building industry.33 SEM images of the prepared rigid PUR
foams displayed homogeneous cell structure even at high
loadings (50 wt %) of both recycled polyols (Figure 3).
The average cell diameter decreased with increasing levels
(up to 50 wt %) of recycled polyols (Table 3). The cell size
decrease might indicate good recycled polyol compatibility with
blowing agents and (analogous to surfactant addition) the
recycled polyol addition decreased surface tension in the polyol
blend.34 The faster foaming and gelling due to recycled polyol
addition (see Figure 3) might also yield PUR foams with
smaller cell size.35 Visible anisotropy of cellular structure was
only observed when 75 wt % of RPCP was applied. The same
replacement of virgin polyol by RPUP led to cell-opening
during foaming, which resulted in collapse of cellular structure.
RPUP might be thus added into low-density rigid PUR foam
system in lower amount compared to RPCP.
However, the highest replacement of virgin polyol by RPCP
(75 wt %) produced the rigid PUR foam with the higher
apparent density (48 kg·m−3) than was desired. From this point
of view, the addition of both recycled polyols was limited to 50
wt % in order to prepare the rigid PUR foams with sufficient
low apparent density in the range of 39.8−43.9 kg·m−3 (Table
3). In literature, only few studies reported a successful
preparation of low density rigid PUR foams with a high
content of recycled polyols. Nikje et al. successfully prepared
rigid PUR foams with densities around 40 kg·m−3 only when
the content of recycled polyols from PUR glycolysis below 30
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wt % was applied.16 Generally, the higher contents (≥50 wt %)
of recycled polyols from PUR waste caused the substantial
increase in density of rigid PUR foams.10,19 Contrary to that,
recycled polyols prepared from polyethylene terephthalate
(PET) waste, the linear and aromatic structure of which is
similar to PC, might be applied in rigid PUR foams at higher
amounts. For example Ghaderian et al. used uniquely recycled
polyols from PET glycolysis for preparation of PUR foams with
a density of 22−41 kg·m−3 and cell diameters of 300−480
μm;36 giving slightly larger cells than in our case. Kacperski et
al. prepared PUR foams with similar densities (26−35 kg·m−3)
but with a much lower amount of the recycled product applied
(10−30 wt %).37 Paberza et al. described the synthesis of
combined bio/recycled polyol from rapeseed oil and glycolyzed
PET, which enabled its application at high loadings (up to 75
wt % virgin polyol replacement) in low-density (40−45 kg·
m−3) rigid PUR foams without unfavorable density increase.33
Thermal Conductivity of Rigid Polyurethane Foams.
The influence of recycled polyol addition on thermal
conductivity (λ) of the prepared PUR foams is seen from
Table 3. The same trend is evident for both types of recycled
polyols; λ was decreased (i.e., heat insulating properties of PUR
foams were improved) with the increasing recycled polyols’
contents. Generally, the thermal conductivity of plastic foams
depends on thermal conductivities of the polymer (solid)
phase, gas trapped in cells plus convective and radiative
components.38 In this study, all prepared materials were low-
density PUR foams, in which the solid polymer phase
represented a negligible fraction and therefore its contribution
to overall foam thermal conductivity might be omitted. The
thermal conductivity of the gas phase was assumed to be the
same for all prepared PUR foams, since the same blowing
agents (combination of carbon dioxide and n-pentane) were
always used. Then, the overall thermal conductivity perform-
ance of rigid PUR foam had to be influenced by the cell size
and the fraction of closed cells.34 The mean cell diameters in
parallel and perpendicular to foam rise determined from the
SEM images are given in Table 3. The results showed that the
progressive addition of recycled polyols decreased the cell size
and narrowed the cell diameter distribution up to a recycled
content of 50 wt %. Only the rigid PUR foam containing 75 wt
% of RPCP exhibited significant cell anisotropy (see SEM
image in Figure 3d). All the other prepared PUR foams
exhibited very fine and homogeneous cellular structure with
isotropic cells. It is well-known that a large number of small
cells resist gas exchange better than a small number of large
cells (the contribution of λ radiative component is reduced),38
which is in agreement with our thermal conductivity results
(Table 3). Moreover, the addition of the recycled polyols’
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ACS Sustainable Chemistry & Engineering Research Article

Figure 5. Thermo-mechanical properties of rigid PUR foams containing (a) RPUP and (b) RPCP; storage modulus (G′) and loss factor (tan δ)
curves.

Table 4. Results of DMTA (Tα, G′G ), TGA (T5%, char yield at 800°C) and Dimensional Stability of Rigid PUR Foams with
Various Amounts of RPCP and RPUP
dimensional stability [%]
recycled polyol content [wt %] Tαa [°C] GG′ [MPa]
b
T5%c [°C] char yield at 800 °C[wt %] l b δ
0 161 2.9 288 14.8 0.09 ± 0.00 0.13 ± 0.05 0.40 ± 0.09
RPUP:
10 158 3.2 273 15.5 0.19 ± 0.02 0.12 ± 0.01 0.40 ± 0.04
30 159 4.2 275 17.6 0.06 ± 0.01 0.14 ± 0.09 0.43 ± 0.03
50 142 4.4 264 17.9 0.15 ± 0.04 0.22 ± 0.03 0.24 ± 0.04
RPCP:
10 156 3.0 285 16.8 0.05 ± 0.03 0.06 ± 0.01 0.31 ± 0.05
30 145 4.1 236 18.5 0.05 ± 0.02 0.07 ± 0.02 0.34 ± 0.01
50 138 5.1 235 22.1 0.04 ± 0.03 0.11 ± 0.04 0.31 ± 0.07
75 n.d. n.d. 231 15.1 n.d. n.d. n.d.
a
Maximum of tan δ peak. bStorage shear modulus at glassy state at 50 °C. cTemperature of 5% weight loss.

slightly increased the content of closed cells (∼91 vol %),
which beneficially decreased both the thermal conductivity
(∼23 mW·m−1·K−1) and the water absorption (∼0.34 vol %) of
PUR foams (Table 3). The negligible water absorption of PUR
foams based on the recycled polyols was also connected to a
hydrophobic character of RPUP and RPCP. Both recycled
polyols were composed of the aromatic and the CCO
glycerides’ structures exhibiting thus “water-repellent” charac-
ter.
Mechanical Properties of Rigid Polyurethane Foams.
It is well-known that the mechanical properties of rigid PUR
foams are closely related to the foam density.38 Therefore, the
measured values of compressive strength in parallel and
perpendicular to foam rise directions at 10% compression
were normalized to apparent density of 40 kg·m−3 according to
(eq 2):39,40
σnorm = σexp(40/ρ)2.1
(2)
where σnorm is the normalized compressive strength [kPa], σexp
is the measured compressive strength [kPa] and ρ is the
apparent density [kg·m−3] of PUR foam. The calculated values
of normalized compressive strength are plotted in Figure 4. The
compressive strength of rigid PUR foams, both parallel and
perpendicular to the directions of foam rise, increased with the
increasing content of both types of recycled polyols in the
range of 0−50 wt % virgin polyol replacement. The
compressive strength parallel and perpendicular to the
directions of foam rise for the sample with 50 wt % of RPUP
content was 28% and 16% higher, respectively, than in the case
6243
of reference PUR foam without recycled polyols. The best
mechanical properties had the PUR foam with 50 wt % of
RPCP, which exhibited the compressive strength values parallel
and perpendicular to foam rise directions, 38% and 29% higher,
respectively, compared to the reference foam. The further
increase of RPCP content (75 wt %) in the rigid PUR foam
caused a slight increase (+10%) and decrease (−15%) in foam
compressive strengths parallel and perpendicular to foam rise
directions, respectively, compared to the reference foam, which
originated from foam structural anisotropy attributed to cell
elongation in the direction of foam rise (Figure 3d).
It is worth mentioning that the compressive strength above
350 kPa (in parallel to foam rise direction) of the rigid PUR
foams with 50 wt % of RPCP was exceptionally high with
respect to the low value (40 kg·m−3) of foam apparent density.
These anomalous increased mechanical properties of PUR
foams probably originated from the high content of aromatic
segments in the RPCP providing stiffness of PUR structure and
from the optimal hard block segregation enabling physical
bonding and thus compensating the lower cross-linking density,
that is an effect of the low functionality of RPCP.30,41
Moreover, the aromatic segments in PUR foam were
interconnected via the flexible glyceride chains of TCCO
avoiding excessive rigidity and brittleness of a PUR network.
Low-density foams with similar mechanical properties and
containing such a high amount of recycled polyols have not
been described yet in the literature. Ivdre et al. prepared the
rigid PUR foam based on the recycled polyol from PET waste
with an apparent density of 45 kg·m−3 and a maximal
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ACS Sustainable Chem. Eng. 2017, 5, 6237−6246
ACS Sustainable Chemistry & Engineering
compressive strength of 310 kPa.42 Prociak et al. prepared the
rigid PUR foam with 40 wt % of the recycled PUR polyol,
which exhibited an apparent density of 38 kg·m−3 and a
compressive strength of 220 kPa.15
Thermomechanical Properties of Rigid Polyurethane
Foams. Figure 5 shows the DMTA results (storage modulus,
G′ and tan δ) of the prepared rigid PUR foams. The different
content of recycled polyols influenced both G′ and Tα values of
rigid PUR foams. The G′ values in the glassy region (GG′ in
Table 4) slightly increased at the higher recycled polyols’
contents (30 and 50 wt %) contrary to the rubbery region
above Tα where the G′ values slightly decreased with the
increasing recycled polyols’ amounts (Figure 5). This behavior
indicated that the addition of recycled polyol promoted
physical bonding (probably via π−π interactions of aromatic
rings and H-bonding of urethane and urea structures) and hard
segment formation (similar to thermoplastic PUR elastomers)
in the PUR cross-linked structure. The highest G′G value
exhibited the PUR foam with 50 wt % of RPCP, which
corresponded well to its highest aromatic content. The physical
cross-linking disappeared as segmental mobility of PUR chains
was released at the main transition temperature region. The Tα
shift of rigid PUR foams (Table 4) depended on the mobility of
chain segments driven by both the cross-linking density and the
weight fraction of aromatic structures in PUR foams.
As expected, the reference PUR foam (without recycled
polyol) exhibited the highest cross-link density and therefore
the highest Tα. However, the PUR foams with 10 and 30 wt %
of RPUP exhibited only a small shift in Tα to lower temperature
(Figure 5a and Table 4). The more significant Tα decrease was
observed in the case of PUR foam with the highest (50 wt %)
content of RPUP. In this case, the broad molecular weight
distribution of RPUP led to the formation of a heterogeneous
PUR network containing highly cross-linked (hard) and more
linear less-cross-linked (soft) segments as evidenced from the
substantial broadening of the tan δ peak (Figure 5a.)44
In contrast, the increasing RPCP content led to the gradual
Tα decrease of rigid PUR foams (Figure 5b and Table 4). The
low average functionality of RPCP (see Table 2) significantly
reduced the degree of chemical cross-linking of rigid PUR
foams. Thus, a less chemically cross-linked structure provided
more free volume for network chain segment relaxation,
shifting Tα of the rigid PUR foams to lower temperatures.
The excellent thermo-mechanical properties of PUR foams
modified with RPCP and RPUP were confirmed by their very
good dimensional stability at 70 °C (Table 4). The extent of
dimensional changes after the test was lower than 1% for all
tested PUR foams.
Thermal Degradation of Rigid Polyurethane Foams.
The thermal stability of the prepared rigid PUR foams was
evaluated using TGA under nitrogen atmosphere (Figure S3
and Table 4). The reference PUR foam degraded in one broad
weight loss in the temperature range of 220−600 °C (with the
maximum DTG peak at 360 °C).
The series of PUR foams based on RPUP exhibited no mass
loss below 220 °C analogous to the reference PUR foam
(Figure S3a). The PUR foam with 10 wt % of RPUP exhibited
the same TGA curve as the reference PUR foam. The DTG
curves of PUR foams with 30 and 50 wt % of RPUP displayed
two shoulders on the DTG peak at low (220−320 °C) and high
(410−600 °C) temperature regions. The first shoulder slightly
shifting the beginning of thermal degradation (expressed as the
temperature of 5% weight loss, T5%, in Table 4) to lower
6244
Research Article
temperature as the result of slightly decreased cross-link density
of PUR network43 and the presence of thermally labile dangling
acylester chains;20 the latter shoulder indicated the improved
thermal stability of the PUR foams at higher temperatures
(above ca. 400 °C) due to the higher aromatic content in the
PUR network.44
The RPCP content of 10 wt % did not influence the thermal
behavior of rigid PUR foam (Figure S3b). The higher contents
(30−75 wt %) of RPCP decreased significantly the initial mass
loss of rigid PUR foam to lower temperatures (to ca. 150 °C).
This first mass loss shift to lower temperature was attributed to
more diluted PUR networks containing thermally less stable
urethane groups.20,34 The novel DTG peak (at 292 °C) was
formed in the case of PUR foam with the highest RPCP
content (75 wt %).
The increased char formation during TGA of PUR foams
based on recycled polyols was due to the increased content of
aromatic structures originating from RPUP and RPCP33,36
confirming the highest aromatic content in the PUR foam with
50 wt % of RPCP.
Structure of Rigid Polyurethane Foams Based on
Recycled Polyols. The two recycled polyols exhibited several
differences. RPUP had a much higher functionality, the broader
molecular weight distribution and contained beside OH groups
also more reactive NH2 groups. Contrary to that, RPCP had a
higher aromatic content, lower molecular weight, and much
narrower molecular weight distribution. Surprisingly, these
differences in recycled polyol structure did not have a
significant effect on foaming (only the slightly higher reactivity
of RPUP compared to RPCP was adjusted lowering the catalyst
amount) and the properties of rigid PUR. The PUR foams with
50 wt % of RPCP exhibited the best mechanical properties at
room temperature, producing a more diluted PUR network
compared to that with RPUP.
On the other hand, both recycled polyols had similar features
which played a crucial role in formation of the structure of the
PUR foam and had an impact on foam properties. The
structure of both recycled polyols (RPUP and RPCP)
combined the rigid aromatic segments (derived from PUR/
PC segments) and the flexible pendant chains derived from
CCO glycerides. The former reinforced the cross-linked
structure of PUR via π−π interactions of aromatic rings and
H-bonding of urethanes and disubstituted ureas, whereas the
latter avoided brittleness of the PUR network creating flexible
glyceride covalent connections between the aromatic units. The
final network of PUR foams at the glassy state (i.e., at
temperatures below Tα) is thus composed of physical and
covalent cross-links providing excellent stiffness as well as
toughness.
On the basis of the above-mentioned findings, the idealized
structure of rigid PUR foam based on the recycled polyol is
proposed (Scheme 2). The schematic structure is derived from
RPCP but we suppose similar structure features for the RPUP-
based PUR foam. The shown foam structure contains the hard
aromatic segments derived from PMDI and BPA, bonded
through urethane (U) or disubstituted urea (UA) groups, and
the flexible glyceride chains derived from CCO. The presence
of diglycerides leads to creation of pendant chains.
■
CONCLUSIONS
Polyurethane (PUR) and polycarbonate (PC) scraps from end-
of-life vehicles were converted into two types of recycled
polyols, RPUP and RPCP, respectively, using medium chain
DOI: 10.1021/acssuschemeng.7b01197
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ACS Sustainable Chemistry & Engineering
Scheme 2. Schematic Structure of Rigid Polyurethane Foam
Containing Recycled Polyol from Polycarbonate Waste
glycerides of coconut oil under microwave irradiation. Thus,
prepared polyols, composed uniquely of renewable and
recycled components, were characterized in detail, having a
hydroxyl number of ca. 300 mg KOH·g−1, which made them
suitable for rigid PUR foam applications. Despite the higher
recycled polyols reactivity, the PUR formulations were
successfully optimized by the decreasing catalyst content.
Then the replacement of a virgin petrochemical polyol up to 50
wt % by the recycled polyols did not bring any important
changes the reactivity of the PUR system, which enabled
preparation of low-density PUR foams with apparent density of
40−44 kg·m−3. The prepared PUR foams exhibited with the
increasing recycled polyols’ contents (up to 50 wt %) a finer
homogeneous cellular structure, a higher content of closed cells
(>91 vol %), and beneficially a lower lambda coefficient (∼23
mW·m−1·K−1) and water absorption (∼0.35 vol %) compared
to the reference PUR foam without recycled polyol. Moreover,
the PUR foams with high content of recycled polyols (50 wt %)
exhibited the best mechanical properties; the compressive
strength above 350 kPa (in parallel to foam rise direction) of
the rigid PUR foams with 50 wt % of RPCP was exceptionally
high with respect to the low value (40 kg·m−3) of foam
apparent density. The unique mechanical properties of PUR
foams with high recycled polyols’ contents probably originated
from the presence of rigid aromatic segments (from PUR and
PC) and flexible connections derived from coconut oil
glycerides, which shifted the main (glass) transition of PUR
foams to lower temperatures. However, all the prepared PUR
foams were thermally stable up to 220 °C. In conclusion, both
recycled polyols can be applied up to 50 wt % virgin polyol
replacement in low-density rigid PUR foams with potential
application as a thermal insulating material in the building
industry.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acssusche-
meng.7b01197.
6245
Research Article
Method of foam size measurements during dimensional
stability test, FTIR spectra of TCCO, RPUP, and RPCP,
and TGA curves of the prepared rigid PUR foams (PDF)
■ AUTHOR INFORMATION
Corresponding Authors
*Phone: +420 296 809 313. Fax: +420 296 809 410. E-mail:
benesh@imc.cas.cz.
*Phone: +48 12 628 30 16. Fax: +48 12 628 29 47. E-mail:
aprociak@pk.edu.pl.
ORCID
Hynek Beneš: 0000-0002-6861-1997
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This work was supported by Ministry of Education, Youth and
Sports and Ministry of Science and Higher Education in the
frame of Polish-Czech bilateral project (ID/CZ 7AMB14PL021
and ID/PL 9023/R14/R15) and by Ministry of Education,
Youth and Sports, National Sustainability Program INPU I,
Project POLYMAT LO1507.
■
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