Received: 7 December 2020 Revised: 19 February 2021 Accepted: 20 February 2021

DOI: 10.1002/app.50690

ARTICLE

Biobased flexible polyurethane foams manufactured from

lactide-based polyester-ether polyols for automotive
applications

Sayli Devdas Bote1 | Alper Kiziltas2 | Ian Scheper1 |

Deborah Mielewski2 | Ramani Narayan1

1
Department of Chemical Engineering
and Materials Science, Michigan State
University, East Lansing, Michigan, USA
2
Materials Research and Advanced
Engineering, Ford Motor Company,
Dearborn, Michigan, USA
Correspondence
Alper Kiziltas, Materials Research and
Advanced Engineering, Ford Motor
Company, 2101 Village Road, Dearborn,
MI 48124, USA.
Email: akizilt1@ford.com
Ramani Narayan, Department of
Chemical Engineering and Materials
Science, Michigan State University, East
Lansing, MI 48824, USA.
Email: narayan@msu.edu
Funding information
Ford Motor Company
Abstract
In this study, biobased polyester-ether polyols derived from meso-lactide and
dimer acids were evaluated for flexible polyurethane foams (PUF) applications.
Initially, the catalyst concentration was optimized for the biobased PUF con-
taining 30% of biobased polyol (70% petroleum-based polyol). Then, the same
formulation was used for biobased PUF synthesis containing 10%–40% of bio-
based polyols. The performance of biobased PUF was compared with the perfor-
mance of the control foam made with 100% petroleum-based polyol. The
characteristic times (cream, top of the cup, string gel, rise, tack-free) of biobased
PUF were determined. The biobased PUF were evaluated for the mechanical
(tensile and compressive) and morphological properties. As the wet compression
set is important for automotive applications, it was measured for all biobased
PUF. The thermal degradation behavior of biobased PUF was also evaluated
and compared with the control foam. The effect of different hydroxyl and acid
values of polyols on the mechanical properties of biobased PUF is also dis-
cussed. The miscibility of all components of PUF formulations is crucial in order
to produce a foam with uniform properties. Thus, the miscibility of biobased
polyols with commercial petroleum-based polyol was studied.

KEYWORDS
biopolymers and renewable polymers, foams, manufacturing, polyurethane, structure-property
relationships

1 | INTRODUCTION are used as packaging materials, cushioning materials

Polyurethanes are used in a variety of applications includ-
ing coatings, adhesive, sealants, elastomers, and foams.
Polyurethane foams (PUF) are a primary application and
form a major market for polyurethanes.1 PUF are classified
as either rigid or flexible foams. The rigid PUF are widely
used in insulating materials (refrigerator, panels for wall
and roof), automotive components (door panel, interior
body), and construction materials. Whereas flexible PUF
(bedding and furniture in a home, car seats, headliner, and
under-the-hood applications in automotive), and insulat-
ing materials. This versatility of PUF is due to their excel-
lent strength to weight ratio and insulation properties
(thermal, electrical, acoustic).2 The polyurethane foam
market is valued at USD 38 billion in 2020 and is expected
to reach USD 54 billion by 2025.3 Polyurethanes are made
from two major components, that is, polyols and isocya-
nates. The conventional petroleum-based polyols are

J Appl Polym Sci. 2021;138:e50690. wileyonlinelibrary.com/journal/app © 2021 Wiley Periodicals LLC. 1 of 15

https://doi.org/10.1002/app.50690
2 of 15
synthesized from ring opening polymerization of propyl-
ene oxide or ethylene oxide on an initiator like glycerol.
Voranol polyol series from The Dow Chemical Company
and Pluracol polyol series from BASF are synthesized
using similar pathway. Over the past decade, biobased
polyols have started replacing some of the petroleum-based
polyols market. In 2005, Biobased Technologies® LLC
introduced AGROL® polyols synthesized from epoxidation
of soybean oil followed by ring-opening of the epoxide
groups. Other companies such as Cargill,4,5 BASF,6
Huntsman,7 and Oleon8 and so forth, also commercialized
biobased polyols from epoxidation of soybean oil.8 Polyols
synthesized from epoxidation route contain secondary
hydroxyl groups. Several other routes such as
hydroformylation, ozonolysis, and transesterification were
also used for polyol synthesis from soybean oil.8,9 Apart
from soybean oil, other triglycerides such as castor oil,9
palm oil,10,11 rapeseed oil,12 sunflower oil,13 and linseed
oil13 were also used for the synthesis of biobased polyols.
The development of biobased PUF containing biobased
polyols is challenging as it involves two competing reac-
tions, that is, gelling and blowing reactions. The gelling
reaction involves reaction of polyol with isocyanate for-
ming urethane linkages, whereas blowing reaction involves
reaction of isocyanate with water forming carbon dioxide
gas. During the foam synthesis, a stable polyurethane net-
work (gelling) must build rapidly before the entrapped gas
(blowing) in cells leaves the cellular structure. However, if
polyurethane network (gelling) builds too fast, then it
might prevent the cell growth.14 If the gelling reaction is
faster than the blowing reaction, then it could produce a
foam with closed cells leading to foam shrinkage.14 The
foam will collapse, if the blowing reaction is faster than the
gelling reaction. Thus, obtaining a balance of gelling and
blowing reactions in all biobased foam formulations is crit-
ical to produce a stable foam with desired properties.
Currently, the biobased PUF are used only in certain
applications and automotive components, as they may
not meet the minimum performance properties required
for specific applications.15 In the production of biobased
PUF, biobased polyols are used along with petroleum-
based polyols. Most of the biobased polyols are polyester
polyols. Whereas majority of the petroleum-based polyols
are polyether polyols. Incorporation of polyester polyols
into polyether polyols during the synthesis of PUF could
increase the tensile strength of foams.16 However due to
structural or density differences, biobased polyester poly-
ols may not be miscible with petroleum-based polyether
polyols. The immiscibility of different polyols might
result in foams with irregular internal structure and infe-
rior performance properties. Thus, currently existing
commercialized biobased PUF available in the market
contain lower percentage of biobased polyols.
BOTE ET AL.
In our previous work, biobased diols were synthesized
from meso-lactide.17 These diols contain ester and ether
linkages with a hydroxyl value of 200 mg of KOH/g. The
polyols used for flexible PUF have hydroxyl value of
100 mg of KOH/g or less.18 Thus, biobased diols were
reacted with dimer acids (C36, soybean oil-based) using
polycondensation chemistry. The use of different meso-
lactide diols and molar ratios of dimer acid to diol pro-
duced a series of biobased polyester-ether polyols with
varying hydroxyl value from about 35 to about 100 mg of
KOH/g. As these polyols contain ether linkages along
with ester linkages, they are predicted to be more com-
patible with petroleum-based polyether polyols. This will
offer added advantage to our biobased polyols over the
existing commercialized biobased polyols.
The objective of this study is to produce biobased flex-
ible PUF containing higher amounts of biobased
polyester-ether polyols for cushioning applications. PUF
are made by mixing polyols, catalysts, blowing agents,
and isocyanate. The optimum concentration of each of
the components is required to obtain a foam with good
internal structure and desirable mechanical properties.
Thus, initially, the concentration of all components was
optimized for a foam containing 30% of biobased polyol.
Then, biobased PUF containing 10%–40% of biobased
polyols were synthesized based on the optimized formu-
lation. As flexible PUF are used in automotive and cush-
ioning applications, the properties of produced flexible
PUF were tested accordingly. The mechanical properties,
that is, wet compression set, tensile properties, tear
strength, and compressive properties, of biobased PUF
containing 10%–40% of biobased polyol were compared
with mechanical properties of PUF made from commer-
cial biobased and petroleum-based polyols. The effect of
different hydroxyl values on characteristic times and
properties of foams is discussed. The thermal degradation
behavior and morphology of biobased PUF were tested.
Finally, the miscibility of biobased polyols with a
petroleum-based polyol was determined.
2 | EXPERIMENTAL
2.1 | Materials and chemicals
All biobased polyols used in this work, that is,
DAMLPEG-7-94, DAMLPEG-7-47, DAPEG-94, and
DAPEG-38, were synthesized from dimer acid using poly-
condensation chemistry as shown in Figure S1, the
details of which are covered in our previous work.17
DAMLPEG polyols having primary as well as secondary
hydroxyl groups were obtained by reacting dimer acid
with diols derived from meso-lactide (MLPEG-7-202).
BOTE ET AL.
TABLE 1 Physical properties of polyols
Hydroxyl value Acid value
Polyols (mg of KOH/g) (mg of KOH/g) Mwa (g/mol)
Voranol 4701 34 - 4950
Agrol Prime-A-56 56 <2 2000
DAMLPEG-7-94 94 ± 9 1±0 1194
DAMLPEG-7-47 47 ± 4 3±0 2387
DAPEG-94 94 ± 5 2±0 1194
DAPEG-38 38 ± 3 1±0 2952
a
Molecular weight calculated based on functionality.
DAPEG polyols having primary hydroxyl groups were
obtained by reacting dimer acid with polyethylene glycol
(PEG-400). These polyols have functionality of two and
their viscosity changes with the change in the hydroxyl
value. As hydroxyl value of a polyol decreases, its molec-
ular weight and viscosity increases. DAMLPEG-7-94 and
DAPEG-94 polyols have lower viscosity and molecular
weight. Whereas DAMLPEG-7-47 and DAPEG-38 polyols
have higher viscosity and molecular weight. DAMLPEG
polyols are viscous than DAPEG polyols for the same
hydroxyl value. These polyols were synthesized at Michi-
gan State University, East Lansing, MI, and used for the
synthesis of flexible PUF for automotive applications at
the Ford Motor Company, Dearborn, MI. The properties
of the biobased PUF were compared with properties of
PUF synthesized from commercially available petroleum-
based and biobased polyols. The commercial petroleum-
based polyether polyol, that is, Voranol™ 4701, was
supplied by The Dow Chemical Company (Michigan),
and biobased polyol, that is, Agrol Prime™ A-56, was sup-
plied by Biobased Technologies® LLC (Arkansas). Agrol
Prime™ A-56 is a commercial soybean oil-based polyol.
The Cargill Incorporated acquired Biobased Technologies
in 2017 and renamed the polyol as BiOH® 7050. The prop-
erties of all polyols are given in Table 1. Rubinate® 7304 is
a specialized flexible foam grade polyisocyanate and was
kindly provided by Huntsman Corporation (Texas). It is a
mixture of monomeric and polymeric methylene diphenyl
diisocyanate. It has a free isocyanate group (NCO) content
of about 32.6% by weight and number average isocyanate
group functionality of about 2.2.19
A silicone-based surfactant, Tegostab B4690 was sup-
plied by Evonik (Virginia). A cell-opener, Lumulse POE
(26) GLYC was supplied by Lambent Corporation
(Illinois). The Niax-A1 (70% bis[2-dimethylaminoethyl]
ether, C8H20N2O and 30% dipropylene glycol, C6H14O3)
and Niax A300 were received from Momentive Perfor-
mance Materials (New York). A crosslinking agent,
diethanolamine was purchased from Sigma-Aldrich
(Wisconsin).
3 of 15
Viscosity @ Renewable carbon
Functionality 25 C (cPs) content (%)
3 888 -
2 5090 75
~2 2980 57
~2 5850 70
~2 1022 50
~2 7130 67
2.2 | Free rise study of PUF
The free rise study of all biobased PUF containing 0%–
40% of biobased polyols was performed as per ASTM
standard D7487-13. The formulations used for the free
rise study are given in Table 2. The PUF formulation with
0% biobased polyol is a control PUF. It was made with
100% of Voranol 4701 polyol, which is the commercial
petroleum-based polyether polyol. The side B (60 g) con-
taining polyols, crosslinking catalyst (diethanolamine),
silicone surfactant (Tegostab B4690), blowing catalyst
(Niax A-1 and Niax A300), cell opener (Lumulse POE
(26) GLYC), and blowing agent (water) was mixed using
a laboratory hand-mixer at high rpm for a few minutes to
which the Side A (Rubinate 7304 isocyanate, 26–30 g)
was added. The entire mixture was thoroughly blended
for a few seconds (mix time). The parts of Rubinate 7304
used for all formulations were calculated using the isocy-
anate index 100. The parts of Rubinate 7304 for PUF for-
mulations increases with an increase in the polyol
content of DAMLPEG-7-94 and DAPEG-94 polyols due
to their higher hydroxyl value compared to Voranol 4701.
The characteristic times (cream, top of the cup, string gel,
rise, and tack free) for each PUF were recorded.
2.3 | Polyurethane foam
characterization
2.3.1 | Box foam synthesis and sample
preparation
A mold of dimensions 30 cm × 30 cm × 6 cm was used to
make a box foam. A mold release Chem-Trend PU-11331
was applied inside the mold which was maintained at
65 C. Meanwhile, all ingredients of side B were measured
in the proportion given in Table 2 and mixed for 2–3 min.
Side A was added to side B and mixed for 12 s. The mix-
ture was immediately poured inside the mold and the lid
was closed. After 6 min, the foam was removed from the
4 of 15 BOTE ET AL.

TABLE 2 Formulation used for flexible polyurethane foams

Biobased polyol content

Materials 0% 10% 20% 30% 40% 50%

Side B (parts)
Petroleum-based Polyol 100.0 90.0 80.0 70.0 60.0 50.0
Voranol 4701
Biobased Polyols 0.0 10.0 20.0 30.0 40.0 50.0
(a) Agrol Prime A-56 or
(b) DAMLPEG-7-94 or
(c) DAMLPEG-7-47 or
(d) DAPEG-94 or
(e) DAPEG-38
Catalysts
Lumulse POE (26) GLYC 1.2 1.2 1.2 1.2 1.2 1.2
Tegostab B4690 0.7 0.7 0.7 0.7 0.7 0.7
Diethanolamine 1.5 1.5 1.5 1.5 1.5 1.5
Niax A-300 0.6 0.6 0.6 0.6 0.6 0.6
Niax A-1 0.4 0.4 0.4 0.4 0.4 0.4
Water 2.8 2.8 2.8 2.8 2.8 2.8
Side A- Rubinate 7304 (parts)
(a) Agrol Prime A-56 51.0 52.0 52.0 53.0 53.0 54.0
(b) DAMLPEG-7-94 51.0 52.0 54.0 55.0 56.0 58.0
(c) DAMLPEG-7-47 51.0 51.0 51.0 52.0 52.0 52.0
(d) DAPEG-94 51.0 52.0 54.0 55.0 56.0 58.0
(e) DAPEG-38 51.0 51.0 51.0 51.0 51.0 51.0
ISO Index 100.0 100.0 100.0 100.0 100.0 100.0

box and kept in an oven at 65 C for 30 min. The PUF con-
taining 0%–40% of a biobased polyol were synthesized on
the same day. After 7 days of foam manufacturing, the
outer skin of the box foam was removed by cutting 1 cm
from all sides using a band saw. Two box foams were used
per formulation to measure its properties. The first box
foam was cut into small blocks of dimension
25 mm × 50 mm × 50 mm for wet compression set, com-
pression, and apparent density testing. The second box
foam was cut into foam sheets of thickness 10 and
12.5 mm, which were used for die-cutting tear and tensile
samples, respectively. A USM Hytronic Model B press was
used to die cut tear and tensile samples.
2.3.2 | PUF mechanical properties
evaluation
ASTM 3574-08 (Test A) was used for apparent density,
ASTM 3574-08 (Test L) was used for wet compression set,
ASTM 3574-08 (Test C) was used for compression force
deflection, ASTM 3574-08 (Test E) was used for tensile
testing, and ASTM D 624 (Die C) was used for tear
strength. An Instron model 5565 with a 500 N load cell
was used to measure mechanical properties of the foam.
The compressive strength of foams was tested in the
direction perpendicular to the rise direction of foam with
a speed of 50 mm/min. The tensile and tear samples were
tested in the direction perpendicular to the rise direction
of foam with a speed of 500 mm/min. Six replicates were
used for each measurement.
2.3.3 | Scanning electron microscopy
images of PUF
Cell morphologies of all foams were studied in perpendic-
ular to the rise direction of foam using a JEOL 6610LV
(tungsten hairpin emitter) Scanning Electron Microscope
(JEOL Ltd., Tokyo, Japan). A foam sample was immersed
BOTE ET AL.
F I G U R E 1 Effect of change in concentration of different catalysts on flexible foams [Color figure can be viewed at
wileyonlinelibrary.com]
in liquid nitrogen for a minute and a thin section was cut
using a double-edged razor blade. The samples were
mounted on aluminum stubs using high vacuum carbon
tabs (SPI Supplies, Pennsylvania). Samples were coated
with gold (30 nm thickness) in an Emscope Sputter
Coater model SC 500 (Ashford, Kent, England) purged
with argon gas.
2.3.4 | Thermogravimetric analysis
of PUF
The thermogravimetric analysis (TGA) was conducted on
foam samples under nitrogen environment using a TGA
Q50 (TA Instruments, Delaware) to study their degrada-
tion behavior. In this analysis, a sample (10–15 mg) was
taken in an aluminum pan and heated up to 550–600 C
at the rate of 10 C/min. The weight loss (%) and deriva-
tive thermogram (%/ C) of a sample as a function of tem-
perature ( C) was recorded.
2.3.5 | Miscibility study of biobased
polyols with petroleum-based polyol
The PUF formulation containing 50% of biobased polyol
content given in Table 2 was used for the miscibility
study. In a plastic cup, all contents of side B were mixed
for 3–4 min and poured into a glass jar. The pictures were
taken after a week and 2 weeks to visually observe
miscibility.
3 | R E S U L T A N D DI S C U S S I O N
In commercial foam synthesis, polyester polyols with an
acid value of 5 mg of KOH/g or less is used.20 During the
polyurethane foam synthesis, it was observed that polyols
with an acid value of greater than 5 mg of KOH/g pro-
duced stiffer foams with a dark yellow color and irregular
internal structure. Thus, biobased polyols with an acid
5 of 15
value of less than 3–4 mg of KOH/g were evaluated for
flexible PUF applications. The biobased PUF formulation
used in the previous studies was used as a starting point
for a new biobased PUF formulation development.21,22
The amount of catalysts, surfactant, and blowing agent
(water) depends on polyol type and primary hydroxyl
group content (%). Thus, a single PUF formulation does
not work for all polyols. Often a slight modification in
the formulation is required with a new polyol. The PUF
formulation containing 30% of DAMLPEG-7-94 polyol
was used to optimize the catalyst concentration. In this
process, one of the catalysts was either increased or
decreased by 0.1–0.2 parts. These changes were based on
the free rise profile of foam. For example, if the string gel
time was lower, then the amount of crosslinking catalyst
was reduced, and if the blowing reaction was faster, then
the amount of gelling catalyst was increased. The internal
cellular structures of foams before and after the change
were compared. If the change adversely affected the
internal cellular structure of the foam, then the change
was reversed. For the next formulation, amount of
another catalyst was changed. This process was contin-
ued until a good foam was obtained. Some of the impor-
tant observations are discussed below.
If strings were present on the edges of a foam
(Figure 1(a)), it was probably due to the high concentra-
tion of the crosslinking agent (diethanolamine). In the
next foam formulation (Figure 1(b)), the amount of
diethanolamine was reduced. The uneven cell size distri-
bution (Figure 1(b)) of the foam was reduced by increas-
ing the surfactant concentration (Tegostab B4690), which
produced a foam with a uniform cell size distribution as
shown in Figure 1(c). Surfactant stabilizes the bubble for-
mation and enhances operating margin between foam
collapse and shrinkage.14 It was noticed that increasing
the cell opener concentration (Lumulse POE 26) reduces
the closed-cell content as well as the shrinkage. It also
increases the resiliency of foam along with the uniform
cell distribution (Figure 1(d)).
Another issue with the flexible polyurethane foam is
shrinkage. The flexible PUF used for cushioning
6 of 15
applications have open-cells.23,24 The isocyanate-water
reaction generates heat and carbon dioxide gas. When
the foam starts cooling, the carbon dioxide gas inside
foam cells starts contracting.25 The gas inside the open
cells gets replaced by the surrounding air and hence
foams containing open cells are stable. Whereas, the gas
trapped inside the unopened cells cannot get replaced by
the surrounding air due to the closed cell structure. Thus,
if the foam has a lot of unopened cells, it collapses after a
few minutes as shown in Figure 2 (right side). The foam
synthesized using exactly the same formulation does not
collapse if it is mechanically crushed after 15–20 min of
foam manufacturing as shown in Figure 2 (left side). The
mechanical crushing opens up closed cells and avoids
further shrinking of the foam. Thus, a slight mechanical
force was applied to each box foam to avoid its shrinking,
which is a common industrial practice.
3.1 | Free rise study of PUF
All biobased PUF formulations are given in Table 2. The
mix time, cream time, top of the cup time, string gel time,
rise time, and tack free time for each formulation were
measured. The mix time represents mixing of polyol (side
B) and isocyanate (side A) components. At cream time,
the viscosity of polyol-isocyanate mixture increases and
foam starts rising. At top of the cup time, the foam
reaches the top of the cup. At string gel time, polyure-
thane network starts building. At rise time, the foam
stops rising. At tack free time, the foam is no longer
sticky. The characteristic times depends on the ratio of
primary to secondary hydroxyl groups, hydroxyl value of
the polyol mixture, and the polyol composition. The
higher concentration of secondary hydroxyl groups
increases the characteristic times as they are less reactive
toward isocyanate compared to the primary hydroxyl
group. The hydroxyl value of polyol mixture increases
BOTE ET AL.
F I G U R E 2 Effect of unopened cells
on flexible foams [Color figure can be
viewed at wileyonlinelibrary.com]
with an increase in the polyol content of DAMLPEG-7-94
and DAPEG-94 polyols, which also increases the amount
of isocyanate (Table 2). As equal amount of catalyst was
added to all formulations, the concentration of catalyst,
that is, the amount per polyol-isocyanate reaction,
decreases with an increase in the hydroxyl value. Thus,
the characteristic times of PUF formulations might
increase with an increase in the polyol content of
DAMLPEG-7-94 and DAPEG-94 polyols. The mix time
and cream time for all formulations were 12 and 15–18 s
respectively. The tack free time for all PUF was higher
than 3–4 min. The characteristic times are given in
Figure 3. A slight difference was observed in the top of
the cup time, string gel time, and rise time for PUF for-
mulations containing 10%–40% of DAMLPEG-7-94,
DAPEG-7-47, DAPEG-38, and Agrol Prime A-56 polyols.
A small increase (0.1–0.2 parts) in Niax-A300 or Niax-A1
catalysts concentration can decrease the slight increase in
the characteristic times. The PUF made with DAPEG-94
polyol showed significantly higher characteristic time
compared to PUF made with DAPEG-38, which could be
due to the higher hydroxyl value of DAPEG-94 polyol.
However, the PUF made with DAMLPEG-7-94 polyol
have characteristic times close to the characteristic times
of PUF made with DAMLPEG-7-47 polyol despite having
higher hydroxyl value. Thus, the PUF made with polyols
containing meso-lactide component did not show a sig-
nificant change in the characteristic times.
The box foams containing 0%–40% of biobased polyols
were made using the formulations given in Table 2. The
box foams containing 30% and 40% of DAPEG-94 polyol
collapsed slightly after a few minutes of manufacturing.
Hence, they were not tested for mechanical properties.
The final biobased content of foams made with the
biobased polyols was 0%–16% (0%–40% of biobased
polyol), as given in Table S1. It can be increased to 25%
by using the biobased PEG for the polyol synthesis
(Table S2).
BOTE ET AL. 7 of 15

Agrol Prime A-56 DAMLPEG-7-94 Agrol Prime A-56 DAMLPEG-7-94

DAMLPEG-7-47 DAPEG-94 DAMLPEG-7-47 DAPEG-94
DAPEG-38 DAPEG-38
80 120
Top of the cup time (s) (a) (b)
100

String gel time (s)

60
80
60
40
40
20 20
0% 10% 20% 30% 40% 0% 10% 20% 30% 40%
Biobased Polyol Content Biobased Polyol Content

Agrol Prime A-56 DAMLPEG-7-94

DAMLPEG-7-47 DAPEG-94
DAPEG-38

(c)
Rise time (s)

160

60
0% 10% 20% 30% 40%
Biobased Polyol Content

F I G U R E 3 (a) Top of the cup time, (b) string gel time, and (c) rise time of flexible PUF foams [Color figure can be viewed at
wileyonlinelibrary.com]

(a) (b)
100 100

80 80
Weight (%)

Weight (%)

60 Control 60
20% Agrol Prime A-56 Control
40 20% DAMLPEG-7-94 40 40% Agrol Prime A-56
20% DAMLPEG-7-47 40% DAMLPEG-7-94
20 20% DAPEG-94 20 40% DAMLPEG-7-47
20% DAPEG-38 40% DAPEG-38
0 0
0 100 200 300 400 500 600 0 100 200 300 400 500 600
Temperature (°C) Temperature (°C)

F I G U R E 4 TGA graphs of flexible PUF containing (a) 20% and (b) 40% of biobased polyols [Color figure can be viewed at
wileyonlinelibrary.com]

3.2 | Thermogravimetric analysis of PUF polyol chain, and the third stage corresponds to the further
degradation of fragments produced in the second stage.27,28
The TGA graphs of PUF containing 20% and 40% of bio- The temperatures for 5% and 10% mass loss increased with
based polyol content are shown in Figure 4(a),(b), respec- increasing biobased polyol content, except for Agrol Prime
tively. In the TGA graphs of the foams, three degradation A-56, as given in Table S3. This increase in temperatures
stages were observed, that is, Stage I (100–250 C), Stage indicates the presence of more stable groups on polyol side.
II (250–360 C), and Stage III (360–450 C). The temperatures for 50% mass loss increased with increas-
The first stage corresponds to the degradation of less sta- ing biobased polyol content for all polyols. This could be
ble groups such as biuret or urethane.26 The second stage due to the presence of long carbon chains and ester linkages
corresponds to the degradation of soft segments of the in biobased polyols. The residual mass at 580 C of all
8 of 15
biobased PUF is slightly higher than the residual mass at
the same temperature of the control PUF.
3.3 | Density of PUF
The density of flexible PUF used in car cushions and
backs is in the range of 20–95 kg/m3 to maintain a cer-
tain amount of strength for commercial applications.21
The density of foam depends on the amount of CO2 pro-
duced, which further depends on the amount of water
added. Also, properties of foam are strongly dependent
on its density. Hence, foam densities should be similar to
compare their properties. The densities of biobased PUF
are shown in Figure 5.
The densities of control foams were in the range of
44–48 kg/m3. The densities of foams containing biobased
polyols (except for Agrol Prime A-56) decreased slightly
with an increase in the biobased content. The biobased
PUF containing 20% and 30% of DAMLPEG-7-94,
DAMLPEG-7-47 and DAPEG-38 polyols had densities in
the range of 42–45 kg/m3, which were lower than control
foam densities. Whereas densities of biobased PUF con-
taining 40% of DAMLPEG-7-47 and DAMLPEG-7-94
polyols were in the range of 49–53 kg/m3, which were
slightly higher than control foam densities. This aberra-
tion in the densities is very difficult to control and should
be considered as a significant factor in the mechanical
properties comparison. For automotive applications, if
better performance properties are obtained with lower
foam densities, then it will reduce overall weight of the
vehicle. This will increase the fuel efficiency and reduce
emissions to the environment.
3.4 | Scanning electron microscopy
images of PUF
The scanning electron microscopy (SEM) images of PUF
containing 0%, 20%, and 40% of biobased polyols are
shown in Figure 6. These images were taken perpendicu-
lar to the rise direction of the box foam. The SEM images
of all PUF showed a majority of open-cell structure. Very
few cells showed closed-cell window. The cell sizes of
foams containing 40% DAMLPEG-7-94 and 40% Agrol
Prime A-56 polyols were comparatively smaller than the
cell size of control foam, as given in Table S4. It can be
seen in the SEM images that PUF containing 0% and 20%
of biobased polyols have some cells with closed windows.
Whereas PUF containing 40% of biobased polyols have
cells with open windows. The cell size did not change
much with the addition of DAPEG-38 and DAMLPEG-
7-47 polyols as given in Table S4. The foams containing
BOTE ET AL.
Agrol Prime A-56 DAMLPEG-7-94 DAMLPEG-7-47
DAPEG-94 DAPEG-38
55
Density (kg/m3)
50
45
40
35
0% 10% 20% 30% 40%
Biobased Polyol Content
F I G U R E 5 Densities of flexible polyurethane foams [Color
figure can be viewed at wileyonlinelibrary.com]
20% DAPEG-94 polyol showed cell size similar to the
control foam.
3.5 | Wet compression set of PUF
For automotive applications, such as seat cushions, arm-
rest, headrest, and so forth, the compression set is critical.
Compression set measures the ability of the foam to
recover after being exposed to heat and compressive
stress. In previous literature, the compression set has
been measured by compressing a foam to 50% of its origi-
nal height and then heating it in an oven at 70 C for
22 h.29 The compression set values were less than 10%–
15%29 for foams containing 40% of biobased polyol con-
tent. In some applications, foams can be exposed to high
temperatures along with humidity, where compression
set values based on dry heat aging will not be adequate.
Thus, the wet compression set testing was performed on
flexible PUF samples instead of compression set. The
foams were compressed between two parallel plates to
50% of its original height and kept in a chamber
maintained at 50 C and 95% humidity. After 22 h, the
compressive stress on the foams was removed and final
height was measured after 2 h. The wet compression set
measures the ability of the foam to go back to its original
shape after being exposed to the wet heat aging. Lower
values of wet compression set indicate a better probabil-
ity of foams going back to the original shape. For general
applications of flexible PUF in automotive, this value
should be less than 40%–50%.24 The wet compression set
values of PUF containing 0%–40% of biobased polyols are
given in Figure 7. The wet compression set increased
above 40% for the foams containing 20% of DAMLPEG-
7-94 and DAPEG-94 polyols. Initially, it was assumed
that the higher compression set values were due to the
presence of ester linkages in the polyol, which are
BOTE ET AL. 9 of 15

F I G U R E 6 a-1, a-2, and a-3 are PUF containing 0%, 20%, and 40% of DAMLPEG-7-94; b-1, b-2, and b-3 are PUF containing 0%, 20%,
and 40% of Agrol prime a-56; c-1, c-2, and c-3 are PUF containing 0%, 20%, and 40% of DAPEG-38; d-1, d-2, and d-3 are PUF containing 0%,
20%, and 40% of DAMLPEG 7–47; e-1 and e-2 are PUF containing 0% and 20% of DAPEG-94

susceptible to the moisture absorption. But the wet com- 38 polyol were lower than 40%. This indicates that the
pression set values of PUF containing 30% of DAMLPEG- increase in the wet compression set of PUF containing
7-47 and Agrol Prime A-56 polyols, and 40% of DAPEG- DAMLPEG-7-94 and DAPEG-94 polyols could be due to
10 of 15
Agrol Prime A-56 DAMLPEG-7-94
DAPEG-94 DAPEG-38
60%
Wet Compression Set
50%
40%
30%
20%
10%
0%
0% 10% 20%
Biobased Polyol Content
F I G U R E 7 Wet compression set values of biobased PUF [Color
figure can be viewed at wileyonlinelibrary.com]
the higher hydroxyl value of polyols, and not because of
the presence of ester groups. The increase in the hydroxyl
value increases the number of urethane linkages, which
also increases the rigidity and reduces the resiliency of a
foam. Thus, the foam containing 40% of a biobased polyol
having a hydroxyl value of 38 mg of KOH/g was found to
have a wet compression set of around 32%.
3.6 | Tensile properties of PUF
The tensile properties of foams, that is, tensile strength at
maximum load (kPa), Young's modulus (kPa), and elon-
gation at maximum load (mm), were measured to com-
pare the strength of foams under tension. Tensile
properties are also a measure of strength of internal
bonds formed during the polyurethane reaction.22 The
elasticity of foam can depend on the number of ester and
ether linkages present in the polyols as well as the
hydroxyl value of polyols. The tensile strength at maxi-
mum load of all biobased PUF slightly increased with
increasing biobased polyol content as shown in Figure 8
(a). The tensile strength at maximum load of PUF con-
taining 30% of DAPEG-38 polyol (78 kPa) was significantly
lower than the tensile strength at maximum load of con-
trol foam (94 kPa). This could be due to the lower density
of PUF containing 30% of DAPEG-38 polyol (42–43 kg/
m3) compared to the control foam (48 kg/m3). The tensile
strength at maximum load values of PUF containing 10%–
30% of DAMLPEG-7-47 and DAMLPEG-7-94 polyols
remained constant. The tensile strength at maximum load
of PUF containing 10%–40% of Agrol Prime A-56 polyol
increased with increasing the biobased polyol content,
which could be due to the increase in the density of PUF,
as shown in Figure 5. The PUF containing 20%–30% of
DAMLPEG-7-47 polyol had densities around 42–45 kg/m3
and tensile strength at maximum load around 90–95 kPa.
BOTE ET AL.
DAMLPEG-7-47 Whereas, the control foam with a density of 47 kg/m3 had
tensile strength at maximum load around 94 kPa. Thus,
some biobased PUF showed similar tensile strength as that
of control PUF at lower foam densities.
The minimum requirement of the tensile strength at
maximum load for headrest and seat cushion applica-
tions is 90 and 130 kPa,29 respectively, for a foam having
a density of 45 kg/m3. Thus, the current biobased formu-
lations are suitable for headrest application. However,
the tensile strength of foams strongly depends on the
30% 40%
cross-linking density, and it increases with an increase in
the isocyanate index.12 Thus, it is possible to increase the
tensile strength by increasing the isocyanate index.
The Young's modulus measures the resistance of a
material to elastic deformation under tension or load.
The higher Young's modulus value indicates a higher
stress is required to stretch the material compared to the
stress required to stretch a material having a lower
Young's modulus to the same extent. The Young's modu-
lus was measured in the region of 0–10 mm extension
and is shown in Figure 8(b) for all biobased PUF. The
Young's moduli of foams containing 10%–30% of
DAMLPEG-7-47, DAPEG-94, and Agrol Prime A-56 poly-
ols increases with increasing the polyol content. How-
ever, Young's moduli slightly decreased for PUF
containing 10%–30% of DAMLPEG-7-94 foams.
The elongation at maximum load is shown in
Figure 8(c) for all PUF samples. It was observed that the
elongation at maximum load of biobased PUF slightly
increases with increasing DAMLPEG-7-47, DAMLPEG-
7-94, DAPEG-94, and Agrol Prime A-56 polyols content.
It was also observed that the elongation at maximum
load does not change with the addition of DAPEG-38
polyol. The minimum elongation at maximum load
required for the headrest application is 80 mm and for
seat cushion application is 105 mm,29 for a foam having a
density of 45 kg/m3. Thus, all biobased PUF can be used
for headrest application as they showed elongation at
maximum load of 80 mm or higher. The PUF containing
20%–40% of DAMLPEG-7-94, DAMLPEG-7-47, and Agrol
Prime A-56 polyols can be used for seat cushion applica-
tion as they showed elongation at maximum load of
105 mm or higher.
3.7 | Tear resistance of PUF
The tear resistance values of biobased PUF are shown in
Figure 8(d). The tear resistance measures the ability of
the foam to resist the growth of any cut under tension.
All PUF containing 10%–30% of biobased polyol content
showed tear resistance equal to or greater than 0.4 N/
mm. The tear resistance of a foam having a density of
BOTE ET AL. 11 of 15

Agrol Prime A-56 DAMLPEG-7-94 Agrol Prime A-56 DAMLPEG-7-94

DAMLPEG-7-47 DAPEG-94 DAMLPEG-7-47 DAPEG-94
DAPEG-38 DAPEG-38
130 250

Tensile strength at max load

(a) (b)
120

Young's modulus (kPa)

200
110
(kPa) 100
150
90
80 100
70
60 50
0% 10% 20% 30% 40% 0% 10% 20% 30% 40%
Biobased Polyol Content Biobased Polyol Content
Agrol Prime A-56 DAMLPEG-7-94 Agrol Prime A-56 DAMLPEG-7-94
DAMLPEG-7-47 DAPEG-94 DAMLPEG-7-47 DAPEG-94
DAPEG-38 DAPEG-38
130 0.55
Elongation at max load (mm)

(c) (d)
120

Tear resistance (N/mm)

0.50
110
100 0.45
90 0.40
80
0.35
70
60 0.30
0% 10% 20% 30% 40% 0% 10% 20% 30% 40%
Biobased Polyol Content Biobased Polyol Content

F I G U R E 8 (a) Tensile strength at maximum load, (b) Young's modulus, (c) elongation at maximum load, and (d) tear resistance of
biobased PUF [Color figure can be viewed at wileyonlinelibrary.com]

45 kg/m3 for use in the interior automotive application Foams made with polyols having a higher hydroxyl
should be at least 0.2 N/mm.29 All biobased PUF had tear value contain more polyurethane linkages compared to
resistance of 0.2 N/mm or higher. the foams made with polyols having a lower hydroxyl
value. The urethane linkages can also affect the stiffness
of foams and hence the compressive properties. The
3.8 | Compressive properties of PUF drastic increase in the compressive modulus of PUF con-
taining 40% of DAMLPEG-7-47 polyol could be due to
The compressive moduli for all biobased PUF samples the higher density of PUF.
are shown in Figure 9(a). The compressive properties of The compressive stress values required to deform a
biobased PUF were measured in order to evaluate its foam sample to 25%, 50%, and 65% of its original height
behavior under compressive load. The compression are shown in Figure 9(b)–(d), respectively. The compres-
modulus measures the stiffness of a foam. The higher sive stress of PUF containing 20%–30% of DAMLPEG-
compressive modulus value indicates higher compres- 7-94, DAMLPEG-7-47, and DAPEG-38 polyols remains
sive stress is required to deform the foam sample com- constant and increases for PUF containing biobased
pared to a foam sample having lower compressive polyol content of 30% or higher. The compressive stress is
modulus. The modulus slightly increased with increas- directly related to the foam density, which means com-
ing the biobased polyol content in PUF. The compres- pressive stress decreases with the decrease in the foam
sion modulus is directly proportional to the PUF density. However, the PUF containing 20%–30% of
density. The densities of foams remained constant for DAMLPEG-7-47 and DAPEG-38 polyols have the same
10%–30% of biobased polyol as shown in Figure 5. Thus, compressive stress as that of control foam despite having
the increase in the compression moduli with an increase lower densities. Thus, the compressive properties of PUF
in the biobased polyol content might be an indicator of made with DAMLPEG-7-47 and DAPEG-38 polyols are
increase in the resistance to deformation of foams. Thus, better than the compressive properties of the control
the backbone of biobased polyols (polyester linkages) foam. The compressive stress increased with the addition
provide a higher resistance to deformation in foams. of Agrol Prime A-56, DAMLPEG-7-94, and DAPEG-94
12 of 15 BOTE ET AL.

Agrol Prime A-56 DAMLPEG-7-94 Agrol Prime A-56 DAMLPEG-7-94

DAMLPEG-7-47 DAPEG-94 DAMLPEG-7-47 DAPEG-94
DAPEG-38 DAPEG-38
4.5

Compressive stress at 25%

Compression modulus (kPa)
140 (a) (b)
4.0

strain (kPa)
3.5
100
3.0

60 2.5
2.0
20 1.5
0% 10% 20% 30% 40% 0% 10% 20% 30% 40%
Biobased Polyol Content Biobased Polyol Content

Agrol Prime A-56 DAMLPEG-7-94 Agrol Prime A-56 DAMLPEG-7-94

DAMLPEG-7-47 DAPEG-94 DAMLPEG-7-47 DAPEG-94
DAPEG-38 DAPEG-38
8 14
Compressive stress at 50%

Compressive stress at 65%

(c) (d)
7
strain (kPa)

11

strain (kPa)
6

5
8
4

3 5
0% 10% 20% 30% 40% 0% 10% 20% 30% 40%
Biobased Polyol Content Biobased Polyol Content

Agrol Prime A-56 DAMLPEG-7-94 Agrol Prime A-56 DAMLPEG-7-94

DAMLPEG-7-47 DAPEG-94 DAMLPEG-7-47 DAPEG-94
DAPEG-38 DAPEG-38
2.4 5.5
(e) (f)
SAG Factor 65%/25%

2.2 5.0
SAG Factor 50%/25%

4.5
2.0 4.0
1.8 3.5
3.0
1.6
2.5
1.4 2.0
0% 10% 20% 30% 40% 0% 10% 20% 30% 40%
Biobased Polyol Content Biobased Polyol Content

F I G U R E 9 (a) Compression modulus (b) compressive stress at 25% strain (c) compressive stress at 50% strain (d) compressive stress at
65% strain (e) sag factor 50%/25% (f) sag factor 65%/25% of biobased PUF [Color figure can be viewed at wileyonlinelibrary.com]

polyols. This increase could be due to the higher hydroxyl
value of polyols producing a higher number of urethane
linkages compared to the other polyols.
The sag factor is another measurement of the cush-
ioning quality of foams. The higher value indicates a
higher resistance to “bottoming out.” The foam used for
cushioning applications should have a minimum sag
factor so that the support used under the foam is not
felt.21 The sag factor is a ratio of compressive stress at
different strains. The ratio of compressive stress at 50%
strain to compressive stress at 25% strain is shown in
Figure 9(e). The ratio of compressive stress at 65% strain
to compressive stress at 25% strain is shown in Figure 9
(f). If the sag factor 50%/25% is close to two, it means
that the compressive force required to compress 50% of
the foam is double of the compressive force required to
compress 25% of the foam. The sag factor either remains
constant or increases slightly with increasing the bio-
based polyol content of PUF. The sag factor of PUF con-
taining DAMLPEG-7-47 and DAPEG-38 polyols is
higher compared the sag factor of control and Agrol
Prime A-56 polyol foams.
BOTE ET AL. 13 of 15

F I G U R E 1 0 Miscibility study of biobased polyols (a) Agrol Prime A-56, (b) DAMLPEG-7-94, (c) DAMLPEG-7-47, (d) DAPEG-94,
(e) DAPEG-38 with Voranol 4701 (after 2 weeks) [Color figure can be viewed at wileyonlinelibrary.com]

TABLE 3 Comparison of different biobased PUF containing 30% biobased polyol with petroleum-based PUF

PUF

Voranol 4701 30% Agrol Prime 30%

Property (control) A-56 DAPEG-38 30% DAMLPEG-7-47
3
Density (kg/m ) 45.2 47.0 42.2 42.4
Compressive strength at 25% strain (kPa) 2.7 4.3 2.0 2.0
Compressive strength at 65% strain (kPa) 7.7 11.2 8.6 7.1
Sag factor 65%/25% 2.8 2.8 4.2 3.5
Tear resistance (N/mm) 0.4 0.4 0.4 0.5
Tensile strength at max. Load (kPa) 75.1 117.8 77.8 89.6
Elongation (mm) 75.1 117.8 96.4 105.7

Temperature at 10% mass loss ( C) 283.0 269.0 290.0 290.0
Wet compression set (%) 27.1 37.0 31.4 37.6
Miscibility with Voranol 4701 - Partial Partial Complete

3.9 | Miscibility study and comparison of
different biobased PUF
It is a common industrial practice to blend different poly-
ols to achieve desired properties. The foams made with
immiscible polyols might show different properties at dif-
ferent locations. Thus, the miscibility of biobased polyes-
ter polyols with the control polyether polyol is important
to obtain foams with a uniform properties. The Side B
components of formulations containing 50% biobased
polyol (given in Table 2) were mixed to obtain a uniform
mixture, and then the mixture was poured into a glass
jar. The mixture was observed over a period of 2 weeks.
The mixtures containing DAMLPEG-7-94 and
DAMLPEG-7-47 polyols with Voranol 4701 did not show
any phase separation after a week or 2 weeks as shown
in Figure S2(b and c) and Figure 10(b),(c), respectively.
It was also observed that the DAMLPEG-7-94 polyol was
completely miscible with Voranol 4701 without the
addition of any catalysts. A very thin layer was observed
at the bottom of the jar containing the mixture of
DAPEG-94 and Voranol 4701 polyols, as shown in
Figure 10(d). Phase separation was clearly observed
(Figure 10(e)) in the mixture of DAPEG-38 and Voranol
4701 polyols, which could be due to the viscosity differ-
ence between DAPEG-38 and Voranol 4701 polyols. The
mixture of Agrol Prime A-56 and Voranol 4701 polyols
did not show phase separation after a week (Figure S2
(a)), but showed some phase separation after 2 weeks
(Figure 10(a)).
14 of 15
4 | C OM P ARISON OF C ONTROL
A ND BI O BAS ED PU F
The biobased PUF formulation was optimized for 30% of
DAMLPEG polyols. Thus, tensile and tear properties of
biobased PUF containing 40% of biobased polyol were
poor. Also, foams containing 50% biobased polyols
showed shrinkage. A further optimization of catalysts
concentration for biobased PUF formulations containing
40%–50% of biobased polyols is necessary to obtain a
stable foam. The comparison of different biobased PUF
containing 30% of biobased polyol is given in Table 3.
The mechanical properties of 30% DAPEG-38 and 30%
DAMLPEG-7-47 PUF were better than the control PUF
at a lower density. The thermal stability of 30% DAPEG-
38 and 30% DAMLPEG-7-47 PUF was better than the
thermal stability of PUF synthesized from commercially
available biobased polyol (Agrol Prime A-56). The
DAMLEPG-7-47 polyol was completely miscible with
Voranol 4701 polyol. As PUF made with 30% of
DAMLPEG-7-47 polyol showed better mechanical and
thermal properties than commercial biobased and
petroleum-based polyols, it can be used for different
applications to increase the renewable carbon content
of PUF.
5 | C ON C L U S I ON
This study demonstrates the optimization of catalyst con-
centrations of biobased PUF formulations containing
higher amounts of biobased polyols. The biobased PUF
containing 10%–40% of biobased polyols were success-
fully synthesized. The free rise profiles of polyols with
lower hydroxyl value did not show any difference com-
pared to the free rise profiles of control PUF. The thermal
degradation behavior of biobased PUF was better than
the thermal degradation behavior of PUF made from the
commercially available biobased and petroleum-based
polyols. The SEM images of all PUF showed an open cell
structure which is required for cushioning application.
The wet compression set, which is very important for car
seating application, improved with the decrease in the
hydroxyl value of a polyol. The biobased PUF containing
40% of DAPEG-38 and DAMLPEG-7-47 polyols passed
the wet compression set test. The tensile properties of
PUF increased with increasing biobased polyol content.
The tear resistance for all biobased PUF increased with
increase in the biobased polyol content. The tear resis-
tance of foams made with DAMLPEG-7-47 and DAPEG-
38 polyols was higher than the tear resistance of foams
made with Agrol Prime A-56 polyol. A slight increase in
the compressive properties was observed with increase in
BOTE ET AL.
the biobased polyol content. In the end, the miscibility
study showed that polyols (DAMLPEG) containing
lactide component were completely miscible with
petroleum-based polyol, that is, Voranol 4701. Some of
the biobased flexible PUF formulations passed the mini-
mum requirement for car seats and headrest applications
used in the automotive industry.
ACKNOWLEDGMENTS
The authors are very grateful to Ford Motor Company,
Dearborn, MI for providing support through Ford-MSU
Alliance funding and the facility for polyurethane foams
testing. The authors also acknowledge Huntsman Corpo-
ration (Texas, USA), Evonik (Virginia, USA), Lambent
Corporation (Illinois, USA), The Dow Chemical Com-
pany (Michigan, USA), and Momentive Performance
Materials (New York, USA) for providing materials
required for foam formulations.
ORCID
Sayli Devdas Bote https://orcid.org/0000-0001-6803-
4053
Alper Kiziltas https://orcid.org/0000-0001-9297-2007
Deborah Mielewski https://orcid.org/0000-0002-4943-
5537
Ramani Narayan https://orcid.org/0000-0003-3715-
5092
RE FER EN CES
[1] T. W. Abraham, Biobased Monomers, Polymers, and Materials,
ACS Publications, Washington, DC 2012, p. 165.
[2] S. Ghasemi, E. N. Amini, M. Tajvidi, A. Kiziltas, D. F. Mielewski,
D. J. Gardner, J. Appl. Polym. Sci. 2020, 138, 49983.
[3] Polyurethane Foam Market by Type (Rigid Foam, Flexible
Foam, Spray Foam), End-use Industry (Building & Construc-
tion, Bedding & Furniture, Automotive, Electronics, Footwear,
Packaging, Others), and Region - Global Forecast to 2025,
https://www.marketsandmarkets.com/Market-Reports/poly
urethane-foams-market-1251.html?gclid=Cj0KC QjwlvT8 BRDe
ARIsAACRFiXYx2JL3exoc HGSbNWkvpjf8hdXeYc Xev_RV8
bgqbcdK0ZMk0 HlCi8aAgdqEALw_wcB (accessed: October
31, 2020).
[4] T. W. Abraham, J. J. Malsam (Cargill Inc). U.S. Patent Appli-
cation 12/740,613, September 23, 2010.
[5] Z. S. Petrovic, I. Javni, A. Zlatanic, A. Guo (Cargill Inc). U.S.
Patent 8,153,746, April 10, 2012.
[6] Y. Roh, R. Kumar, C.-l. Zhao, D. Kaczan, T. M. Smiecinski
(BASF SE). U.S. Patent 8,308,975, November 13, 2012.
[7] H. Zhao, R. Herrington, F. Rodriguez (Huntsman Petrochemi-
cal LLC). U.S. Patent Application 13/003,023, May 19, 2011.
[8] M. Desroches, M. Escouvois, R. Auvergne, S. Caillol, B.
Boutevin, Polym. Rev. 2012, 52, 38.
[9] Y. Li, X. Luo, S. Hu, Bio-based Polyols and Polyurethanes,
Springer, Heidelberg 2015.
[10] H. Pawlik, A. Prociak, J. Polym. Environ. 2012, 20, 438.
BOTE ET AL.
[11] R. Jaratrotkamjorn, V. Tanrattanakul, J. Appl. Polym. Sci.
2020, 137, 49310.
[12] P. Rojek, A. Prociak, J. Appl. Polym. Sci. 2012, 125, 2936.
[13] A. Zlatanic, C. Lava, W. Zhang, Z. S. Petrovic, J. Polym. Sci.,
Part B: Polym. Phys. 2004, 42, 809.
[14] G. D. Soto, N. E. Marcovich, M. A. Mosiewicki, J. Appl. Polym.
Sci. 2016, 133, 43833.
[15] A. Kiziltas, D. F. Mielewski, E. C.-c. Lee. (Ford Global Tech-
nologies LLC). U.S. Patent 9,868,835, January 16, 2018.
[16] M. Barikani, M. Barmar, Iran. Polym. J 1996, 5, 231.
[17] S. D. Bote, Engineering of Biobased Industrial Products from
Renewable (agricultural) Resources. Ph.D. Thesis, Michigan
State University, MI, December 2019.
[18] E. Malewska, S. Bąk, A. Prociak, J. Appl. Polym. Sci. 2015,
132, 42372.
[19] R. J. Lockwood, V. D. Poole (Huntsman International LLC).
U.S. Patent 7,022,746, April 4, 2006.
[20] I. Sendijarevic, K. W. Pietrzyk, C. M. Schiffman, V. Sendijarevic,
A. Kiziltas, D. Mielewski, J. Cell. Plast. 2020, 56, 1.
[21] M. DeBolt, A. Kiziltas, D. Mielewski, S. Waddington, M. J.
Nagridge, J. Appl. Polym. Sci. 2016, 133, 44086.
[22] M. Bedell, M. Brown, A. Kiziltas, D. Mielewski, S. Mukerjee,
R. Tabor, Waste Manage. 2018, 71, 97.
[23] J. Sauniere, A. Timbre (J.S.O.). U.S. Patent Application
10/372,165, October 2, 2003.
[24] A. Kiziltas, Z. Dowling, M. Bedell, D. Mielewski (Ford Global
Technologies, LLC). International Application PCT/-
US2018/053344, Sepetmber 28, 2018.
15 of 15
[25] Firm-Grade Flexible Open-Cell Foam, http://www.
northstarpolymers.com/NorthstarPolymers/Foam/
FlexibleFoam/FFM-1_Firm_Flexible_Foam.htm (accessed:
June 20, 2019).
[26] P. Kosmela, A. Hejna, K. Formela, J. T. Haponiuk, Ł.
Piszczyk, Cellulose 2016, 23, 2929.
[27] Y. Feng, H. Liang, Z. Yang, T. Yuan, Y. Luo, P. Li, Z. Yang, C.
Zhang, ACS Sustainable Chem. Eng. 2017, 5, 7365.
[28] D. Ji, Z. Fang, W. He, K. Zhang, Z. Luo, T. Wang, K. Guo, ACS
Sustainable Chem. Eng. 2015, 3, 1197.
[29] C. Flanigan, D. Mielewski, C. Perry (Ford Global Technologies
LLC). U.S. Patent Application 11/160,279, December 22, 2005.
SU PP O R TI N G I N F O RMA TI O N
Additional supporting information may be found online
in the Supporting Information section at the end of this
article.
How to cite this article: Bote SD, Kiziltas A,
Scheper I, Mielewski D, Narayan R. Biobased
flexible polyurethane foams manufactured from
lactide-based polyester-ether polyols for
automotive applications. J Appl Polym Sci. 2021;
138:e50690. https://doi.org/10.1002/app.50690