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org/IECR Article

Synthesis of Biobased Polyols from Soybean Meal for Application in

Rigid Polyurethane Foams
Sayli Devdas Bote and Ramani Narayan*
Cite This: Ind. Eng. Chem. Res. 2021, 60, 5733−5743 Read Online

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ABSTRACT: Soybean meal or soymeal is an inexpensive

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protein−carbohydrate biomass and a coproduct of soybean

processing. The composition of soymeal was determined before
using it for the polyol synthesis. The soluble carbohydrates (SC)
content of soymeal was determined by separating the carbohy-
drates from the other components using an ethanol−water
solution. The protein content of soymeal was determined by the
factor method. The moisture and ash content of soymeal was also
determined. The entire soymeal without any purification was
directly converted to a biobased polyol in a one-pot, two-step
sequential process. The reaction of soymeal with ethanolamine
yielded intermediate amine derivatives which were reacted with
propylene carbonate to obtain the desired soymeal polyol. Both
steps were conducted sequentially in the same reactor without any separation or purification. Different mass ratios (1:2, 1:3, 1:5) of
soymeal to ethanolamine produced polyols with different hydroxyl values. The synthesized soymeal polyols had hydroxyl values of
550−650 mg of KOH/g and contained less than 2% insoluble matter. 13C NMR was used to determine the ratio of primary hydroxyl
groups to secondary hydroxyl groups. The newly synthesized polyols contain urethane and amide backbone linkages which are less
susceptible to degradation by UV-radiation and hydrolysis. The soymeal polyol was successfully used in the synthesis of biobased
rigid polyurethane foams (PUF) containing 20% and 50% biobased polyol content. The compressive strength of a biobased PUF was
higher than 200 kPa for a foam with a density of 40 kg/m3. Scanning electron microscopy was used to study the foam morphology.

1. INTRODUCTION
Polyurethanes are the most versatile polymers having a variety
of applications in foams, coatings, adhesives, sealants, and
elastomers. Polyols (HO−R1−OH), in combination with
isocyanates (OCN−R2−NCO), form the basis for
the manufacturing of polyurethanes (−O−R1−O−CO−NH−
R2−NH−CO−) in many industrial applications, specifically
rigid and flexible polyurethane foams (PUF). Conventionally,
petroleum feedstocks were used to make polyols and
isocyanates, but in recent years, biobased feedstocks are
being used in combination with petroleum feedstocks.1,2
Recently, many companies are incorporating renewable
biomass carbon in their products (e.g., Ford Motor Company’s
polyurethanes, NatureWorks’s Ingeo polymers) in order to
reduce product’s carbon footprint and environmental impacts.
The synthesis of biobased polyols and polyurethanes using
different biomass resources such as cardanol (obtained from
cashew nutshell liquid),3,4 cellulose,5 lignin,6 and algae oil7 has
been reported. Commercially available biobased polyols are
derived from plant oils, for example, soybean oil,8 or from
saccharides such as sucrose. Various routes have been used to
produce polyols from plant oil including transesterification,9
epoxidation,10 ozonolysis,11 and hydroformylation.8 The
epoxidation route is most commonly used by industry for
the synthesis of polyols from plant oil.8 However, this route
gives secondary hydroxyl groups which are less reactive toward
isocyanates than the primary hydroxyl groups.11 Plant oils used
for polyol synthesis include canola oil, castor oil, rapeseed oil,
and soybean oil, with soybean oil most commonly used.11−14
Soybean comprises 18% soybean oil and 82% soybean meal or
soymeal. Approximately 68% of the total soybean oil
consumed in the United States is used in food applications,15
and rest of it is used in the production of biodiesel16,17 and
industrial products such as polyols.8,15 There are many studies
on polyol synthesis from plant oils, but very few studies report
the use of soymeal for polyols synthesis.18−20
In certain studies, soymeal or soy protein isolate has been
incorporated in polyurethane foams as an additive to improve
their mechanical and thermal properties.21,22 Soymeal is
primarily used as an animal feed.23,24 Soymeal proteins have
Received: December 27, 2020
Revised: March 27, 2021
Accepted: March 29, 2021
Published: April 14, 2021

© 2021 American Chemical Society https://doi.org/10.1021/acs.iecr.0c06306

5733 Ind. Eng. Chem. Res. 2021, 60, 5733−5743
Industrial & Engineering Chemistry Research
been extracted and concentrated to provide protein-rich
components, that is, soy protein concentrate (SPC, 70% of
proteins) and soy protein isolate (SPI, 90% of proteins). These
are primarily used in human and animal nutrition, but they are
also used in the production of bioplastics16,25 and other
industrial products, for example, adhesives and compo-
sites.19,22,26 Other biomass resources such as Jatropha meal
(a byproduct of biodiesel production) and distiller’s dried
grains with solubles (DDGS, a byproduct of ethanol
production from corn via the dry milling process) can also
be used for synthesis of industrial products. However, the
crude protein content of soymeal is approximately 40−50%
higher than the crude protein content of Jatropha meal or
DDGS.16
Our group is developing processes to directly utilize a low-
cost biomass such as soymeal, without any separation and
purification, for the manufacture of value-added industrial
products.27,28 In this paper, we report on the direct conversion
of soymeal to polyols and demonstrate its use in producing
rigid polyurethane foams. The detailed composition analysis of
the soymeal is necessary to design and engineer the polyol
synthesis. The percent composition of proteins, soluble
carbohydrates, ash, moisture, and other components (insoluble
carbohydrates, minerals) of soymeal was determined. On the
basis of the analysis, a two-step, single-pot process was
conceived to transform the soymeal into new and usable
biobased polyols. This newly designed process successfully
transforms the whole soymeal to polyols without the need to
separate or purify the soymeal constituents.18 This provides
considerable cost advantage and makes these soymeal polyols
the lowest cost biobased polyols on the market. The ability of
these polyols to be converted to rigid polyurethane foams was
established by making PUF containing 20% and 50% of
soymeal polyol. The free rise profiles, compressive strength,
and internal structure of biobased PUFs were compared with
PUF made with a commercial polyol.
2. EXPERIMENTAL SECTION
2.1. Materials and methods. Soymeal used in these
experiments was received from Zeeland Farm Services, Inc.
(Michigan, USA) with a particle size of 18F (mesh size).
Propylene carbonate (PC) (99%) was purchased from Sigma-
Aldrich (Wisconsin, USA). Ethanolamine or monoethanol-
amine (MEA) (99%) was purchased from Fisher Scientific
(Pennsylvania, USA). The Jeffol-SG-360 with hydroxyl value of
360 mg of KOH/g is a commercially available sucrose−
glycerine based polyol, and Rubinate M is a polymeric
methylene diphenyl diisocyanate (pMDI). Both were received
from Huntsman Corporation (Texas, USA). Catalysts Dabco
DC-193 (silicone-based surfactant), Polycat 77 (tertiary
amine), and Dabco 33LV (33% triethylene diamine,
C6H12N2 and 67% dipropylene glycol, C6H14O3) were received
from Air Products and Chemicals, Inc. (Pennsylvania, USA).
The Niax-A1 catalyst (70% bis(2-dimethylaminoethyl) ether,
C8H20N2O and 30% dipropylene glycol, C6H14O3) was
received from Momentive Performance Materials (New York,
USA).
2.2. Soymeal Composition Analysis. The amounts of
proteins, soluble carbohydrates, ash, moisture, and other
(insoluble carbohydrates, minerals) components present in
the soymeal were determined. This soymeal was used for
polyol synthesis without any separation or purification.
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2.2.1. Soluble Carbohydrates Content (%). Soluble
carbohydrates were separated from soymeal using ethanol−
water (50% v/v) solution. In a round-bottom flask, 8 g of
soymeal and 100 mL of ethanol−water (50% v/v) solution was
taken and stirred at room temperature (20 °C) for 8−10 h.
Following that, a simple filtration method was used to separate
the insoluble components of soymeal. This insoluble part was
dried in an oven. Water and ethanol were removed from the
filtrate containing soluble components, that is, soluble
carbohydrates. The soluble carbohydrates had some residual
moisture which can be determined by a thermogravimetric
analysis (TGA) and is discussed in section 3.1.2. The soluble
carbohydrates content of soymeal was determined using the
following formula,
soluble carbohydrates content (%)
soluble carbohydrates (g ) − moisture (g )
= × 100
soymeal (g )
(1)
2.2.2. Protein Content (%). The protein content of soymeal
was calculated using a factor method given in eq 2. The
conversion factor for soymeal harvested in the USA was
determined and is discussed in section 3.1.3. The nitrogen
content of soymeal was determined using a CHN analyzer
(PerkinElmer, Massachusetts, USA).
protein content (%)
= conversion factor × nitrogen content (%) (2)
2.2.3. Ash and Moisture Content (%). The ash content of
soymeal was determined by TGA. Soymeal was heated to 550
°C with a heating rate of 10 °C/min in air atmosphere, and the
weight percent residue at 550 °C was the ash content of
soymeal. The moisture content of soymeal was determined by
the MX-50 moisture analyzer (A&D Weighing, California,
USA).
2.3. Soymeal Polyol Synthesis. Soymeal composed of
soluble carbohydrates, proteins, ash, moisture, and other
components (insoluble carbohydrates, minerals) was directly
used without any purification for the polyol synthesis. It is a
two-step process but conducted in the same reactor with the
stepwise addition of reactants.
2.3.1. Polyol Synthesis from SoymealChemistry. Step 1:
Transamidation Reaction to Convert Soymeal Proteins to
Amine Derivatives. Soymeal and ethanolamine (1:2, 1:3, and
1:5 mass ratios) were reacted in a reactor. The reactor was
purged with nitrogen gas for 15 min before start of the
reaction. The reaction was conducted for 2 h at a temperature
of 100−105 °C. The intermediate products obtained
containing amino groups were referred to as amine derivatives.
Step 2: Ring Opening of Carbonates to Convert Amine
Derivatives to Polyol. After the transamidation step (step 1),
10% molar excess of propylene carbonate was added to the
reactor. The reaction mixture containing amine derivatives and
propylene carbonate was heated at a temperature of 70−75 °C
for 2 h. A mole of amino groups reacts with a mole of
propylene carbonate producing a polyol with hydroxyl end-
groups. This soymeal polyol contained soluble carbohydrates,
polyol obtained from soymeal proteins, insoluble carbohy-
drates, ash, and minerals.
2.3.2. Model Compound Synthesis. Ethanolamine (MEA)
was reacted with 10% molar excess of propylene carbonate
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(PC). This MEAPC polyol was used as a model compound to Table 1. Formulations for Free-Rise Study of Rigid PUF
determine the ratio of primary to secondary hydroxyl groups
materials JPF SPF 20 SPF 50 SPF 80
resulting from the ring opening reaction of propylene
carbonate with amines. Side B (Parts)
2.3.3. Characterization of Amine Derivatives and Polyols. Jeffol-SG-360 100 80 50 20
The amine derivatives were characterized by amine value, soymeal polyol (SP 1:3) 0 20 50 80
thermogravimetric analysis (TGA), and Fourier transform- Dabco DC193 2.5 2.5 2.5 2.5
infrared spectroscopy (FTIR). The MEAPC and soymeal 33 LV 1.8 1.8 1.8 1.8
polyols were characterized by hydroxyl value, amine value, Niax A1 0.5 0.5 0.5 0.5
viscosity, specific gravity, TGA, FTIR, and insoluble content Polycat 77 1.0 1.0 1.0 1.0
(%). The hydroxyl value of polyols was determined by ASTM water 6 6 6 6
E1899-16, and the amine value was determined by ASTM Side A (Parts)
D2073-92. All titrations were performed using 857 Titrando Rubinate M 191 201 217 233
(Metrohm, Florida, USA) autotitrator. The viscosity of polyols ISO Index 105 105 105 105
was measured at room temperature using a Brookfield
viscometer-LVDV-E model (AMETEK Brookfield, Massachu- 2 min. Rubinate M isocyanate was side A (35−40 g), and its
setts, USA). amount required for all formulations was calculated using the
TGA was performed on a sample using thermogravimetric isocyanate index 105. Side A was added to side B, and the
analyzer, TGA Q50 (TA Instruments, Delaware, USA). In this mixture was thoroughly blended for ∼10−15 s (mix time).
analysis, a sample (10−15 mg) was taken in an aluminum pan The characteristic times (cream, top of the cup, string gel, rise,
and heated to 550 °C with a heating rate of 10 °C/min. The and tack-free) for each PUF were recorded. At cream time, the
weight loss (%) of the sample as a function of temperature viscosity of polyol and isocyanate mixture increases; at top of
(°C) was obtained from this analysis. The derivative the cup time, the foam reaches top of the cup; at string gel
thermogravimetric graphs (DTG) (%/°C) were used to time, polyurethane network starts building; at rise time, the
identify the degradation temperatures. foam stops rising; and at tack-free time, the foam is no longer
Attenuated total reflection-Fourier transform infrared spec- sticky.
troscopy (ATR-FTIR) spectra of soymeal, amine derivatives, 2.4.2. Properties of Rigid PUF. A mold of dimensions 13 cm
and soymeal polyol were acquired on a FTIR (Shimadzu Co., × 18 cm × 37 cm was used to make a box foam. A mold
Tokyo, Japan, IRAffinity-1) equipped with a single reflection release was applied inside the box and the box was kept in the
ATR system (PIKE Technologies, Wisconsin, USA, MIRacle oven for 10 min at 65 °C. Meanwhile, all ingredients of side B
ATR). The ATR-FTIR used with a resolution 4 cm−1, Happ- was measured in the proportion mentioned earlier and mixed
Genzel apodization function, and 64 scans were conducted on for 2−3 min. Side A was added to side B and mixed for 12 s.
the sample. The output from FTIR was recorded as The mixture was immediately poured inside the preheated box
transmittance (%) as a function of wavenumber (cm−1). and lid was closed. After 10−15 min, the foam was removed
The 13carbon-nuclear magnetic resonance (13C NMR) from the box and kept at room temperature. After 7 days of
spectrum was recorded on a 500 MHz NMR spectrometer foam manufacturing, the foam was cut to measure its
(Varian Inc., USA, Unity Plus 500 MHz) using deuterated properties. The outer skin of the box foam was removed by
dimethyl sulfoxide (DMSO-d6) as a solvent having tetrame- cutting 1 cm from all sides. ASTM 1622-14 and ASTM 1621-
thylsilane as an internal standard. The spectrum of MEAPC 16 standards were used to determine density, and the
polyol was recorded at ambient temperature (22 °C), compressive strength of the foam samples of dimension 6 cm
relaxation delay was 25 s, the number of scans were 256, × 6 cm × 3.5 cm, respectively. The compressive strength of
and inverse gated decoupling was used (decoupling only foams was tested in the direction perpendicular to the rise
during acquisition). This spectrum was used to quantify the direction of foams with a speed of 3.4 mm/min and it was
ratio of primary to secondary hydroxyl groups obtained during measured at a deformation of 13% or yield point, whichever
the ring opening reaction of propylene carbonate (step 2 of the occurs first.
soymeal polyol synthesis). Cell morphologies of all foams were studied in parallel and
The amount of insoluble content was measured at different perpendicular to the rise direction of foams using a JEOL
time intervals for the transamidation reaction to study its 6610LV (tungsten hairpin emitter) scanning electron micro-
reaction kinetics. A small amount of sample was dissolved in scope (SEM) (JEOL Ltd., Tokyo, Japan). The samples were
water followed by filtering out the liquid and finally drying the mounted on aluminum stubs using high vacuum carbon tabs
residue in an oven for 24 h. A similar method was used to (SPI Supplies, Pennsylvania, USA). Samples were coated with
determine the insoluble content of the soymeal polyol. platinum (Pt) of approximate thickness of 8 mm in a Quorum
2.4. Biobased Polyurethane Foams (PUF). 2.4.1. Free- Technologies/Electron Microscopy Sciences Q150T turbo
Rise Study of PUF. The free-rise study of PUF was performed pumped sputter coater (Quorum Technologies, Laughton,
as per ASTM standard D7487-13. The catalyst concentration East Sussex, England BN8 6BN) purged with argon gas.
was optimized for Jeffol polyurethane foam (JPF, control
PUF), and it is given in Table 1. The same catalyst 3. RESULT AND DISCUSSION
concentration was used for soymeal polyol polyurethane 3.1. Composition Analysis of Soymeal. The soymeal
foams (SPF 20, SPF 50, SPF 80). In a plastic cup, side B contains proteins, carbohydrates, and other components as
(20 g) components, that is, polyols, gelling catalyst (Dabco 33 shown in Figure S1. To fully utilize the whole soymeal without
LV), silicone surfactant (Dabco DC 193), blowing catalyst separating carbohydrates or protein components, it is
(Niax A-1), catalyst (Polycat 77), and blowing agent (water), necessary to determine the composition of soymeal compo-
were homogeneously mixed using a stirrer at high rpm for ∼1− nents and characterize it. Soymeal composition may vary
5735 https://doi.org/10.1021/acs.iecr.0c06306
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Industrial & Engineering Chemistry Research
depending on species or crop location. Also, the composition
of proteins and carbohydrates is different for different biomass
such as DDGS, Jatropha meal, etc.
3.1.1. Separation of Soluble Carbohydrates. The carbohy-
drates present in soymeal consist of 10% free sugars (mono-,
di-, and oligosaccharide), 20−30% of nonstarch polysacchar-
ides (NSP), and 1% of starch.29 Free sugars present in soymeal,
that is, sucrose, stachyose, and raffinose, are soluble in water as
well as in the ethanol−water solution.30,31 Nonstarch
polysaccharides (NSP) consist of pectins and cellulose.29
Pectins are mainly composed of rhamnose, fucose, arabinose,
xylose, mannose, galactose, glucose, and uronic acids, and they
are partially soluble in water.29 Cellulose and starch are
insoluble in water. The soluble carbohydrates which consist of
free sugars and some pectins can be separated from soymeal
using aqueous alcoholic solution.29 Water can be used for the
extraction of free sugars, but it is also a good solvent for some
proteins.30 Therefore, the extraction was carried out using an
alcohol−water solution. Incomplete extraction of soluble
sugars was observed with an increase in the strength of
alcohol from 50% (v/v) to 90% (v/v).30−32 Also, the effect of
50% (v/v) ethanol or methanol was the same on the extraction
of soluble carbohydrates from soymeal, and the effect of
temperature was also negligible.30 Considering these, the
separation of soluble carbohydrates was carried out at an
ambient temperature and using 50% (v/v) ethanol−water
solution. The experimental results of the separation of soluble
carbohydrates from soymeal are given in Table 2. Soymeal (8
Table 2. Composition of Soluble Carbohydrates and
Insoluble Components of Soymeal
components of soymeal
(soymeal initial degradation
weight = 8.00 g) stages components
soluble carbohydrates 25−150 °C moisture
(1.96 ± 0.05 g) 150−250 °C soluble carbohydrates and
250−350 °C some soluble proteins
350−550 °C
insoluble components of 150−350 °C insoluble carbohydrates,
soymeal (5.58 ± 0.02 g) 350−550 °C proteins, and minerals
g) approximately contains 70% (5.58 g) of insoluble
components and 25% (1.96 g) of soluble components. The
insoluble components of soymeal are proteins, insoluble
carbohydrates, and minerals, whereas the soluble component
of soymeal is soluble carbohydrates (SC). The soluble
carbohydrates separated from soymeal may contain some
soluble proteins along with the residual moisture. The percent
Figure 1. (a) Thermogravimeric analysis (TGA); (b) derivative thermogravimeric (DTG) graphs of soymeal, soluble carbohydrates, and insoluble
components of soymeal.
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residual moisture present in soluble carbohydrates was
analyzed by TGA and is discussed in the next section.
3.1.2. Thermogravimetric Analysis (TGA). The TGA and
DTG graphs of soymeal, soluble carbohydrates, and insoluble
components of soymeal are shown in Figure 1a,b. The DTG
graph of soymeal gave three major degradation peaks at 91 °C,
226 °C, and 296 °C as shown in Figure 1b. The first
degradation stage (25−140 °C) could be due to the residual
moisture present in soymeal.26 The second degradation stage
(150−300 °C) could be due to the degradation of soy
proteins,26 cleavage of peptide bonds with dissociation of some
bonds25 or degradation of hemicellulose, starch, polysacchar-
ide, proteins.16 The third degradation stage (250−400 °C)
could be due to the degradation of proteins in soymeal.25,26
Also, the degradation of stable metal traces and minerals was
observed after the third degradation stage around ∼500 °C.16
The degradation stages observed in the DTG graph of soluble
carbohydrates and insoluble components of soymeal are given
in Table 2. In the DTG graph of soluble carbohydrates, the
degradation peak around ∼210 °C is present, which is also
observed in the DTG graph of soymeal. However, this peak is
absent in the DTG graph of insoluble components of soymeal.
Thus, we can say that some soluble carbohydrates present in
soymeal degrade around 210 °C. The first degradation stage
(25−150 °C) present in the soluble carbohydrates is due to
the residual moisture. The soluble carbohydrates approx-
imately contain 10% (weight loss at 150 °C) of residual
moisture. Using eq 1, the soluble carbohydrates content of
soymeal was calculated as 22%. The soluble carbohydrates may
contain some soluble proteins.
3.1.3. Protein, Moisture, and Ash Content (%). The crude
protein content in food can be determined by multiplying a
conversion factor to the nitrogen content of the food.33 Jones
found that the nitrogen content in total proteins of a variety of
food varies from 13% to 19%.33 Since then it was assumed that
the average nitrogen content in food is 16% of total proteins,
thereby using 6.25 (conversion factor = 100/16) as a
conversion factor to get the crude protein content.34 Morr
used the factor method to calculate the conversion factor for
soymeal by dividing total amino acid content by nitrogen
content.35 Later, Morr corrected the factor method by using
residue weights of amino acids instead of molecular weights,
and the conversion factor for soymeal was calculated as 5.6−
5.7.36 In the present study, the composition of amino acids of
soymeal harvested in the USA37 was used in conjunction with
the factor method to determine the conversion factor for
soymeal, which was calculated as 5.56 (refer to Table S1). The
analytically measured nitrogen content of soymeal was 8.23%
(determined by CHN analyzer). Hence, the crude protein
content of soymeal was calculated as 45.8% using eq 2. The ash
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content of soymeal was 6.4%, and the moisture content of
soymeal was 6.5%. The amount of insoluble carbohydrates and
minerals present in the soymeal is 19%.
3.2. Soymeal Polyol Synthesis. The soymeal having 46%
protein, 22% soluble carbohydrates, 7% moisture, 6% ash, and
19% other components (insoluble carbohydrates and minerals)
was used for polyol synthesis. Polyols from soymeal have been
reported by us and others as shown in Figure 2. In the first
Figure 2. Different routes used for synthesis of polyols from soymeal:
(1) hydrolysis,20,27 (2) activation,22 (3) transamidation (present
work).
route (hydrolysis), soymeal was hydrolyzed to a mixture of
amino acids which were further converted to a polyol.20,27 In
the second route (activation), the alkali treatment method was
used to modify soymeal which was directly used in PUF
synthesis.22 However, the number of steps involved, and
resultant product properties make these approaches commer-
cially nonviable (see Figure 2). In the third route (present
work), a polyol from soymeal was synthesized without
removing any of the soymeal components, which eliminated
multiple steps and reagent usage. It allowed us to synthesize
the polyol using a two-step one-pot chemistry approach. In the
transamidation route, proteins of soymeal were converted to
amine derivatives which were further converted to polyol. The
other constituents of soymeal, that is, carbohydrates and
minerals, remain as it is (as shown in Figure 2).
Thus, the soymeal polyol is a mixture of polyol obtained
from proteins, carbohydrates, and other components (miner-
als) of soymeal. The detailed polyol synthesis process is
discussed in the next section.
3.2.1. Polyol Synthesis from SoymealChemistry. The
process flow diagram of soymeal polyol (SP 1:3) synthesis is
shown in Figure 3. This process does not require any solvent
or generate any waste.
Step 1: Transamidation Chemistry to Convert Soymeal
Proteins to Amine Derivatives. Soymeal was directly used
without separating proteins or other components. Proteins are
chains of amino acids containing amide linkages as shown in
Figure 4. In the transamidation reaction between proteins of
soymeal and amine of ethanolamine (MEA), the amino group
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Figure 3. Process flow diagram (PFD) and material costs of soymeal
polyol synthesis (SP 1:3).
of ethanolamine attacks the carbonyl carbon of proteins
forming the hydroxylamine derivative (product A, Figure 4).
There was another possibility of the hydroxyl group of
ethanolamine reacting with acid groups of proteins, and giving
a diamine derivative (product B, Figure 4). When soymeal was
reacted with ethylene glycol (two hydroxyl end-groups) at a
temperature of 100−105 °C (mass ratio 1:3), it was found that
the unreacted or water-insoluble content was more than 90%.
Also, when soymeal was reacted with ethylene diamine (two
amino end-groups) at the same conditions, the water-insoluble
content was less than 12%. This proves that the amine group is
more reactive than the hydroxyl group in its reaction with
soymeal. Thus, the amine derivatives obtained from the
reaction of soymeal and ethanolamine contain hydroxylamine
derivatives (A) as a major product along with diamine
derivative as a minor product. The mechanism of trans-
amidation reaction is given in Figure S3 and Figure S4.
When soymeal was reacted with ethanolamine, the water-
insoluble content decreased with time as shown in Figure 5.
The water-insoluble content was less than 3% after an hour.
This indicates that the amine derivatives and most of the
carbohydrates were soluble in the liquid phase. These
carbohydrates contain hydroxyl groups which might react
with isocyanate in the final PUF reaction. The insoluble matter
(<3%) of amine derivatives may contain minerals or insoluble
carbohydrates of soymeal.
Step 2: Ring Opening of Carbonates to Convert Amine
Derivatives to Polyol. The amino end-group of amine
derivatives (hydroxylamine and diamine derivative) can be
converted to the hydroxyl end group by reacting it with
ethylene carbonate (EC) or propylene carbonate (PC). We
discovered that using propylene carbonate, which is a liquid at
room temperature, instead of ethylene carbonate, provided a
solution with much reduced viscosityan essential require-
ment for manufacturing foams.38 Viscous polyols hinder
uniform mixing which is a primary requirement to obtain a
good foam.39 Also, the cost of propylene carbonate (0.5−1.0
$/kg) is considerably lower than the cost of ethylene carbonate
(1.1−1.5 $/kg).
The reaction of amine derivatives with propylene carbonate
was carried out at a lower temperature of 70−75 °C to avoid
formation of substituted ureas.40 Also, previous studies have
shown that the ring-opening of propylene carbonate with
aliphatic amines is instantaneous41 and can be carried at lower
temperatures.42 The reaction of hydroxylamine derivative (A)
with propylene carbonate is shown in Figure 6. The amino
group can break any one of the two ester linkages of propylene
carbonate giving products containing 1° or 2° hydroxyl groups
(Figure 6). The diamine derivative also reacts in a similar
pathway.
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Figure 4. Transamidation of soymeal proteins with ethanolamine to produce amine derivatives.
Figure 5. Percent change in the water-insoluble content during the
transamidation reaction.
The ring-opening reaction of propylene carbonate with the
amine derivative was instantaneous, as the amine value of
amine derivatives decreased drastically during the reaction.
The probable structures of polyol obtained from soymeal
proteins is shown in Figure 6. This polyol contains amide and
urethane linkages, which are less susceptible to degradation by
hydrolysis or UV-radiation as compared to ester or ether
linkages. The conventional polyols typically contain ester and
ether linkages. The soymeal polyol comprises carbohydrates,
polyol obtained from proteins, and other components
(minerals) of soymeal.
Soymeal polyols were synthesized using different mass ratios
of soymeal to ethanolamine (MEA), that is, 1:2, 1:3, and 1:5.
The intermediate product, amine derivatives (AD), and the
corresponding soymeal polyols (SP) were characterized, and
results are shown in Table 3. The amine value of amine
derivatives, after their reaction with propylene carbonate,
decreases from 500 to 700 mg of KOH/g to 5−10 mg of
KOH/g (Table 3). This confirms the reaction of amines with
propylene carbonate. The SP 1:2 polyol (613 mg of KOH/g)
had a higher hydroxyl value as compared to SP 1:3 polyol (568
mg of KOH/g) which could be due the presence of higher
amounts of soluble carbohydrates contributing to the hydroxyl
value. Whereas the higher hydroxyl value of SP 1:5 polyol (647
mg of KOH/g) as compared to SP 1:3 polyol could be due to
the increase in ethanolamine amount. Also, the soymeal polyol
Figure 6. Ring opening of propylene carbonate with the amine of hydroxylamine derivative.
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SP 1:2 was very viscous compared to SP 1:3 and SP 1:5
polyols.
The SP 1:3 polyol was chosen to make PUF due to its higher
biobased content as compared to the SP 1:5 polyol. The
hydroxyl value of soymeal polyols can be reduced by using a
long-chain amino-alcohol instead of ethanolamine. The
soymeal polyols have some amine content which might act
as a catalyst in PUF synthesis, thereby reducing the catalyst
amount required in PUF. Soymeal polyols also have 1−4% of
insoluble matter, which could be due to the insoluble
components of soymeal, that is, carbohydrates and minerals.
As proteins were involved in the reaction chemistry of polyol
synthesis, the properties of polyol given in Table 3 depend on
the protein content. The hydroxyl value and other properties
might change with changing the biomass used for polyol
synthesis.
3.2.2. Fourier Transform Infrared Spectroscopy (FTIR).
The ATR-FTIR spectra of soymeal, amine derivative (AD 1:3),
and soymeal polyol (SP 1:3) are given in Figure 7. The peak at
3200 cm−1 present in the spectrum of soymeal was attributed
to the OH stretch,43 which was also present in the spectra of
amine derivative and soymeal polyol. The additional peaks
around 3300 cm−1 present in the spectrum of amine derivatives
were attributed to the N−H stretch of 1° and 2° amines.43 The
C−H stretch was observed around 2900 cm−1 in the spectra of
all compounds. The small peak around 1750 cm−1 present in
the spectrum of soymeal polyol was expected due to the CO
group of esters43 or urethane linkages. The peaks around 1690
and 1530 cm−1 present in the spectrum of soymeal polyol were
attributed to the CO and N−H groups of amide linkages.43
3.2.3. Nuclear Magnetic Resonance (NMR) Spectroscopy.
The ratio of a secondary (2°) to primary (1°) hydroxyl group
produced from a ring-opening reaction of cyclic carbonates
with different primary amines, has been determined
previously.40,44 Baizer et al. used infrared spectroscopy
technique to obtain the ratio as 65:35.45 Steblyanko et al.
found the ratio as 82:18 using 1H NMR spectroscopy.46 This
ratio was also obtained by 13C NMR spectroscopy.47 In this
study, the ratio was determined using 13C NMR spectroscopy,
as the reactivity of polyol toward isocyanate depends on the
relative concentration of 2° to 1° hydroxyl group.47 The ring-
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Table 3. Characterization of Different Amine Derivatives and Polyols

amine derivatives (AD) polyol properties
amine value amine value hydroxyl value specific viscosity@ 25 °C insoluble content
polyols (mg of KOH/g) (mg of KOH/g) (mg of KOH/g) gravity (Pa·s) (%)
SP1:2 563 ± 11 10 ± 1 613 ± 10 1.15 230 <4
SP1:3 772 ± 8 6±2 568 ± 10 1.18 37 <2
SP1:5 716 ± 15 5±1 647 ± 15 1.15 28 <1
MEAPC 3±1 709 ± 12 1.20 5

hydroxyl carbon from ethanolamine,47 whereas the peak at

Figure 7. FTIR spectra of soymeal, amine derivative (AD 1:3), and
soymeal polyol (SP 1:3).
opening of propylene carbonate (PC) with ethanolamine was
used as a model reaction, and the probable structures of the
obtained MEAPC polyol are given in Figure 8(a,b). All peaks
present in the 13C NMR spectrum of MEAPC polyol are
assigned to the carbon atoms present in both chemical
structures (a and b) as shown in Figure 8. The peaks at 60.45
ppm (5) and 60.48 ppm (6) correspond to the primary
65.05 ppm (8) corresponds to the secondary hydroxyl
carbon.47 The peak at 64.46 ppm (7) also corresponds to
the primary hydroxyl carbon. These peaks were integrated to
calculate the ratio of secondary to primary hydroxyl groups and
this was found to be 27:73. Thus, it was confirmed that the
soymeal polyol contains more primary hydroxyl groups than
secondary hydroxyl groups. Also, using this ratio, the chemical
structures (a:b) distribution in MEAPC polyol was found as
approximately 50:50.
3.2.4. Thermogravimetric Analysis (TGA). The thermogra-
vimetric analysis (TGA) graphs of soymeal, amine derivatives
(AD 1:3), and soymeal polyol (SP 1:3) are shown in Figure 9.
In the TGA graph of amine derivatives, the degradation stage I
(50−150 °C) was due to ethanolamine and water, the
degradation stage II (150−250 °C) and stage III (250−350
°C) were due to the low and high molecular weight amine
derivatives, respectively, whereas in the TGA graph of the
soymeal polyol, the two degradation stages, that is, stage I
(75−175 °C) and stage II (175−275 °C) could be due to the
polyols with different molecular weights.

Figure 8. 13C NMR spectrum of ethanolamine and propylene carbonate reaction product (MEAPC polyol).

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Figure 9. TGA graphs of soymeal, amine derivative (AD 1:3), and
soymeal polyol (SP 1:3).
3.3. Polyurethane Foams. The reaction chemistry of PUF
synthesis from soymeal polyol (polyols from proteins, and
carbohydrates) is shown in Figure 10. In PUF synthesis, two
Figure 10. Synthesis chemistry of PUF: (A) gelling reaction; (B)
blowing reaction.
reactions occur simultaneously,2 that is, (A) gelling and (B)
blowing, as shown in Figure 10. In the gelling reaction,
hydroxyl groups of polyols react with isocyanate groups of
isocyanates forming urethane linkages. In the blowing reaction,
water reacts with isocyanate forming carbon dioxide gas. As the
blowing reaction is faster than the gelling reaction, catalysts are
required in PUF synthesis to balance both reactions. The
catalyst concentration was optimized to obtain a good control
foam (JPF), and the same catalyst concentration was used for
soymeal polyol foams (SPF 20, SPF 50, SPF 80). JPF is made
with commercial Jeffol-SG-360 polyol. Whereas SPF 20, SPF
50, and SPF 80 are biobased PUF made with 20%, 50%, and
80% of soymeal polyol (SP 1:3), respectively.
3.3.1. Free-Rise Study of PUF. The free-rise profiles of
formulations given in Table 1 are shown in Figure 11. It was
Figure 11. Free rise profiles of JPF (0% SP), SPF 20 (20% SP), SPF
50 (50% SP), and SPF 80 (80% SP).
observed that at the end of rise, all foams were tack free. It was
also observed that the rise time of foam increases as the
soymeal polyol content increases except for SPF 20, where rise
time decreased as compared to the control foam. This could be
due to the presence of amines in the soymeal polyol acting as a
catalyst in the PUF synthesis. The increase in the characteristic
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time for SPF 50 and SPF 80 foams could be due to the
decrease in the amount of catalysts per polyol-isocyanate
reaction. The hydroxyl value of soymeal polyol is higher than
the hydroxyl value of Jeffol-SG-360 polyol. Increasing the
concentration of soymeal polyol increases the amount of
isocyanate used in PUF. As the same amount of catalysts was
added in each formulation, the catalysts concentration per
polyol-isocyanate reaction was actually lower for SPF 20, SPF
50, and SPF 80 foams compared to JPF foam (control foam).
The SPF 20 and SPF 50 foams were comparable to control
foam with respect to characteristic times and internal foam
structure. Thus, PUF containing 20% and 50% of soymeal
polyol were further evaluated for compressive strength and cell
structure.
3.3.2. Properties of PUF. The density of rigid PUF should
be greater than 30 kg/m3 to maintain a certain amount of
strength for commercial applications.22 The density of foam
depends on the amount of CO2 produced, which further
depends on the amount of water added. Properties of foam are
strongly dependent on its density.2,48 Thus, densities of foam
should be similar in order to compare their properties. The
density and compressive strength of JPF, SPF 20, and SPF 50
are given in Table 4. The compressive strength of SPF 20 is
Table 4. Properties of Polyurethane Rigid Foams
density compressive cell size cell size
PUF (kg/m3) strength (kPa) (μm) ∥el (μm) ⊥er
JPF (control) 39.2 ± 0.5 218.8 ± 21.6 336 ± 31 333 ± 28
SPF 20 41.7 ± 0.8 257.1 ± 15.1 280 ± 27 302 ± 19
SPF 50 41.0 ± 2.0 203.4 ± 39.0 386 ± 27 337 ± 24
slightly higher than the compressive strength of JPF and SPF
50. This could be due to the slightly higher density of SPF 20
as compared to JPF and SPF 50. Overall the compressive
strength of JPF, SPF 20, and SPF 50 are comparable.
The SEM was used to study the foam morphology. The
SEM images of JPF, SPF 20, and SPF 50 foams, in parallel (∥el)
and in perpendicular (⊥er) to the rise direction of foams are
shown in Figure 12. The SEM images of all foams showed
closed cell structure which is important for insulation
applications. The smaller average cell size of SPF 20 (∥el)
compared to the JPF (∥el) (Table 4) could be due to the
higher viscosity of the soymeal polyol. The higher viscosity can
affect the pulling of cells against gravity during rising, thus
leading to smaller average cell size.3 An increase in water
content produces more CO2 due to which the average cell size
increases,5 and a higher rise time provides cells sufficient time
to grow. Thus, the average cell size of SPF 50 (∥el) was greater
than the JPF, as water content and rise time of SPF 50% was
higher compared to the JPF.
As cell size of a foam increases, its compressive strength and
density both decrease.3 Thus, the compressive strength of JPF
and SPF 50 was lower compared to the SPF 20. The cell size of
foams in perpendicular to the rise direction did not change
much with the addition of soymeal polyol. The aging and water
absorption studies of these biobased PUF are included in the
Supporting Information.
4. CONCLUSION
This study reports on manufacturing greener, value-added, and
cost-effective polyols from undervalued soymeal. Detailed
characterization of the soymeal was necessary to benchmark
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Industrial & Engineering Chemistry Research
Figure 12. SEM images of (a) JPF, (b) SPF 20, (c) SPF 50 foams parallel to the rise direction; SEM images of (d) JPF, (e) SPF 20, (f) SPF 50
foams perpendicular to the rise direction (rise direction is shown with an arrow for a, b, c; rise direction is perpendicular to the plane of paper for d,
e, f).
the properties of the resultant soymeal polyol. The biobased
polyol was synthesized by using a two-step one-pot process
chemistry. Soymeal without any purification was reacted with
ethanolamine to yield amine derivatives (Figure 4, hydroxyl-
amine, and diamine derivative), which were then reacted with
propylene carbonate in a sequential second step to yield the
desired polyols (Figure 6). 13C NMR showed that the majority
of the hydroxyl groups were primary. The insoluble content in
the soymeal polyol was less than 2% which confirmed that the
majority of soymeal constituents were taking part in the
reaction. Typically, commercial polyol manufacturing pro-
cesses require catalysts and longer reaction times. In our
manufacturing process, polyols were synthesized in 2−4 h
without the addition of any catalyst (reducing costs and
catalyst recovery or contamination issues). The hydroxyl value
of soymeal polyol is 550 mg of KOH/g which makes it suitable
for use in the manufacture of rigid polyurethane foams. This
hydroxyl value depends on the chain length of amino-alcohol
used. Thus, polyols with lower hydroxyl value can also be
synthesized using long-chain amino-alcohol or diamines such
as hexamethylene diamine (HMDA). The material costs for
the manufacture of soymeal polyols fall in the $0.6−0.7/lb
range (Figure 3) and make its commercial use viable. The
performance properties of biobased rigid PUF were com-
parable to the PUF made with commercial polyol.
The key innovation in this work is the direct conversion of
soymeal (without any purification or separation) to a usable
polyol for rigid PUF applications and the new process
chemistry developed. This polyol manufacturing process is
not limited to using soymeal but can be applied to any
available and low-cost biomass such as Jatropha meal or
DDGS.
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.iecr.0c06306.
Soybean oil separation, factor method, FTIR of soymeal
and soluble carbohydrates, transamidation mechanism,
kinetic study of transamidation reaction, overall polyol
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synthesis pathway, 1H NMR of MEAPC polyol, aging
study of PUF at 25 and 70 °C, water absorption study of
PUF at 25 °C (PDF)
■ AUTHOR INFORMATION
Corresponding Author
Ramani Narayan − Department of Chemical Engineering and
Materials Science, Michigan State University, East Lansing,
Michigan 48824, United States; orcid.org/0000-0003-
3715-5092; Email: narayan@msu.edu
Author
Sayli Devdas Bote − Department of Chemical Engineering and
Materials Science, Michigan State University, East Lansing,
Michigan 48824, United States; orcid.org/0000-0001-
6803-4053
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.iecr.0c06306
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors thank Zeeland Farm Services, Inc. for providing
the soymeal sample. The authors also acknowledge Huntsman
Corporation (Texas, USA), Air Products and Chemicals, Inc.
(Pennsylvania, USA), and Momentive Performance Materials
(New York, USA) for providing materials for foam
formulations.
■
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