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Flame Retardant Characteristics of Recycled- and

Lignin-Based PET Polyols for Rigid Foam


Applications
KEVIN A. ROGERS SHAKTI L. MUKERJEE
Resinate Materials Group, Inc. Resinate Materials Group, Inc.
46701 Commerce Center Drive, Suite C 46701 Commerce Center Drive, Suite C
Plymouth, MI 48170 Plymouth, MI 48170

JOSHUA N. CUPP RICK L. TABOR


Resinate Materials Group, Inc. Resinate Materials Group, Inc.
46701 Commerce Center Drive, Suite C 46701 Commerce Center Drive, Suite C
Plymouth, MI 48170 Plymouth, MI 48170

ABSTRACT

Halogenated flame retardant agents have protected the public from injury and death by helping to prevent
fires in buildings and dwellings for many decades. Today, new flame retardant options are being sought
that are based on green chemistry and that contain no halogens for use in rigid foam applications. Resinate
Materials Group, Inc. has developed green-content aromatic polyester polyols that provide improved flame
retardant performance in polyisocyanurate (PIR) insulating foams. The green content of these new polyol
products originates from biorenewable lignin and recycled polyethylene terephthalate. This paper details
the performance of these emerging sustainable-content polyols in PIR foam applications.

INTRODUCTION

Aromatic polyester polyols are commonly used intermediates for the manufacture of polyurethane
products, including spray, flexible, and rigid foams, polyisocyanurate foams, coatings, sealants, adhesives,
and elastomers. The aromatic content of these polyols contributes to strength, and thermal stability of the
urethane product. Generally an aromatic polyester polyol is produced by condensing aromatic diacids,
diesters, or anhydrides (e.g., terephthalic acid, dimethyl terephthalate) via reaction with glycols such as
ethylene glycol, propylene glycol, or diethylene glycol. These starting materials are usually derived
exclusively from petrochemical sources. As companies increasingly seek to offer products with improved
sustainability, the availability of intermediates produced from bio-renewable and/or recycled materials
becomes more leveraging. However, there remains a need for these products to deliver equal or better
performance than their traditional petroleum-based alternatives economically.
The deliberation over whether or not bio-renewable content can be considered an indicator of
“green” chemistry has vacillated over the past decade. In the past when a food source such as corn was
needed to provide the bio-renewable content, a prevalent school of thought acknowledged clear trade-offs
between feeding people and providing them with performance-based chemical products. Additionally, these
advocates alleged that chemical or biochemical transformations needed to convert sugars or other bio-
friendly feeds to useful chemical intermediates such as polyols might consume more natural resources and
energy and release more greenhouse gases and pollutants into the environment than their petro-based
alternatives in the effort to achieve “green” status.1
Nevertheless, recent findings reported in the European Bio-plastics journal2a and a news report by
Emmanuel Desplechin in the European Union ePure science section in EU Politico entitled “The Five
Myths about the Food versus Fuel Debate” 2b explicitly dispel many of the longstanding misrepresentations
with regard to the adverse effects of utilizing land resources for biofuels; particularly as they relate to their
utility for agricultural purposes for human and animal consumption. Moreover, comparisons of life cycle
analysis for products obtained from bio-renewable and petroleum feedstocks in the EU report provide
persuasive evidence indicating that less than 1% of the total bio-renewable feedstocks being produced

©2017 American Chemistry Council


might have had any undesirable consequence on food production. Likewise, the same report has presented
that production of bio-fuels from bio-feedstocks has resulted in economic benefits for many of the EU
countries both in terms of agriculture and commerce.
Waste thermoplastic polyesters, including waste polyethylene terephthalate (PET) streams (e.g.,
from plastic beverage containers or from carpet), provide an abundant source of raw material for making
new polymers. Usually, when PET is recycled, it is used to make new PET beverage bottles, PET fiber, or
it is chemically transformed to produce polybutylene terephthalate (PBT). Other recycled raw materials are
also available. For example, recycled propylene glycol is available from aircraft deicing or RV winterizing
and other operations, and recycled ethylene glycol is available from spent vehicle coolants. Urethane
formulators demand polyols that meet required specifications for color, clarity, hydroxyl number,
functionality, acid number, viscosity, and other properties. These specifications will vary and depend on the
type of urethane application. For instance, rigid foams generally require polyols with higher hydroxyl
numbers than the polyols used to make flexible foams.
Many references describe digestion of rPET with glycols (also called “glycolysis”), usually in the
presence of a catalyst such as zinc, titanium, or tin. Digestion converts the polymer to a mixture of glycols
and low-molecular-weight PET oligomers. Although such mixtures have desirably low viscosities, they
often have high hydroxyl numbers or high levels of free glycols. Frequently, the target product is a purified
bis(hydroxyalkyl) terephthalate.3 or terephthalic acid.4-6 D. Paszun and T. Spychaj in a review article have
described some of the efforts that have been undertaken to use glycolysis product mixtures for urethane
manufacture.7
Lignin is a principal component of vascular plants, contributing 20-30 wt.% to dry softwoods and
hardwoods. It is an amorphous, polyphenolic material produced from an enzyme-catalyzed polymerization
of coniferyl alcohol, sinapyl alcohol, and p-coumaryl alcohol (Figure 1). Industrial lignin is a by-product of
the pulp and paper industry.

Figure 1: Structure of mono-lignols and lignin

Two types, kraft lignin (also called “alkali lignin”) and lignosulfonates, are available
commercially.8 Organosolv lignins, a more soluble form of lignin, can be obtained by pulping wood with
solvents such as alcohols or aqueous acetic acid, but organosolv lignins have not yet become widely
available. Lignosulfonates have been used as water reducers for concrete and as dispersants for gypsum
wallboard. Alkali lignins generally have lower molecular weight, narrower molecular weight distribution,
and lower water solubility (except at higher pH) compared with lignosulfonates. Once sulfonated, however,
alkali lignin is generally useful in a variety of dispersant applications. So far, organosolv lignins have had
only limited practical utility. Lignins have been incorporated into polyurethane foams and other products,
typically by including the lignin as a filler or additive.9-11 Lignin has also been modified by reaction with
maleic anhydride, propylene oxide, or other reactants to give polyetherester intermediates for

©2017 American Chemistry Council


polyurethanes.12 Furthermore, Enerlab 2000 Inc., has reported on the process for the preparation of lignin
based polyurethane products employing lignin sulfonic acids.13

EXPERIMENTAL

A. Preparation of Aromatic Polyester Polyols using rPET

Typical Two-Step Procedure


The synthesis of the aromatic polyester polyols (APP) described in this paper have been
previously described elsewhere.14a, b, c Briefly, a reactor equipped with an overhead mixer, stir-shaft and
blade, heating mantle, thermocouple, nitrogen inlet, short-path condenser equipped to 15°C chiller, and
round-bottom receiving flask was charged with recycled polyethylene terephthalate pellets and the glycols
chosen for digestion. The mixture was heated and stirred until the reactor contents reached 180°C. 50% of
the catalyst required (500ppm) was added to the reaction and the heating continued to 225°C. The mixture
was heated until no particles of recycled PET remained (about 4 h). When the digestion reaction was
considered complete, the mixture was cooled to about 100°C. All remaining components were added to the
reactor, including hydrophobes, diacids, and lignin. After the addition, the temperature of the reaction was
set to 130°C. The lignin of choice for our reactions, Lignin A, contains about 50% water by weight. This
water was removed before any of the esterification of the dicarboxylic acids occurred in the reaction. After
the head temperature of the distillate fell below 50°C, the temperature was increased to 185°C. If the polyol
does not contain lignin its temperature is set to 185°C from the start of esterification. Once the reaction
reached 185°C and the head temperature of the distillate fell below 50°C the second half charge of catalyst
(500ppm) was added to the reaction and the temperature was increased to 225°C. The reaction was run to
completion, described by an acid value of less than 2.0 mgKOH/g obtained by potentiometric titration. It
may be necessary for minor increases in nitrogen flow rate from 0.2 SCFH to 0.6 SCFH, wrapping
insulation around the reactor, and increasing mixing speed from 200 to 400 rpm to shorten the length of the
reaction. Typically the reaction time for the second step was 10-12 hours. When the reaction was
considered complete, the polyol product was allowed to cool to 100°C and poured through a 100 micron
paint filter into a glass jar. Properties such as hydroxyl value, acid value, viscosity, and density were
recorded for each polyol.

B. Preparation of Aromatic Polyester Polyols using PA

Typical One-Step Procedure


In a reactor equipped with an overhead mixer, stir-shaft and blade, heating mantle, thermocouple,
nitrogen inlet, short-path condenser equipped to 15°C chiller, and round-bottom receiving flask was
charged with the desired aromatic source material (phthalic anhydride), and any glycols, diacids, and
hydrophobes chosen for the reaction. If the aromatic source was phthalic anhydride and the composition
contained lignin it was also added at start since no digestion of a large polymer is required prior to reaction
of the lignin. The mixture was heated and stirred at 200 rpm with nitrogen at 0.2 SCFH until the reactor
contents reached 185°C. Water was removed as the esterification reaction proceeded. When the head
temperature dropped below 75°C, 50% of the catalyst required (500 ppm) was added to the reaction and the
heating continued to 225°C. The reaction heat was turned off after 8 hours and cooled to room temperature
overnight. The following morning, the remaining amount of catalyst was added and the reaction
temperature was set to 225°C with stirring and nitrogen. After approximately 6 hours a sample was
removed and the acid value was found to be less than 2. The reaction was considered complete and the
mixture was cooled to about 100°C and poured through a 100 micron paint filter into a glass jar. Properties
such as hydroxyl value, acid value, viscosity, and density were recorded for each polyol.

C. Preparation of Rigid Foam

Part B of the foam formulation listed in Table 1 was made in a stainless steel griffin beaker by
adding the desired polyol followed by tris(1-chloro-2-propyl)phosphate (TCPP), two different catalysts, a
silicone surfactant, and water. The contents of the beaker were mixed at 2000 rpm for 90 seconds using an
overhead mixer equipped with a 3-inch cowles blade. N-pentane was added to the polyol mixture and
mixed at 2000 rpm for 30 seconds or until homogenous. Weights of the beaker and cowles blade are

©2017 American Chemistry Council


recorded before and after mixing to account for any pentane loss that is added in when necessary and mixed
for another 15 seconds. Part A, comprised of a polymeric form of methylene diphenyl diisocyanate (MDI)
with an equivalent weight of 135 and a functionality of 2.7 of was quickly added at an index of 260.
Immediately after addition of Part A to Part B, the beaker was held under the mixer at up to 2,000 rpm for
fifteen seconds. The mixing time was controlled with an electronic timer and foot pedal attachment.
Immediately after mixing stopped, the well-mixed foam was poured into a 165 oz paper bucket or an
8”x8”x8” cardboard box depending on the desired tests and allowed to rise. The foam was held at ambient
conditions for at least 24 hours before being cut for testing as explained in the sections below.

Material PPH
Aromatic Polyester Polyol 100
Halogenated FR 18
Catalyst 1 2.3
Catalyst 2 0.2
Surfactant 3.8
Water 0.5
n-Pentane 25.5
Table 1: Typical Part B formulation for rigid foam preparation

D. Muffle Furnace Char Test Procedure

The purpose of the muffle furnace char test is to measure dimensional changes and mass loss
caused by high temperatures. At least 2 samples having dimensions of 4 by 4 by 2 inches are cut from a
rigid foam sample. Each sample has its dimensions recorded using a digital caliper to the thousandth inch.
A high temperature paint marker is used to mark each side. The sample is wrapped in a single layer of
aluminum foil with the folds on the length sides. Once the weight is recorded the sample is placed into an
open top metal box with a lid placed over the sample. The box is placed inside a muffle furnace at 450°C
and a timer of 20 minutes is started. Once the time expires, the container is removed from the furnace and
allowed to cool to room temperature. The sample is carefully removed from the box and its weight is
recorded. The foil is removed and the new dimensions of the block are recorded. The charred sample is cut
in the middle, parallel to the width sides, and a picture is taken to show the char formation of the foam
block.

E. Physical Properties of Foam

While all foam samples were produced in the lab at Resinate Materials Group, not all of the
characterization of the foams was completed there. Two external testing facilities: Troy Polymers (Troy,
MI) and 3-B Combustion, Explosion and Fire Consultants (Okemos, MI) were contracted to complete
particular foam characterization tests. The tests conducted are shown in Table 2 below.

Test Name Testing Facility Method Result Form


Core Density ASTM D1622 lb/ft3 (pcf)
Troy Polymers
Thermal Conductivity ASTM C518 W/mK
Troy, MI
Compressive Strength ASTM D1621 psi
3-B Combustion,
Explosion and kW/m2, MJ/m2, MJ/kg,
Cone Calorimeter Testing ASTM E1354
Fire Consultants m2/m2, kg/kg, g/s
Okemos, MI
Table 2: External Foam Characterization Tests

Rigid foam samples were cut to the appropriate sizes for each ASTM. Core density was tested
using six 2 by 2 by 1 inch blocks followed by compressive strength testing on the same blocks. Thermal
conductivity was tested on three 6 by 6 by 1 inch blocks. The cone calorimeter testing required blocks sized
at 4 by 4 by 1 inch.

©2017 American Chemistry Council


RESULTS AND DISCUSSION
There is precedence in the literature about flame retardancy and thermal stability exhibited by
rigid foams and elastomers that are made with APPs.15 Although the importance of studying thermal
degradation, and understanding the processes occurring during thermal stress as well as the parameters
affecting the thermal stability of PU rigid foams are crucial in order to effectively design the foam products
for displaying tailor-made properties suitable for the particular environment where they are to be used, our
objective for this project was much narrower; and was fundamentally designed to see, if a quantification of
any enhancement in the flame spread inhibition or the flame retardant characteristics could be discerned
when lignin was added to the polyol composition.
A. Effect of Lignin Incorporation in rPET Based Polyols

To assess the ability of lignin to improve flame retardant properties we designed a set of
experiments where the amount of recycled PET is held constant and varying amounts of lignin are added
from 2.5 wt% up to 15 wt%. The recycled PET used was in the form of a pellet sourced from 100% post
consumer recycled bottles. The glycols and diacids used were the same throughout the entire study and
only varied in weight percent to equate the same value of theoretical overall molecular weight and hydroxyl
value. Although we have incorporated lignin from various suppliers into our polyester polyols, this
endeavor primarily focused on a specific kraft lignin received from a single supplier, Hinton Pulp, a
division of West Fraser Mills Ltd in Alberta, Canada, who provided the material under the commercial
name Lignin A. To determine the efficacy of lignin incorporation as a flame spread inhibitor and a flame
retardant for rigid foams, the project was split into two separate groups. Table 3 presents the composition of
the polyols in reference to the experiments that were carried out for the first set of investigation utilizing
recycled PET as the main aromatic polyester. For all the polyester polyols synthesized in this set of
experiments, the theoretical hydroxyl value (OHV) was targeted at 250 mgKOH/g and functionality of the
polyol was set to an average of 2 based on the hydroxyl functional material added not including lignin.

Polyol Example 1 2 3 4 5
Kraft lignin - 2.5 5 10 15
Table 3: Amount of lignin in PET Polyol
Example 1 was specifically planned to substantiate the base performance of an rPET based polyol
in flame retardant conditions when the polyol does not contain lignin. Examples 1 through 5 all have
equivalent amounts of rPET with all other components being the same as well. Our hypothesis for these
experiments was that an inclusion of lignin into the polyol composition would improve rigid foam
performance when tested in a cone calorimeter and char forming conditions. Presumably, the high
percentage of aromatic rings in the lignin structure would provide improvements in performance over a
similar polyol with less aromatic content.14

B. Effect of Lignin Incorporation in Phthalic Anhydride Based Polyols

A second set of experiments was planned to determine what the resulting performance of lignin
incorporation in a polyester polyol exhibits when other aromatic sources are utilized. Using example 1 as a
typical polyol formulation containing rPET we calculated the aromatic content in the polyol. First, the
aromaticity of PET itself was calculated by dividing the mass of the benzene ring with the mass of the rPET
monomer unit to obtain 39.6% aromaticity per repeat unit of rPET. The 39.6% is multiplied by the weight
of rPET in the polyol to achieve a total weight percentage of aromaticity, not including the contributions
from the lignin. Finally, using the calculated value for the percent aromatic content we calculated the
required amount of phthalic anhydride (PA) to achieve the same level of aromaticity as the rPET polyol.
For all the polyester polyols synthesized in this second set of experiments listed in Table 4, the hydroxyl
value (OHV) was targeted at 250 mgKOH/g and functionality of the polyol was set to an average of 2
based on the hydroxyl functional material added.

Polyol Example 6 7
Kraft lignin 0 5
Table 4: Amount of lignin in PA Polyol

©2017 American Chemistry Council


Furthermore, besides the rPET-based polyol we chose the phthalic anhydride based polyol (Table
4), as it is a common aromatic source material used for producing commercially available polyols for rigid
foams. If the presence of lignin would play any role in phthalic-based polyesters it could become apparent
in the comparison testing within this set of experiments.
For the above set of experiments, it must be noted that the aromatic contribution from the phenyl
moiety in each polyol was kept constant for two reasons. The first was to ensure that the flame suppressant
properties, produced from the aromatic content would be consistent across the board. The second reason
was to be able to validate whether a measurable advantage would be seen in the lignin containing polyol
formulation when these results were compared.
C. Polyol Properties
The results for all polyol examples are quite similar in hydroxyl value (OHV), acid value (ACV),
and density. The hydroxyl and acid values are controlled based on composition and total time of reaction.
Monitoring the acid value of an in-process reaction will provide an indication of a complete reaction, as
described by an acid value of less than 2. Where the examples differ the most is with their viscosity. As
anticipated, both polyol examples containing no lignin show the lowest viscosity when tested at 25°C.
However, the rPET polyols exhibit a higher viscosity than its PA counterpart, as might be expected by
virtue of its polymeric nature. Furthermore, increasing lignin results in an increase in the solution viscosity
as demonstrated in Figure 2. The density of each polyol tested resulted in approximately 10.3 lb/gal
regardless of the composition.

80,000
70,000
Viscosity at 25° C (cP)

60,000
50,000
40,000
30,000
20,000
10,000
-
0 2.5 5 10 15
Lignin (Wt%)

Figure 2: Viscosity of rPET polyols containing lignin

For examples 1 and 6 there is no lignin contained in the polyols as they are used for direct
comparison to the polyols that are of equivalent aromatic content and contain lignin. For examples 3 and 7
we chose to include 5.0 wt% of kraft lignin to the polyol formulation in order to determine lignin’s role in
enhancing the flame retardant characteristics of the aromatic polyester polyols irrespective of the aromatic
polyester source.

Polyol Lignin Content Aromatic Hydroxyl Value Acid Value Viscosity at


Example (Wt%) Source (mgKOH/g) (mgKOH/g) 25°C (cP)
1 0 rPET 247 0.3 2,400
2 2.5 rPET 245 0.2 3,900
3 5 rPET 250 0.2 4,600
4 10 rPET 247 0.5 16,200
5 15 rPET 251 0.6 70,500
6 0 PA 248 0.1 1,500
7 5 PA 263 8.0 2,800
Table 5: Polyol properties

©2017 American Chemistry Council


It is important to note the high viscosity of example 5. During a foam formulation it is preferred to
have the room temperature viscosity to be less than 20,000 cP and more preferably less than 10,000 cP for
sufficient mixing and dispensing. It is believed that a reduction in the amount of rPET while keeping lignin
content at 15 wt% would generate a polyol with a viscosity low enough to allow for processing on
commercial rigid foam manufacturing lines. Additionally, the inclusion of hydrophobes such as corn oil or
soybean oil can be transesterified into the polyol to provide a considerable reduction in viscosity. However,
as will be discussed later, our data surprisingly indicates that inclusion of soybean oil in the polyol
composition has a deleterious effect on pentane formulation stability.
The resulting polyol for example 7 proved to be difficult to react and had to be repeated several
times. The lowest acid value achieved was 8.0 mg KOH/g of sample after significantly increased reaction
times. Due to the higher acid content, the polyol did not provide a suitable foam reaction profile when used
in the standard B-side formulation. For all foams made with example 7, the amount of each catalyst was
doubled to overcome this problem. This observation warrants further investigation in order to optimize a
lignin polyol based on phthalic anhydride.

D. Pentane Stability Testing

Pentane was chosen as the main blowing agent for the purposes of this paper due to widespread
use. For typical systems it is important to assess the storage stability of the B-side formulation after the
pentane has been mixed into the formulation and prior to blending with polymeric MDI. Ideally, the
mixture should be stable for at least 12-24 hours or longer. Previous research has shown that the inclusion
of large amounts of hydrophobes such as soybean oil (typically 30-50 wt.%), improves the stability of the
B-side formulation in phthalate polyester polyols.16 Further, Shieh, et al reported an increase in the
solubility of pentane for PET polyols when a hydrophobe such as corn oil or soybean was transesterified in
amounts of 20-30 wt.%.17 Seven polyols were selected to determine the effect that the inclusion of lignin or
the introduction of a hydrophobe will have on pentane solubility and stability. Examples 8 and 10 were
replications of examples 1 and 3. Similarly, examples 12 and 14 are the same formulation as examples 6
and 7 above. Three new polyols were made utilizing an identical composition as described above but
included 10 wt.% soybean oil as a hydrophobe. The hydrophobe was added prior to the esterification step
of the reaction and at the same time as lignin and other diacids. A typical 2-step procedure was followed for
all examples with the exception of example 12, which was run in a single step process.

Polyol Lignin Aromatic Hydrophobe Hydroxyl Acid Value Viscosity Overnight


Example Content Source Content Value (mgKOH/g) at 25°C Pentane
(Wt%) (Wt%) (mgKOH/g) (cP) Stability
8 0 rPET 0 236 0.2 5,400 Stable
9 0 rPET 10 242 0.4 1,700 Separates
10 5 rPET 0 232 0.3 2,300 Stable
11 5 rPET 10 247 0.3 4,000 Separates
12 0 PA 0 248 0.1 1,500 Separates
13 0 PA 10 246 0.3 1,300 Separates
14 5 PA 0 263 8.0 2,800 Separates
Table 6: Polyol properties with and without a hydrophobe

After characterization, the polyol and other components were added according to the formulation
of Table 1 and blended with a Cowles blade at 2,000 rpm for 10 minutes to ensure the contents were
adequately mixed. Weights of the container and mixing blade were recorded before and after mixing to
assess the amount of pentane lost. Additional pentane was added and blended a second time for roughly 1
minute or until the mixture was homogenous to create the same formula for each sample. It was noted that
for the samples containing a hydrophobe the effort required to blend the pentane into a stable emulsion was
significantly less than without. After the mixing observations were recorded the samples were left to sit
overnight before assessing whether or not the emulsions were stable.
After 15 hours, each mixture was checked for separation. Interestingly, all samples containing a
hydrophobe exhibited a bilayer of pentane above the other B-side components. The two rPET based polyols
without hydrophobe were stable for more than 24 hours. Another interesting result was that all PA based
polyols showed complete separation. It is clear from these results that lignin does not play a major role in

©2017 American Chemistry Council


overall stability of the B-side and that the inclusion of soybean oil via transesterification will destabilize a
previously stable rPET based polyol.

E. Reactivity Profiles of Foam Formulations

After each polyol from the above examples were characterized, they were formulated according to
Table 1 above. The mixture was blended at 2,000 rpm prior to isocyanate addition. Subsequently, the
isocyanate was blended for 15 seconds, and the contents were poured into a paper cup for testing reactivity
profile. Table 7 details the time for each sample and figure 3 shows the trends for rPET polyols only.

30

25

20
Gel Time (s)

15

10

0
0 2.5 5 10 15
Lignin (Wt%)

Figure 3: Gel time trend of rPET polyols with lignin

The cream time was recorded as the time when the mixture began to foam or have a slight color
change, the gel time was recorded when the foam split when cut with a wooden tongue depressor, the rise
time was when the foam stopped rising, and the tack free time was recorded after scraping the skin off the
top of the foam and testing whether the surface below was not tacky. For examples 1 through 5 there is a
trend towards an increasing gel time with the addition of more lignin. However, the rise and tack free time
showed no distinct correlation with the amount of lignin in the polyol.

Example Cream (s) Gel (s) Rise (s) Tack Free (s)
1 4 7 93 54
2 2 5 70 88
3 9 11 96 62
4 6 15 81 94
5 5 24 112 106
6 2 15 95 74
7 5 9 122 172
Table 7: Reactivity profile of rigid foam formulations

Due to the high acid value of example 8, it was necessary to double both catalyst loads to achieve
near typical reaction times. However, the resulting reactivity profile remained the longest time of the
polyols tested.

F. Physical Properties of PIR Rigid Foams

For the physical properties of the rigid foams it was determined that the density should be
increased to more closely reflect the actual product density of PIR boards. A reduction in the level of
pentane (from 25.5pph to 19pph) in the formulation allowed us to achieve an average density of 1.85 lb/ft3

©2017 American Chemistry Council


(pcf). The resulting foams were aged for at least 24 hours at ambient conditions before being cut.

Polyol Lignin Foam Compressive Elongation Thermal


Example (Wt%) Density Strength (psi) (%) Conductivity
(pcf) (W/mK)
1 0 1.83 27.0 6.4 0.0239
2 2.5 1.86 30.7 8.5 0.0243
3 5 1.83 35.1 9.5 0.0241
4 10 1.89 33.2 9.0 0.0243
5 15 1.89 34.2 6.3 0.0245
6 0 1.89 34.1 9.0 0.0236
7 5 1.73 32.2 7.8 0.0244
Table 8: Foam physical properties results

The compressive strength of the foam exhibited an increasing trend as the level of lignin was
increased in the PET based polyols. Unfortunately the phthalic anhydride polyol containing lignin
displayed a lower than expected density. However, since the difference in compressive strength was minor
and the difference in density greater, one could argue that a similar trend might be seen for increasing
strength with increasing levels of lignin regardless of the polyester source.
The potential effect that lignin has on the thermal conductivity of the foam seems to be
indistinguishable and independent of the density of the foam sample. When analyzed for standard deviation
the results yield a 1.3% relative standard deviation.

G. Cone Calorimeter Results

To determine the potential benefit of lignin on flame retardancy a cone calorimeter test was set up
utilizing all of the 7 examples described above. 3-B Combustion, Explosion, and Fire Consultants in
Okemos, MI, carried out the test according to ASTM E1354. A heat flux of 50 kW/m2 was set for each
sample tested.
Research and testing has gone into the use of a cone calorimeter as a means of predicting
performance in ASTM E-84 tunnel testing.18, 19 Unfortunately, there is no small scale predictive test that
can be used for all types of materials and when a screening test has been developed it is mainly only useful
to assist with passing the E-84 in fewer attempts.20 General assumptions can be made as to the potential for
a material to pass flame spread index but it has proven hard to define the correlation to a passing rating on
smoke developed index.21 The average and peak heat release rate (HRR) has been found to be useful for
distinguishing which foams may perform better in flame spread index.

Polyol Foam Peak Avg TSR EHC MLR CO2


Example Density HRR HRR (m2/m2) (MJ/kg) (g/s) (kg/kg)
(pcf) (kW/m2) (kW/m2)
1 1.64 153 31.0 137 17.3 0.016 1.23
2 1.60 128 24.9 123 15.8 0.014 1.25
3 1.70 142 35.4 191 18.9 0.017 1.42
4 1.59 152 30.8 252 19.9 0.014 1.53
5 1.74 156 38.1 249 23.9 0.014 1.67
6 1.46 142 34.2 187 15.6 0.019 1.35
7 1.45 148 39.2 309 18.4 0.019 1.48
Table 9: Results of cone calorimeter testing
HRR: Heat release rate, TSR: Total smoke released, EHC: Effective heat of combustion, MLR: Mass loss rate

Typically, when a foam sample has a lower heat release rate it would likely perform well in E-84
testing. The cone calorimeter results demonstrate the effect of lignin on the heat release rates. Polyol
examples 1 through 5 represent constant rPET content and increasing lignin content from 2.5 to 15 wt.%.
There is a clear benefit when 2.5 and 5 wt.% of lignin is added into the polyol but negligible improvement
when the lignin amount is augmented to 10 wt.%. Each of the 2.5 to 10 wt.% lignin examples demonstrate

©2017 American Chemistry Council


reductions in peak HRR and average HRR with the largest reduction seen at a lignin content of 2.5 wt.%.
When the lignin amount is increased to 15 wt.%, it appears to negatively impact the heat release.

H. Muffle Furnace Results

A muffle furnace test as described in the experimental section is a good method for determining
the difference in char formation and mass loss of a foam at 450°C over a 20 minute interval.22 Each sample
was made into 2 blocks for testing after being wrapped in a layer of aluminum foil. The results are
averaged and tabulated in Table 10 and provided visually as figure 4.

Polyol Lignin Foam Density Mass Loss Height


Example No. (Wt%) (pcf) (%) Change (%)
1 0 1.64 36.3 +20.9
2 2.5 1.60 31.7 +19.9
3 5 1.62 34.9 +6.6
4 10 1.59 35.1 +47.7
5 15 1.74 37.1 +26.0
6 0 1.46 34.4 -3.1
7 5 1.45 35.5 -8.1
Table 10: Results of muffle furnace testing

Height Change (%) Mass Loss (%)

50
35
40
30
Height Change (%)

30 25

Mass Loss (%)


20 20

15
10
PA 10
0
5
0 2.5 5 10 15 0 5
PET
-10 0
Lignin (Wt%)

Figure 4: High temperature muffle furnace testing

In this instance, the polyols made with comparable rPET contents and increasing levels of lignin
showed a reduction in mass loss at 2.5 and 5 wt.% lignin contents, supporting the heat release rate results
for cone calorimeter testing.
Meanwhile, the amount of char height decreased from a 20.9% height increase for the non-lignin
rPET foam to a 6.6% height increase for the 5% lignin content foam, and significantly increased for 10 and
15% lignin contents to 47.7% and 26.0%, respectively.
Another interesting result is the relatively poor char performance of the phthalic anhydride based
polyols, either with or without lignin. Both PA based polyols yielded a decrease in the height of the
resulting char sample, suggesting that the recycled PET content provides a significant flammability
performance benefit over the petroleum based phthalic anhydride.

©2017 American Chemistry Council


CONCLUSIONS

Commercially available kraft lignin was incorporated via reaction with glycolyzed recycled PET
to produce lignin-containing polyols. These polyols were subsequently converted to pentane-blown
polyisocyanurate rigid foams. The resulting lignin-content PIR foams yielded improved flammability
performance as demonstrated by both cone calorimeter and muffle furnace test results.
Conclusions that can be drawn from a comparison of PIR rigid foams based on both lignin-content
rPET polyols and non-lignin content rPET polyols include the following.
• Relatively low lignin contents (2.5-5 wt.%) provide a reduction in heat release rate as
measured by cone calorimeter testing.
• Relatively high lignin contents (10-15 wt%) provide an increase in char formation shown by
the height increase as measured by 450°C muffle furnace testing. Meanwhile, a reduction in
the total mass loss with low lignin content was observed.
• Compressive strengths increase with lignin content.
• Thermal conductivity is essentially unaffected by the inclusion of lignin in rPET polyols.
• Relatively high lignin contents (10-15 wt.%) reduce the foam reaction profile as demonstrated
by increasing gel times with lignin content.

Surprisingly, the use of soybean oil as a reacted-in hydrophobe at 10 wt% in the polyol negatively
affected storage stability of pentane formulations with both lignin and non-lignin content rPET and PA
polyols versus polyols without the inclusion of this hydrophobe.
This study and these polyol compositions demonstrate that sustainable recycle- and biorenewable-
content can work together to provide an effective approach and viable alternative option to halogenated
flame retardants.

©2017 American Chemistry Council


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©2017 American Chemistry Council


BIOGRAPHIES

Kevin A. Rogers
Kevin earned his bachelor’s degrees from the University of Michigan in
Chemical Engineering and Materials Science and Engineering in 2012. As a
Lead Chemical Engineer with Resinate since 2012, Mr. Rogers has been
involved with the development and scale up of multiple products and has been
listed as a co-inventor on 10 patents.

Shakti L. Mukerjee
Shakti’s responsibility as the Director of Product and Process Development at
Resinate Materials Group is to help develop novel technologies and ensure the
feasibility of scale up processes. Prior to joining Resinate, Shakti was a Senior
Scientist at Byk Additives and Instruments developing Associative Thickeners
for rheology modifiers. Shakti’s career has produced 19 publications in ACS
Journals including co-authoring two book chapters and 15 US patents. Shakti
graduated with a Ph.D. in Chemistry from the University of Miami, and carried
out post-doctoral research work at the University of Pennsylvania receiving
funding from the DuPont company before joining industry.

Joshua N. Cupp
Josh earned his associate’s degrees from Cornerstone University in Mathematics
and Biology in 2015. As a laboratory technician with Resinate since 2016, Mr.
Cupp has been involved with the development of multiple products. Mr. Cupp
will be responsible for carrying out the production and testing methods of
foams.

Rick L. Tabor
Rick’s responsibility as the Chief Technology Officer of R&D at Resinate
Materials Group is to drive strategic new business development efforts and
intellectual property creation for sustainable, recycle-content polyols and
functional oligomers. Prior to serving at Resinate, Rick created value-added
polyurethane, surfactant and polyolefin product concepts and commercialized
them at both Stepan Company and the Dow Chemical Company. Rick’s career
has produced 18 publications, 43 patents, and commercial products that have
generated more than $100MM in revenue. Rick graduated with a B.S. in
Chemistry from Texas A&M University.

©2017 American Chemistry Council


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©2017 American Chemistry Council