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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
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
EXPERIMENTAL
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
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
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.
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.
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.
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
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
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%)
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.
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.
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
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%)
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.
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
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.
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.
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
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.
50
35
40
30
Height Change (%)
30 25
15
10
PA 10
0
5
0 2.5 5 10 15 0 5
PET
-10 0
Lignin (Wt%)
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.
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.
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.