This presentation describes a Shimadzu study, where a novel biomass-based rigid polyurethane foam (RPUF) was compared against a control sample of commercially available petroleum-based RPUF, using the complementary techniques of thermogravimetric analysis and pyrolysis GC/MS. Costs of polyurethane foams (PUF) are rising, as they are primarily derived from petroleum-based products whose price is tied directly to the cost of crude oil. PUFs are used widely throughout the automotive, insulation and housing industries, prompting recent advances in their production, using less expensive and renewable biomass.

1. Characterization of Biomass-Derived
Rigid Polyurethane Foam by Pyrolysis GCMS
and Thermogravimetric Analysis
Courtney Taylor, Shimadzu Scientific Instruments, Inc.
Columbia, Md., USA

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Introduction
Polyurethane foams (PUF), in both structural and
non-structural forms, are commonly used throughout the
automotive, insulation and housing industries.
These PUFs are primarily derived from petroleum-based
products whose price is tied directly to the cost of crude oil.
Due to these rising costs, manufacturers are looking for
alternatives. Recent advances in the production of PUFs,
using less expensive and renewable biomass, makes this
material a viable alternative.

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Various biomass feed stocks were investigated to this end,
with some being more promising than others. In this
investigation we:
 Compare a novel biomass-based rigid polyurethane foam (RPUF)
against a control sample of commercially available petroleum-based
RPUF
 Use the complementary techniques of thermogravimetric analysis and
pyrolysis GC/MS

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Methodology
 This study used a Shimadzu GCMS-QP2010SE coupled
with a PY-3030D Double Shot Pyrolizer and a Shimadzu
TGA-50 thermogravimetric analyzer to characterize the
samples.
 All samples for the TGA portion of this study were
measured at programmed temperature rates of 2 °C, 5 °C,
10 °C and 20 °C/min. for kinetics analysis.
 Sample weights were kept between 2-4 mg.

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Rigid PUF samples were prepared in the lab with various
ratios of glycerol and other biomass-related components.
A control sample of commercial manufacture was obtained
and used to develop the pyrolysis GCMS method.
This sample was analyzed at various temperatures in the
pyrolizer to determine the optimal conditions (see Figure 1).

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GCMS Analytical Conditions
GC Conditions
MS Conditions
Py-3030D Temp 500 C
Injector Temp 300 C
Flow Mode Constant Linear Velocity 39 cm/sec
Split Ratio 100:1
Oven Program 30 C (1 min) → 20 C/min → 275 C (12 min)
Column ZB-5HT 30 M X 0.24 mm X 0.25 µm (Phenomenex Inc.)
Interface Temp 280 C
Source Temp 200 C
Scan Range 45-500 m/z
Tune type Normal

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Pyrolysis Scan of Commercial PUF
Figure 1
A temperature of 500 °C was found to give the best
pyrolysis-GCMS results and was used as the test condition
for all samples.

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Figure 2 shows a comparison of the three prepared samples
with different glycerol content and the commercial control.
BioPUFs vs. Commercial
Figure 2

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The control shows early eluting peaks as manufacturing
blowing agents, followed by DEG and various species related
to diisocyanate.
The lab samples show no blowing agents were used, and the
DEG peak is replaced by crude glycerine. All samples contain
components related to diisocyanate (see Figure 2).

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TGA Kinetics
TGA kinetics analysis was performed by the Ozawa method.
 The heating rates used were: 2 °C, 5 °C, 10 °C and 20 °C/min.
 Sample weights were kept between 2-4 mg and were sliced from a
representative cross-section.
 All runs used a nitrogen purge at 40 ml/min. As seen in the
thermograms, different formulations show slightly different curves and
the kinetics analysis was performed on the primary weight loss (see
Figures 3-6).

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TGA Kinetics Analysis Commercial PUF
Figure 3

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Kinetics 4 PUF
Figure 4

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Kinetics C4 PUF
Figure 5

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Kinetics 5 PUF
Figure 6

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Conclusion
Pyrolysis GCMS and thermogravimetric analysis can provide
useful information regarding various formulations of
biomass-derived rigid polyurethane foams.
In this study, some difficulties encountered included relatively
busy GCMS chromatograms and less than stable TGA
kinetics runs. Further investigations will include a more
detailed pyrolysis EGA analysis and better care will be taken
regarding sample morphology in TGA runs.

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