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Effect of Formulation Parameters on Performance of

Polyisocyanurate Laminate Boardstock Insulation

SACHCHIDA N. SINGH, JODY S. FIFE, SHEILA DUBS AND PAUL D. COLEMAN


Huntsman Advanced Technology Center
8600 Gosling Road
The Woodlands, TX 77381

ABSTRACT

The continued success of polyisocyanurate laminate boardstock insulation (polyiso) in the construction industry can be
attributed to many factors. These include its superior thermal resistance, good structural properties and excellent fire
performance, but above all, its cost-effectiveness. Polyisocyanurate insulation boards have always been positioned as the
lowest installed cost insulation per unit of R-value while meeting the structural and fire requirements of the building codes
and blowing agent mandates of the Environmental Protection Agency. Such attributes are essential for maintaining a
competitive edge over alternative insulation materials.
With conversion to pentane blowing agents fully completed a few years ago, the focus of the board manufacturers and
material suppliers has shifted to formulation and process optimization. Learning from ongoing commercial production
using pentanes, and building on prior published works, this study systematically looks at the effects of selected
polyurethane formulation and processing variables on the key foam and laminate board performance characteristics.
Formulation variables examined include isocyanate index, polyol, and fire retardant. In particular, this study looks at
interplay between polyol hydroxyl number, fire retardant level and isocyanate index on board performance. Measured
performance characteristics include structural and thermal properties of laminate boards and its fire performance, including
some Factory Mutual Calorimeter test.
This work suggests that the performance of the polyiso board is strongly dependent on weight % of isocyanate in the
foam formulation. The structural performance of the board as expressed by compressive strength and dimensional stability
is satisfactorily met only when the weight % of the isocyanate in total foam is 57% or higher irrespective of the OH # of the
polyol at the tested foam density. Reducing the weight % of isocyanate in the foam formulation is unlikely to improve cost-
effectiveness as a higher density would then be needed to meet all of the performance requirements. Increasing the fire
retardant level is found to be beneficial to improving the fire properties, but high levels of non-reactive fire retardant
plasticize the foam and thus increase the dimensionally stable density.

INTRODUCTION

With a production of over 5.4 billion board feet in 2004, polyiso board is the insulation of choice for commercial
roofing in USA [1]. It represents over 50% of all insulation used in new roof construction and at least 40% of all insulation
used in re-roofing applications. Such wide acceptance by the construction industry is attributable to the fact that no other
competitive product can match its combination of thermal resistance, fire performance, structural integrity and cost-
effectiveness. The polyiso industry has been able to maintain its position of the lowest installed cost insulation per unit R-
value through all the blowing agent and other changes. This drive for lowest cost while meeting the performance
requirements has meant constant re-examination of all the factors that contribute to cost and performance. Recent high
energy prices have added a new dimension to this re-examination. Higher energy prices spur the demand for more energy-
efficient building practices which translates to higher demand for insulation. Higher energy prices have generally gone
hand in hand with higher petrochemical prices, which generally mean higher raw material costs for polyiso. Higher demand
along with concurring higher raw material cost creates a unique situation for re-examination of all factors contributing to
cost and performance.
Raw material costs are by far the largest component of the polyiso product variable cost. Among the various
components of polyiso board, the foam formulation is the one that is generally optimized to yield lowest cost per unit R-
value while meeting the mechanical and fire requirements. Polyiso boards are currently manufactured by a continuous
lamination process, using aromatic polyester polyols, high functionality polymeric MDI, fire retardant, catalyst, surfactant,

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and water and pentane as a blowing agent. Column 2 of Table 1 shows a typical formulation currently in use. High
functionality polymeric methylenediphenyl diisocyanate (HF-PMDI) such as RUBINATE 1850 isocyanate is the largest
single component of the foam formulation and thus the single largest cost. Though the isocyanate index which determines
the amount of the HF-PMDI in the formulation has always been in play in any formulation optimization, lately there have
been initiatives to lower the hydroxyl number of the aromatic polyester polyol, which in turn lowers the amount of HF-
PMDI at the same index [2-4]. Similarly, though the type and level of fire retardant has always been a variable in
formulation optimization, there has lately been an emphasis by some to increase the amount of fire retardant and
simultaneously lower the amount of HF-PMDI [2,5].
The objective of this paper is to critically examine the role of high functionality polymeric MDI, aromatic polyester
polyol and fire retardant in meeting all the performance requirements of the polyiso board. This is done with the aim of
finding the most cost-effective approach to manufacture board.

Table 1. Typical Formulations


Standard OH Polyol Low OH Polyol Low OH polyol w/ high FR
PHP % Total PHP % Total PHP % Total
Aromatic Polyester Polyol
Std. OH of 240 100 30.50
Low OH of 208 100 33.18 100 32.4
TCPP 10 3.05 9.2 3.05 15 4.9
K-octoate (15% K) 6.0 1.83 5.5 1.83 5.66 1.83
K-acetate (10% K) 1.0 0.30 0.92 0.30 0.94 0.30
JEFFCAT PMDETA catalyst 0.2 0.06 0.18 0.06 0.19 0.06
Silicone surfactant 2.0 0.61 1.84 0.61 1.88 0.61
Iso- and/or n-pentane 22.0 6.71 20.22 6.71 20.72 6.71
Water 0.4 0.12 0.37 0.12 0.38 0.12
Total Polyol Side 141.6 43.19 138.25 45.87 144.76 46.90
RUBINATE 1850 isocyanate 186.2 56.81 163.2 54.13 163.9 53.10

Isocyanate Index 260 260 260


Aromatic in foam, wt % 37.6 36.6 35.9
Isocyanurate in foam, wt % 10.7 10.2 10.0
Nitrogen in foam, wt % 5.8 5.5 5.4
Chlorine in foam, wt % 1.0 1.0 1.6
Phosphorous in foam, wt % 0.3 0.3 0.5
Non-reactive/mono-functional 8.1 8.4 10.2
in polymer, wt %

Requirements on Polyiso Boards

The physical property requirements for polyiso insulation are specified in ASTM C 1289 - 06 Standard Specification for
Faced Rigid Cellular Polyisocyanurate Thermal Insulation Board. This standard specifies the compressive strength,
dimensional stability, flexural strength, thermal resistance, moisture resistance to name a few of the many performance
requirements on the boards. Though each of the requirements are critical to the use of board, it is generally understood that
compressive strength, dimensional stability, thermal resistance and fire performance are the properties that determine the
formulation and operating board density.

Though polyiso insulation boards are available in a range of compressive strengths, as per ASTM C 1289, a minimum of
16 psi on the faced product in the thickness direction is required for all polyiso products. Generally, it has been a practice
of the board manufacturer to target a compressive strength of 20 psi. Dimensional stability of polyiso board is tested at
three different environmental conditions: -40oF, 158oF/97% relative humidity and 200oF in accordance with ASTM D2126
on 12 by 12 by board thickness specimen. In addition, our prior work has demonstrated that the most severe field
exposure condition on board is simulated by exposure to -40oF under the Dimvac test conditions on 4 by 4 by 1 core
foam [6].

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Even though, ASTM C 1289 only specifies the minimum thermal resistance of the board measured after 180 days of
conditioning at room temperature, most polyiso manufacturers have adopted the Long Term Thermal Resistance (LTTR) as
the exclusive means to market thermal performance of roof insulation. LTTR is measured using ASTM C 1289-06, Annex
A, by predicting the 15 year time-weighted average R-value.

In order to meet the requirements of model building codes throughout the USA, polyiso products must meet a series of
fire performance tests developed by ASTM, Factory Mutual Research Corporation (FMRC) and Underwriters Laboratories
(UL). The exact fire performance test that the polyiso board must meet depends on building location, roof design and
insurance underwriters of the property. Reference 7 gives an overview of many of the widely used tests. Polyiso roof
insulation is known for being the only foam plastic board product that meets the strict standards of both FM Approvals
(Standard 4450) for Class 1 roof systems and UL (UL1256) without the use of an additional thermal barrier layer between
the insulation and the supporting steel deck. As such any formulation re-examination must retain this quality. It is
generally understood that FMRC Calorimeter (FM Standard 4450/4470), used to assess the fuel contribution rate of a roof
assembly so as to reduce the potential to spread fire on the underside of the roof deck, is the most challenging test to meet
to get a Class 1 rating. Exterior combustibility tests conducted in accordance with ASTM E 108 on a roof assembly and
ASTM E 84 flame spread and smoke developed ratings on core foam are two other tests that present some challenge.

In addition, polyiso must have good adhesion to faces, low water absorption, low water vapor transmission, prescribed
flexural strength and tensile strength perpendicular to board surface.

Material Requirements

Before we explore the most cost-effective approaches to meet the above requirements on polyiso boards, let us discuss
the structural and thermal stability requirements on the polymer to meet such performance. During FM Calorimeter testing,
temperatures at the underside of the steel deck have been reported to go from near ambient temperature to 1000oF within
minutes and then creep as high as 1500-1600oF in the 30 minute duration of the test [5, 8, 9]. Such temperatures are well
above the decomposition temperature of most organic polymers including Polyiso foam, a low density poly(isocyanurate-
urethane) material. The decomposition temperature of the isocyanurate linkage, the most thermally stable bond in polyiso
foam, is in the range of 570-620oF [9, 10]. Other linkages such as urethane, ester, urea, allophanate, and uretonimine break-
down at lower temperatures. It is the char forming ability of the polyiso foam that keeps the asphalt on the roof assembly
from melting and dripping into the calorimeter and not contributing to the allowable BTU limits of the FM Calorimeter test.
Polyiso foam board must form a dimensionally stable char as a result of thermal decomposition so that the char maintains a
continuous surface and does not form wide and deep cracks due to excess shrinkage. The char must have low thermal
conductivity so as to prevent heating up the coverboard and asphalt. Molten asphalt would find its way into the calorimeter
through the build-in joints and any cracks thorough the coverboard and char layer. Intumescent and oxidation resistant char
would be beneficial but not essential.
Surprisingly there has not been any study to understand the mechanism or composition of char formation in the FM
calorimeter. A review of the general polymer literature suggests that char yield should have a direct relationship to the
number of aromatic ring structures in the polymer back-bone [9, 11]. Literature also suggests that the char is primarily a
carbonaceous residue and is best described as a conglomerate of loosely linked small graphitic regions, i.e., aromatic
carbons [12]. A recent study of the composition of char in polyiso foam exposed to direct flame also suggests the presence
of primarily aromatic carbon [13]. Though the polyiso foam board is not exposed to direct flame in the FM Calorimeter, it
is in the ASTM E 84 and E 108 tests.
All this suggests that while investigating the polyiso formulation to meet the fire requirements of board, we should
consider not only the isocyanurate content of the foam but also the aromatic content. Pentane blown formulations have
generally used a fire retardant (FR) to meet all the fire requirements [2]. Despite numerous efforts to find alternatives,
phosphate esters, in particular tris(2-chloro-isopropyl)-phosphate (TCPP), have remained the FR of choice for the US
boardstock industry due to their unique cost-performance balance. The fire retardation mechanism of phosphate esters is
fairly well characterized and generally works as free radical scavenger in the gas phase and char promoter in the condensed
phase [14, 15]. It is generally accepted that phosphate esters go through the following steps:
Phosphoric acid ester phosphoric acid metaphosphoric acid poly(metaphosphoric) acid.

Through their strong dehydrating and dehydrogenating action, these acids accelerate the carbonization of the polymer
and formation of a carbonaceous charred structure [14-16]. It is likely that the aromatic content and the cross-link density
of the polymer (and thus inherent thermal stability) plays a role in the effectiveness of the above char formation mechanism.
Mechanical properties of the polyiso foam board, i.e., compressive strength and dimensional stability, follow many of
the rules of general polymer science. Those rules suggest such properties are enhanced by the formation of a long polymer

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chain, high cross-link density, presence of high main-chain aromatic content, and absence of non-reactive or chain-
terminating mono-functional additives. Early polyisocyanaurate foams from the 1970s were too brittle and the
introduction of di-functional aromatic polyester polyols, especially those of decreasing OH # from 350 to 250, improved
conversion, reduced friability and paved the way for the development of present day urethane modified polyisocyanurate
foam [3, 8]. The use of roughly 240 hydroxyl aromatic polyester polyol as the sole polyol in polyiso foam became a
standard in the mid-80s and has performed well through all the changes in blowing agents.

Formulation Parameters

Table 2 shows the characteristics of the key reactive components of a typical polyiso foam. The aromatic content is
defined as weight % of aromatic ring alone, i.e., phenyl content. This is different than phthaloyol (an aromatic ring with
two carbonyl groups) content which is how the polyester polyol industry sometime defines aromatic content. It is very
unlikely that the carbonyl attached to the phenyl ring would participate in or facilitate char formation. Nitrogen content is
listed here as it is thought to lower flammability [17]. The weight % of non-reactive and mono-functional additives is listed
too, as non-reactives would plasticize the foam polymer and mono-functional species would terminate the chain, thus
lowering the cross-link density and molecular weight. The amount of such additives in aromatic polyester polyols varies
significantly depending on the supplier and the exact polyol. Ten weight % is on the lower end of the typical level of such
additives in polyols. HF-PMDI with its average functionality of 2.9 is the only network forming component in the polyiso
formulation. Of course, isocyanates promote additional cross-linking by formation of isocyanaurate, allophanate, biuret and
uretonimine all of which are network forming.

Table 2. Typical properties of key reactive components


HF-PMDI Polyol K-octoate Water
Aromatic content, wt. % 55.5 ~20 0 0
Nitrogen content, wt. % 10.2 0 0 0
Number average functionality 2.9 < 2.0 <2 2
Equivalent weight 137 250 - 300 165 9
Non-reactive & mono-functional, wt. % 0 >10 ~30 0

The effect of decreasing the hydroxyl number of the polyol on the aromatic and isocyanurate content of the foam at a
fixed index and blowing level is illustrated in Figure 1. Blowing level, defined as the volume of gas generated per unit
weight of polymer, is fixed to compare foams at the same density. Table 1 shows the impact of decreasing the hydroxyl
number along with the effect of increasing the FR content on weight % of nitrogen, chlorine, phosphorous and non-
reactives. Clearly all these parameters change significantly when OH # of the polyol or the FR content is changed.
In this study, we used a full factorial experimental design with formulation variables as shown in Figure 2. The choice
of fixed weight % of HF-PMDI as opposed to fixed index is exactly that, a choice. The findings of the study are not
dependent on this choice.

Board Manufacture

Boards from 12 different formulations shown in Table 3 and 4 were produced on a commercial fixed gap laminator in
the USA using raw materials that are commercially available. In order to limit the quantity of boards produced, only four
batches of polyol side, one each with two polyols at each level of TCPP were made and then the weight % of isocyanate
was changed by adjusting the relative flow rates through the pumps. The amount of pentane in the formulation was
controlled independently in order to insure a constant core foam density throughout the 12 formulations. All this meant
that the amount of the additives such as catalyst and surfactant changed a bit among the boards made using the same polyol
and FR level. At the same isocyanate level though, e.g. compare A-57 to C-57 or B-55 to D-55, the level of all components
except the independent variables remained the same.

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38 12

Isocyanurate, wt %
Aromatic content,
37
11
wt %
36
10
35
34 9
150 200 250
OH # of Polyol

Aromatic Content Isocyanurate

Figure 1. Effect of the OH # of a polyol on aromatic and isocyanurate content of a foam at a fixed index of 260

All boards were made using typical production conditions (line speed, laminator/facer/chemical temperatures, and
stacking sequence). All laminates had a nominal thickness of 1.5 and used an ASTM C1289, Type II black facer typical of
roofing boards. A minimum of 30 minutes of laminator run time was used for each formulation to assure a properly lined
up process before collecting boards for testing. All laminates used for testing were bundle cured for 24 hours in the middle
of the bundle, sorted for shipment and then stored indoors as a bundle for many days prior to any testing.
Hydroxyl # of polyol

OH # 240

5.2
PP
TC

OH# 208
%

2.6
% Isocyanate
57 55 53

Figure 2. Schematic of the full factorial experimental design

RESULTS AND DISCUSSIONS

Whenever applicable, foam laminates were tested using the standard test method described in the polyiso material
standard ASTM C 1289 06. Two tests not described by ASTM but widely used in industry, namely Hot Plate fire test and
Dimvac dimensional stability tests were also used. A full factorial modeling of the data, which included analysis of
variance and assessment of main effects and interactions among the variables were performed using a commercial statistical
analysis software. A critical p-value of 0.05 was chosen to determine whether a property was significantly affected by the
chosen variable or not. Tables 3 and 4 show average values of all the results along with the formulations.
All of the 12 formulations processed well giving fine celled foam, with soft, straight knit-lines and no visible post-
growth. The reactivity for all systems were fairly close to each other and typical of current commercial practice. The low
hydroxyl polyol seems to process better, with less frothiness, better flow, and easier line up of the product. The core foam
density and the defaced board density were fairly constant for all the runs. This was purposely done by fine tuning the level
of pentane added in-line so as to compare the effect of the control variables without interference from density. The core
foam density was 1.56 0.02 pcf and the defaced board density was 1.74 0.04 pcf. Such densities are likely to be on the
low end of the commercial production range and were targeted to enable us to discriminate among the variables chosen
here.

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Table 3: Formulations Using Standard Hydroxyl Aromatic Polyester Polyol (APP)
Standard OH Polyol + Low TCPP Standard OH Polyol + High TCPP
Formulation, % total system A-57 A-55 A-53 B-57 B-55 B-53
APP, Std. OH of 240 30.15 32.02 33.87 27.85 29.56 31.28
TCPP 2.44 2.60 2.75 4.88 5.18 5.48
K-octoate (15% K) 1.76 1.87 1.98 1.77 1.88 1.98
K-acetate (10% K) 0.29 0.31 0.33 0.29 0.31 0.33
JEFFCAT PMDETA catalyst 0.06 0.07 0.07 0.07 0.07 0.07
Silicone surfactant 0.65 0.69 0.73 0.65 0.69 0.74
Water 0.13 0.14 0.15 0.13 0.14 0.14
Pentane 7.52 7.32 7.12 7.36 7.18 6.98
Total Polyol Side 43.00 45.00 47.00 43.00 45.00 47.00
RUBINATE 1850 isocyanate 57.00 55.00 53.00 57.00 55.00 53.00

Isocyanate Index 260 236 215 278 252 230


Aromatic in foam, wt. % 37.5 36.7 36.0 37.0 36.3 35.5
Isocyanurate in foam, wt % 10.7 9.7 8.7 11.1 10.1 9.1
Nitrogen in foam, wt % 5.8 5.6 5.4 5.8 5.6 5.4
Chlorine in foam, wt % 0.79 0.84 0.89 1.58 1.68 1.78
Phosphorous in foam, wt % 0.23 0.25 0.26 0.46 0.49 0.52
Non-reactive/mono- in polymer, wt % 7.6 8.1 8.6 10.0 10.6 11.2

Physical Properties
Density, pcf
Core foam 1.6 1.5 1.6 1.6 1.6 1.6
Defaced laminate 1.7 1.7 1.7 1.7 1.7 1.7
Compressive Strength, psi
Laminate across thickness 20.3 18.1 17.2 18.8 16.8 17.4
Dimensional stability, Laminate
2 weeks @ -40oF, Rank* 1-4 1 2 2-3 1-2 2 2-3
Dimensional stability, core foam
2 weeks @ -40oF, Rank* 1-4 1 1 1 1 1 1
2 wks @ -40oF after Dimvac, Rank* 1-4 1 2-3 2-3 1-2 2 2-3
2 wks @ 70oF/97%RH, % linear change 3.1 3.7 6.3 3.1 3.8 6.3

Thermal Resistance, ft2.h.oF/Btu.in


Initial, 6.1 6.1 6.1 6.0 6.0 6.0
Predicted LTTR for 2.5 5.7 5.7 5.7 5.6 5.6 5.7

Fire Performance
FM Calorimeter Pass NT NT NT NT NT
Hot Plate
Weight retention, % 79 79 77 83 80 79
Thickness retention, % 74 71 65 74 80 85
Butler Chimney
Weight retention, % 66 63 59 85 83 79
Extinguish time, sec. 19 19 22 12 12 14
Oxygen Index 22.8 22.6 22.6 23.5 23.4 23.0
NBS max. smoke density 70 73 84 32 33 48

* Rank 1- No distortion, 2 Some edge collapse, 3 - Severe edge collapse, 4 Severe distortion
NT Not Tested

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Table 4: Formulations Using Low Hydroxyl Aromatic Polyester Polyol (APP)
Low OH Polyol + Low TCPP Low OH Polyol + High TCPP
Formulation, % total system C-57 C-55 C-53 D-57 D-55 D-53
APP, Low OH of 208 30.15 32.02 33.87 27.85 29.56 31.28
TCPP 2.44 2.60 2.75 4.88 5.18 5.48
K-octoate (15% K) 1.76 1.87 1.98 1.77 1.88 1.98
K-acetate (10% K) 0.29 0.31 0.33 0.29 0.31 0.33
JEFFCAT PMDETA catalyst 0.06 0.07 0.07 0.07 0.07 0.07
Silicone surfactant 0.65 0.69 0.73 0.65 0.69 0.74
Water 0.13 0.14 0.15 0.13 0.14 0.14
Pentane 7.52 7.32 7.12 7.36 7.18 6.98
Total Polyol Side 43.00 45.00 47.00 43.00 45.00 47.00
RUBINATE 1850 isocyanate 57.00 55.00 53.00 57.00 55.00 53.00

Isocyanate Index 291 264 241 310 282 256


Aromatic in foam, wt. % 37.5 36.7 36.0 37.0 36.3 35.4
Isocyanurate in foam, wt % 10.7 9.7 8.7 11.1 10.1 9.1
Nitrogen in foam, wt % 5.8 5.6 5.4 5.8 5.6 5.4
Chlorine in foam, wt % 0.79 0.84 0.89 1.59 1.68 1.78
Phosphorous in foam, wt % 0.23 0.25 0.26 0.46 0.49 0.52
Non-reactive/mono- in polymer, wt % 7.6 8.1 8.5 10.0 10.5 11.2

Physical Properties
Density, pcf
Core foam 1.6 1.6 1.6 1.6 1.6 1.5
Defaced laminate 1.8 1.8 1.8 1.8 1.8 1.7
Compressive Strength, psi
Laminate across thickness 19.7 18.2 17.3 19.7 18.2 18.9
Dimensional stability, Laminate
2 weeks @ -40oF, Rank* 1-4 1-2 2 2 1-2 1-2 2-3
Dimensional stability, core foam
2 weeks @ -40oF, Rank* 1-4 1 1 1 1 1 1
2 wks @ -40oF after Dimvac, Rank* 1-4 2 2-3 3 1 1-2 1-2
2 wks @ 70oF/97%RH, % linear change 3.1 3.9 5.6 3.0 4.1 6.6

Thermal Resistance, ft2.h.oF/Btu.in


Initial, 6.0 5.8 5.8 5.8 5.9 5.8
Predicted LTTR for 2.5 5.6 5.4 5.4 5.4 5.6 5.5

Fire Performance
FM Calorimeter Pass Fail Predict Fail + NT Pass NT
Hot Plate
Weight retention, % 79 77 77 76 79 76
Thickness retention, % 77 71 69 77 75 70
Butler Chimney
Weight retention, % 64 56 52 71 65 61
Extinguish time, sec. 21 23 24 17 18 20
Oxygen Index 22.6 22.6 22.3 23.2 23.2 22.8
NBS max. smoke density 52 65 84 36 46 52

Rank 1- No distortion, 2 Some edge collapse, 3 - Severe edge collapse, 4 Severe distortion
+ test aborted at 27th minute out of 30 minute
NT Not Tested

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Structural Properties of Polyiso Board

The compressive strength of the laminate in the thickness direction is key to the ability to properly install the roof assembly.
It is generally targeted to be 20 psi or higher. Figure 3 shows the average compressive strength and it is higher for boards
containing higher weight % of HF-PMDI. Mathematical modeling of the compressive strength data suggests that increasing
the isocyanate content of the foam and reducing TCPP content would lead to higher strength. There also seems to be a
statistically sound interaction between polyol and TCPP level with higher level of TCPP with the low hydroxyl polyol
giving a higher strength.
CS in rise dir., psi

20

18

16
57 55 53
Isocyanate (HF-PMDI), w t%

Std OH + Low TCPP Std OH + High TCPP Low OH + Low TCPP Low OH +High TCPP

Figure 3. Compressive strength of the laminate in thickness direction

Cold dimensional stability of the polyiso board as measured by aging 12 by 12 by full-faced boards for two weeks at
-40oF showed little change in the measured dimensions but the edges of many samples shrank. Figure 4 contains pictures
of the samples showing varying degree of edge shrinkage. Results were similar for boards made using Low OH polyol, i.e.,
C and D samples. Tables 3 & 4 give an average visual ranking of the samples based on criteria defined at the bottom of the
table. An analysis of the numerical rank data suggests that a higher isocyanate level is the only statistically plausible way to
avoid edge shrinkage at the chosen board density. Of course, higher board density would be the other but that was not
evaluated here.

Figure 4. Picture of 12 by 12 laminate after two weeks at -40oF

Dimensional stability of the core foam was evaluated under three sets of conditions, namely two weeks at -40oF, 2
weeks at 158oF/97% relative humidity both in accordance with ASTM D 2126 and two weeks at -40oF after Dimvac
conditioning. Dimvac test condition exposes the foam to a greater pressure difference as CO2 in foam is allowed to escape
while no air is allowed to diffuse in foam [6].

None of the core foam samples showed dimensional change of higher than 1% after two weeks at -40oF under the
conventional dimensional stability test, but many shrank significantly under the Dimvac condition. This is an extremely

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important finding as it suggests that under the nominal testing conditions used by quality control laboratories, all of the
foam boards made in this study would appear dimensionally stable. However, under a more severe test condition, a
condition still very plausible in the field, some boards would shrink. One such scenario that would simulate the Dimvac
condition is making of the boards in late summer, the board being exposed to weeks of high temperature in the warehouse
or in trucks and then being used in the field in a relatively cool climate, all in one season [6]. Statistical analysis on visual
rank results suggests that higher isocyanate (HF-PMDI) content is the only statistically sound way to reduce/eliminate
shrinkage. Similar to the findings with compressive strength, there seems to be a statistically sound interaction between
polyol and TCPP level with the higher level of TCPP and the low hydroxyl polyol giving less shrinkage.

8
% Linear change

0
57 55 53
Isocyanate (HF-PMDI), w t%

Std OH + Low TCPP Std OH + High TCPP Low OH + Low TCPP Low OH + High TCPP

Figure 5. Average linear change in length and width direction after 2 weeks at 158oF/97% relative humidity

Figure 5 above shows the average linear change in length and width direction of core foam after exposure to 158oF/97%
relative humidity. A higher isocyanate level is the only statistically sound way to reduce expansion of the foam sample
under these conditions.
Thus it is clear that the structural performance of the board as expressed by compressive strength and dimensional
stability is satisfactorily met only at 57% isocyanate (HF-PMDI) content in the formulation irrespective of the OH # of the
polyol at the tested foam density. At lower isocyanate content in the foam, the density would need to be higher to avoid any
structural performance issues. Keep in mind, the index will have to be as high as 310 to get 57% isocyanate when using
lower OH polyol and higher level of FR. Lower FR level does improve structural performance but that could hurt fire
performance. It does appear that a unique combination of low hydroxyl polyol and high level of TCPP gives unusually
improved structural performance. It is likely that the lower viscosity of this combination improves mixing and thus network
forming capability. This may be a topic for future work.

Thermal Resistance of Boards

Initial and 2.5 predicted LTTR values are listed in Table 3 & 4 and the LTTR values are shown in Figure 6. LTTR
values were measured following Annex-A of ASTM C 1289 06, with a slice thickness of 9 mm. Statistical analysis
suggest

5.8
LTTR value

5.6

5.4

5.2
57 55 53
Isocyanate (HF-PMDI), w t %

Std OH + Low TCPP Std OH + High TCPP Low OH + Low TCPP Low OH + High TCPP

Figure 6. Predicted LTTR values for 2.5 thick board in ft2.hoF/Btu.in

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that isocyanate and TCPP level has much lower impact on initial and LTTR values as compared to the hydroxyl # of the
polyol. Lower hydroxyl polyol gave a lower initial and LTTR value by about 2 - 4%. Further measurements to predict the
LTTR value of 1.5 thick product are ongoing.

Fire Performance of Boards - FM Calorimeter

Given the high cost and limited availability of the FM Calorimeter, only selected boards were tested using a decision
tree. The roof assembly used for the test consisted of a FM approved steel deck, 1.5 thick polyiso board fastened to the
deck, 0.5 wood fiber coverboard adhered to the insulation using hot asphalt applied at a rate of 20-25 lb/sq (100 sq. ft.),
four-ply fiberglass felt reinforced built-up roof cover with each ply adhered using hot asphalt applied at a rate of 20-25
lb/sq, and a flood coat of asphalt at a rate of 60 lb/sq. This roof assembly is widely used by the polyiso industry as it is
considered the most difficult to pass. However, once attained it means that the board can be used in a wide variety of roof
assemblies including three-ply built up and membrane, provided other approval bodies and building code criteria are met.
Table 5 shows the result of all the FM Calorimeter tests conducted here. The allowable maximum average rate of fuel
contribution for the three, five, ten and 30 minute time intervals is 410, 390, 360 and 285 Btu /ft2 /min. respectively for a
Claas 1 roof assembly. The boards made using 57% isocyanate, low level of TCPP and either the standard (Board A-57) or
the low hydroxyl (Board C-57) polyol passed the FM Calorimeter test whereas the board made using the low hydroxyl
polyol, low level of TCPP but only 55% isocyanate failed. Actually the board C-55 using low hydroxyl polyol, low level of
TCPP but only 55% isocyanate was tested twice, first in the beginning of the test series and then at the end, and it failed
both times. The board C-53 made using low OH polyol, low level of TCPP but only 53% isocyanate was tested but an
instrument failure in the calorimeter stopped the test during the 27 minutes of the 30 minute long test. Comparison of the
flue outlet temperature and the residual foam char of the board C-53 with that of other boards, especially C-55,
unambiguously suggests that C-53 would have failed the test if taken to completion. This along with the poor structural
performance of boards made using 53% isocyanate led us to not retest C-53. Another board, D-55 made using the low
hydroxyl polyol, 55% isocyanate but the higher level of TCPP did pass the FM Calorimeter test.

Table 5. FM Calorimeter test results


Board ID C-57 C-55 C-55 repeat C-53 D-55 A-57
Isocyanate (HF-PMDI), wt% system 57 55 55 53 55 57
Aromatic polyester polyol type Low OH Low OH Low OH Low OH Low OH Std. OH
TCPP, wt % system 2.44 2.60 2.60 2.75 5.18 2.44
Maximum average rate of fuel
contribution , Btu /ft2 /min.
3 min. rate (410 max to pass) 228 450 469 Test aborted 204 375
5 min. rate (390 max to pass) 226 421 452 at 27th min. 188 368
10 min. rate (360 max to pass) 216 340 386 out of 30 min 151 317
30 min. rate (285 max to pass) 139 206 230 108 177
Rating Pass Fail Fail Predict fail Pass Pass

Given the high cost to conduct the FM Calorimeter test, above results were supplemented by a variety of small scale
laboratory tests, such as Hot plate, Butler Chimney, Oxygen index, and NBS smoke density which have traditionally been
used in the industry to compare fire performance of boards. Recently there has been a proliferation of small scale tests but
surprisingly, no data has been published showing any correlation of results from the small scale tests with the FM
Calorimeter [5, 18, 19].
The hot plate test is among the widest used to correlate with the FM calorimeter and Figure 7 compares the thickness
retention results on full thickness boards. Statistical analysis of the data suggests that the thickness retention is increased
by going to higher isocyanate and TCPP content with OH # of polyol making a very minor impact. When we compared the
thickness retention in the hot plate test with that of residual char in the FM Calorimeter test, we concluded that the hot plate
test used in this study was not severe enough. For example, the board made using formulation C-55, i.e., low OH polyol,
low TCPP with 55% isocyanate, had a char thickness of only ~ 50% after the end of the FM calorimeter test, but the
corresponding number in the hot plate test was ~70%. A more severe hot plate test is being designed.

828
90
Thickness retention, %

80

70

60
57 55 53
Isocyanate (HF-PMDI), wt %

Std OH + low TCPP Std OH +High TCPP Low OH + Low TCPP Low OH + High TCPP

Figure 7. Thickness retention in a Hot Plate test on full thickness boards

The Butler Chimney test is widely used to compare the performance of materials to direct flame fire tests such as ASTM
E 84. The temperature of the flame of the burner used in the Butler Chimney has been recorded to be 960 5oC [13].
Therefore, the weight retention and extinguish time in this test show the effect of a 960 5oC open flame applied vertically
to bare foam in air. Weight retention, i.e., char yield and the extinguish time of the flame after the burner is removed from
the bottom of the foam is given in Tables 3 & 4. As can be seen from Figure 8, and confirmed by data analysis, raising the
FR level had the most impact on improving weight retention, followed by increasing the isocyanate content. Lower
hydroxyl polyol gave a lower char yield as compared to standard hydroxyl.
But. Chim. wt. ret, %

80

60

40
57 55 53
Isocyanate (HF-PMDI), wt%

Std OH + Low TCPP Std OH + High TCPP Low OH + Low TCPP Low OH + High TCPP

Figure 8. Weight retention in the Butler Chimney test on core foam

Oxygen Index is a widely used test in the polymer industry and it measures the minimum oxygen concentration in a
gaseous oxygen-nitrogen mixture necessary to support the combustion of a vertical sample burning downwards. Small
changes in the index can indicate large differences in fire performance, e.g., the oxygen index for pentane is 15.6 whereas
the same for polypropylene is only 17.4. Results from the oxygen index test are consistent with findings from the Butler
Chimney test.
The NBS smoke density test is widely used to assess the smoke generation in the ASTM E 84 test and Figure 10 shows
the results of this study. All the maximum smoke density numbers are well below what would be needed to meet the
maximum smoke density requirements of the ASTM E 84 test.

829
24
Oxygen index

23

22

21
57 55 53
Isocyanate (HF-PMDI), wt %

Std OH + Low TCPP Std OH + High TCPP Low OH + Low TCPP Low OH + High TCPP

Figure 9. Oxygen index on core foam

It is clear from all the fire test results that the FM calorimeter requirements and most likely ASTM E 84 and ASTM E-108
requirements as suggested by small scale tests simulating open flame fire, can be satisfactorily met when isocyanate content
of the foam is 57% even with low amounts of TCPP and irrespective of the OH # of the polyol. As the weight % of the
isocyanate in the formulation is reduced, good fire performance are achieved only when FR level is relatively high.
Maximum smoke density

100

80

60

40

20
57 55 53
Isocyanate (HF-PMDI), wt%

Std OH + Low TCPP Std OH + High TCPP Low OH + Low TCPP Low OH + High TCPP

Figure 10. Maximum smoke density in the NBS smoke test on core foam

Overall Findings

The results of this study suggest that higher isocyanate (HF-PMDI) content in the foam formulation improves the
structural, thermal and fire performance of the polyiso board whereas increasing the FR content improves fire but
deteriorates structural performance. Lowering the hydroxyl number of the polyol at a fixed isocyanate level seems to have
a neutral impact at best.
Much of these findings can be explained on the basis of basic polymer science. Increasing the isocyanate amount
increases the aromatic content, the nitrogen content, isocyanurate content, and average functionality and decreases the
amount of non-reactive and chain-terminating mono-functional additives. This makes the foam more cross-linked and
thermally stable allowing it to meet the dimensional stability requirements at lower density and the FM Calorimeter
requirements at lower density and/or thickness. To the polyiso formulator, it has been always known that a high
isocyanurate content is advantageous as it imparts several desirable properties to the foam, low flammability, low smoke
evolution, good thermal stability and good dimensional stability. What may not have been clear is that high isocyanurate
content in foam brings along higher aromatic content, nitrogen content, average functionality and lower non-reactives
which together yield the better properties. Lowering the hydroxyl number of polyol while keeping the index the same may

830
appear to keep the isocyanurate content unchanged, but it does not. By virtue of its definition, index only calculates excess
NCO equivalents as a multiple of total OH groups. Thus when the hydroxyl number of the polyol is lowered, the total
number equivalents of OH decreases and thus excess NCO equivalent decreases which in turn lowers the isocyanurate
content at the same index.
The hydroxyl value of the polyol had been constant until recently, and thus it made no difference whether one used a
fixed index or fixed weight % of isocyanate. However, with the hydroxyl value of polyols changing, it would be more
prudent to formulate keeping the weight % of isocyanate constant rather than the index. Thus when looking to improve the
cost-effectiveness of polyiso foam, one should remember that board density dominates all other factors affecting cost. Any
efforts to optimize the isocyanate (HF-PMDI) content of the foam should be checked to ensure that they do not
inadvertently increase the overall cost of the polyiso foam by raising the minimum stable density of the foam.
Increasing the FR level may be beneficial to improving the fire performance, but it plasticizes the foam and thus
increases the dimensionally stable density [20]. Certainly some level of FR is essential to meeting the fire requirements
with pentane blown foam [2], and at those low levels it may not act as a plasticizer. Thus one needs to carefully look at the
cost-performance balance when adding fire retardant, while keeping in mind the dimensionally stable density. It is prudent
to determine the dimensionally stable density using not just the conventional tests, but also tests such as Dimvac which
simulate a worst case scenario. This would minimize the chance of cost prohibitive surprises.
The results of selected FM Calorimeter tests along with those of small scale laboratory tests demonstrate that higher
isocyanate content improve all aspects of fire performance and lowering the OH # of polyol hurts the fire properties even at
the same isocyanate level let alone the same index. We must remember, foam failure in the FM Calorimeter test is a self-
accelerating process and thus small differences in char forming ability is likely to make a large difference in the outcome.
It does appear that the lower hydroxyl polyols may ease processing of the foam by having less froathing, and better
flow. It is not clear whether the underlying cause for the easier processing is lower OH# of the polyol, better pentane
compatabilizers, or viscosity modifiers added to these polyols.
There are many what if questions that a polyiso formulator may raise at this point. What if the functionality or the
aromatic content of the polyol was raised, simultaneous to lowering the OH number? What if the FR was reactive, or even
cross-link forming? Though some of these possibilities are limited by other constraints such as viscosity requirements on
the polyol side and pentane compatibility, there is always room for further innovation.

CONCLUSIONS

The performance of the polyiso board is strongly dependent on the weight % of isocyanate in the foam formulation.
This is because of all the attributes, such as high aromatic and nitrogen content, high inherent functionality, and ability to
form thermally stable, cross-linking bonds, that high functionality polymeric MDI such as RUBINATE 1850 isocyanate
brings to the formulation. In other words, high thermal stability of polyiso foam is related not just to high cross-link density
and high thermal stability of the isocyanurate structure but also to accompanying high aromatic content. If the urethane
content in the foam is increased, the advantages of the isocyanaurate linkages would decrease. Maintaining high
isocyanurate and aromatic content is advantageous as it imparts several desirable properties to the foam, low flammability,
low smoke evolution, good thermal stability and good dimensional stability.
The structural performance of the board as expressed by compressive strength and dimensional stability is satisfactorily
met only when the weight % of the isocyanate is 57% irrespective of the OH # of the polyol at the tested foam density. At a
lower weight % of isocyanate in the foam, the density would need to be higher to avoid any structural performance issues.
Keep in mind, the index will have to be as high as 310 to get 57% isocyanate when using lower OH polyols and higher
levels of TCPP. Lower TCPP levels do improve structural performance but also would hurt fire performance.
The fire performance of the board as measured by the FM calorimeter can be easily met when isocyanate content of the
foam is 57% even with low amounts of TCPP and irrespective of the OH # of the polyol. As the weight % of the isocyanate
in the formulation is reduced, good fire performance is achieved only when the FR levels is relatively high. But higher FR
level do hurt structural performance at the same density [20].
This work suggests that it may be more prudent to formulate keeping the weight percent of isocyanate in the total foam
constant rather than the index. Thus when looking to improve the cost-effectiveness of polyiso foam, one should remember
that board density dominates all other factors affecting cost. Any efforts to optimize the isocyanate (HF-PMDI) content of
the foam should be checked to ensure that they do not inadvertently increase the overall cost of the polyiso foam by raising
the minimum stable density of the foam. A plausible route to decrease density is by using alternative blowing agents as
suggested in our paper at the last API [21].

All information contained herein is provided "as is" without any warranties, express or implied, and under no
circumstances shall the authors or Huntsman be liable for any damages of any nature whatsoever resulting from the use or

831
reliance upon such information. Nothing contain in this publication should be construed as a license under any intellectual
property right of any entity, or as a suggestion, recommendation, or authorization to take any action that would infringe any
patent. The term "Huntsman" is used herein for convenience only, and refers to Huntsman Corporation, its direct and
indirect affiliates, and their employees, officers, and directors.
RUBINATE and JEFFCAT are registered trademark of Huntsman Corporation or an affiliate thereof in one or more,
but not all, countries.

ACKNOWLEDGEMENTS

The authors wish to thank Tom Piazza and David Dorsey for their invaluable help in producing this paper. The authors
would also like to thank all the associates at Huntsman Advanced Technology Center who helped set up the laboratories
and testing facilities in time to make this work possible.

REFERENCES

1. PIMA. 2005. Polyiso Foam Roof Insulation: Its More than R-value, Its Meeting the Codes, Advisories and other
documents on www.polyiso.org
2. Berrier, R. E., S. N. Singh, and J. S. Costa. 1998. Hydrocarbon Blown Rigid Polyurethane Foam for the Boardstock
Industry A Novel Approach, Proceedings of the Polyurethanes Expo 98, pp. 5-13.
3. Gilbert, D. R.. 1985. Index Versus Flammability in Urethane Modified Isocyanurate Foam Systems, Proceedings of
the SPI 30th Annual Technical Conference, pp. 172-175.
4. David Shieh, R. Donald, J. Luna, and A. DeLeon. 2006. Low OH number Polyester Polyols for Lamination,
Proceedings of the Polyurethanes Expo 06.
5. Feske, B. and J. Canaday. 2001. Optimization of Flame-Retardants for Rigid PIR Foams: A new Screening
Apparatus, and Correlation to Large-Scale Flammability Tests, Proceedings of Polyurethanes Expo 2001, pp. 627.
6. Singh, S. N., J. J. Lynch and D. Daems. 1995. Techniques to Assess the Various Factors affecting the Long Term
Dimensional Stability of Rigid Polyurethane Foam, Proceedings of the Polyurethane 1995, pp. 11-19.
7. Ross, L. and J. Hagan. 2002. Polyurethane Products: Overview of US Model Building Code Fire Performance
Requirements, Proceedings of Polyurethanes Expo 2002, pp.217-233.
8. DeLeon, A. 1981. Isocyanaurate Foam in F.M. Class I Steel Roof Deck Construction, Proceedings of the SPI 25th
Annual Technical Conference, pp. 45-50.
9. Tideswell, R. B. 1982. Development of a Factory Mutual Class I Isocyanurate Foam Laminate, Proceedings of the
SPI 26th Annual Technical Conference, pp. 314-19.
10. Simon., J, F. Barla, A. Kelemen-haller, F. Farkas, and M. Kraxner. 1988. Thermal Stability of Polyurethanes,
Chromatographia, Vol 25, No. 2 pp. 99-106.
11. Nelson, G.L. 1995. Surfaces and Char, in Fire and Polymers II, ACS Symposium Series 599, G. L. Nelson, ed.
Washington, ACS pp. 159-160.
12. Factor, A. 1990 Char Formation in Aromatic Engineering Polymers, Chapter 19 in Fire and Polymers, G. L. Nelson,
ed. Washington, ACS pp. 274-287.
13. Tang, Z., M. M. Maroto-Valer, J. M. Andresen, J. W. Miller, M. L. Listermann, P. L. McDaniel, D. K. Morita, and W.
R. Furlan. 2002. Thermal Degradation of Rigid Polyurethane Foams Prepared with Different Fire Retardant
Concentrations and Blowing Agents, Polymer 43. pp. 6471-6479.
14. Bleuel, e., U. Totermund, C. Seitz, P. Boehme, and M. Reichelt. 2002. Fundamentals of Flame Retardation: The
Burning Process and the mode of Action of Flame Retardants, Proceedings of Polyurethanes Expo 2002, pp. 234-
243.
15. Matuschek, G. 1995. Thermal Degradation of Different Fire Retardant Polyurethane Foams, Thermochimica Acta
263, pp.59-71.
16. Tokuyasu, N., K. Fujimoto, and T. Hamada. 2004. Halogen Free Flame Retardant Technology for Polyurethane
Foam, Proceedings of Polyurethanes 2004, pp. 234-243.
17. Chamberlain, D. L. 1978. Flame Retardancy of Polymeric Material, W. C. Kuryla and A. J. Papa, eds. Vol. 4, New
York, Marcel Dekker, Inc. pp. 109-168.
18. Williams, W., G. R. Alessio, and S. V. Levchik, Development of a Bench-scale and Micro-scale Test to Correlate
with FM 4450 Calorimeter Test, Proceedings of Polyurethanes Expo 2005. pp. 409-414.
19. Falloon, S. and R. Roark. 2003. Novel Flame Retardants for Hydrocarbon Blown Polyisocyanurate Foam,
Proceedings of Polyurethanes Expo 2003. pp. 42-45.

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20. Prociak, A., J. Pielichowski, M. Modesti, F. Simioni, and M. Checchin. 2001. Influence of Different Phosphorous
Flame Retardants on Fire Behaviour of Rigid Polyurethane Foams Blown with Pentane, Polymery, 46, nr 10. pp. 692-
696.
21. Singh, S. N., M. Ntiru-Karamagi, and M. Ritchie. 2005. Optimizing Polyiso Blowing Agents, Proceedings of
Polyurethanes Expo 2005. pp. 402-408.

BIOGRAPHIES

Sachchida N. Singh

Sachchida is currently a Scientist Fellow for the Polyurethanes business at Huntsman. Since
joining in 1987, he has held increasingly responsible positions in the technology development
departments of the business. He has worked in many different application areas of polyurethane
chemistry and technology and has lately spent significant efforts in the rigid foam sector. He has
a doctoral degree in Materials Science and Engineering from Massachusetts Institute of
Technology and a Master of Science degree in Chemical Engineering from Rensselaer
Polytechnic Institute.

Jody S. Fife

Jody S. Fife is currently a Technical Service Representative for the Polyurethanes business at
Huntsman. Since joining in 1992 he has worked in many different positions with the production
facility in Geismar, LA. He has held positions such as Laboratory technician, Foam technician,
and Equipment Inspector. His latest position has been a technical service representative of
polyurethanes chemistry in the rigid foam sector. He has a Bachelor of Science in Management
and Chemistry from Southeastern Louisiana University.

Sheila Dubs

Sheila Dubs is currently a Senior Technical Service Representative for the Polyurethanes
business at Huntsman. Since joining the business in 1999, she has worked in many different
application areas, namely, automotive, flexible foam, elastomers, and rigid foam, in a variety of
technical service and development roles. She earned a Bachelor of Science in Chemical
Engineering degree from University of Michigan.
.

Paul D. Coleman

Paul is currently a Technical Manager for the Polyurethanes business at Huntsman. Since
joining the business in 1986, he has held a variety of positions in different application areas of
the rigid foam technical group. He earned a Bachelor of Science in Chemical Engineering
(BSChE) degree with a concentration in Economics from Tufts University.

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