Investigation of Fire Resistant Polyurea Systemscradpdf.drdc-rddc.gc.ca/PDFS/unc101/p533664_A1b.pdf · Investigation of Fire Resistant Polyurea Systems Final Report Brenda DiLoreto

Defence R&D Canada – Atlantic

Investigation of Fire Resistant Polyurea

SystemsFinal Report

Brenda DiLoreto and Sam DiLoretoElastochem Specialty Chemicals Inc

Elastochem Specialty Chemicals Inc37 Easton RoadBrantford, Ontario N3P 1J4

Project Manager: Brenda DiLoreto, 519-754-1678 ext 229

Contract Number: W7707-088115/001/HAL

Contract Scientific Authority: Royale S. Underhill, 902-427-3481

The scientific or technical validity of this Contract Report is entirely the responsibility of the contractor and thecontents do not necessarily have the approval or endorsement of Defence R&D Canada.

Contract Report

DRDC Atlantic CR 2009-071

October 2009

Copy No. _____

Defence Research andDevelopment Canada

Recherche et développementpour la défense Canada

This page intentionally left blank.

Investigation of Fire Resistant Polyurea SystemsFinal Report

Brenda DiLoreto

Sam DiLoreto

Elastochem Specialty Chemicals Inc

Prepared by:

Elastochem Specialty Chemicals Inc.

37 Easton Road

Brantford ON N3P 1J4

Project Manager: Brenda DiLoreto 519-754-1678 ext 229

Contract Number: W7707-088115/001/HAL

Contract Scientific Authority: Dr. Royale S. Underhill 902-427-3481

The scientific or technical validity of this Contract Report is entirely the responsibility of the contractor and the

contents do not necessarily have the approval or endorsement of Defence R&D Canada.


Contract Report


October 2009

Approved by

Royale S. Underhill

Contract Scientific Authority

Approved for release by

Calvin V. Hyatt

Chair/Document Review Panel

c© Her Majesty the Queen in Right of Canada as represented by the Minister of National

Defence, 2009

c© Sa Majeste la Reine (en droit du Canada), telle que representee par le ministre de la

Defense nationale, 2009

Original signed by Royale S. Underhill

Original signed by Ron Kuwahara for

Abstract

DRDC Atlantic is interested in evaluating polyurea coatings for use in enclosed spaces

as damage control materials. For such applications, their fire resistant properties need to

be improved. The work reported here is divided into two parts. In Part 1, three base

polyurea formulations were developed and evaluated by cone calorimetry. The goal was

to replace portions of the organic polyurea backbone to improve the flame retardancy. The

first sample utilized an diisocyanate prepolymer with a portion of its backbone made up of

a phosphorous polyol, the second sample replaced a portion of the polyether amine with an

amine terminated polydimethylsiloxane and the third sample combined the phosphorous

polyol with the amine terminated polydimethylsiloxane. Cone calorimetry determined that

the third sample yielded the best results for lowering smoke production and increasing

time to ignition. It is believed that the phosphorous polyol and polydimethylsiloxane have

a synergistic effect in improving the flame properties.

In Part 2 of this work, the phosphorous polyol/ polydimethylsiloxane based polyurea was

used as the base formulation and various combinations of flame retardant additives were

incorporated in an attempt to further improve the flame properties. Cone calorimetry in-

dicated that the best combinations included sodium phosphate, ammonium polyphosphate

(APP)/triisocyanurate 3:1, treated graphite, urea, zeolite and melamine.

Resume

RDDC Atlantique s’interesse a l’evaluation de revetements en polyuree devant servir dans

des espaces clos comme materiaux pour limiter les dommages. Pour de telles applications,

il faut ameliorer leurs proprietes ignifuges. Le present rapport est divise en deux parties.

Dans la partie 1, on rapporte le developpement de trois formulations de polyuree de base et

leur evaluation par calorimetrie a cone. L’objectif etait de remplacer des parties du squelette

organique de la polyuree afin d’ameliorer l’ignifugation. Pour le premier echantillon, on

a utilise un prepolymere de diisocyanate avec une partie de son squelette en un polyol

renfermant du phosphore. Pour le deuxieme echantillon, on a remplace une partie de la

polyetheramine par un polydimethylsiloxane a terminaisons amines. Pour le troisieme

echantillon, on a combine le polyol renfermant du phosphore avec le polydimethylsiloxane

a terminaisons amines. La calorimetrie a cone a permis de determiner que le troisieme

echantillon conduisait au meilleur resultat pour la reduction de la production de fumee et

l’augmentation du delai avant inflammation. On pense que le polyol renfermant du phos-

phore et le polydimethylsiloxane ont des effets synergiques conduisant a l’amelioration des

proprietes ignifuges.

Dans la partie 2 du present travail, on a utilise la polyuree a base de polyol renfermant

du phosphore et de polydimethylsiloxane comme formulation de base a laquelle diverses

DRDC Atlantic CR 2009-071 i

combinaisons d’additifs ont ete incorporees afin d’essayer d’ameliorer encore plus les

proprietes ignifuges. La calorimetrie a cone a montre que les meilleures combinaisons com-

portaient du phosphate de sodium, du polyphosphate/triisocyanurate d’ammonium (3/1),

du graphite traite, de l’uree, une zeolite et de la melamine.

ii DRDC Atlantic CR 2009-071

Executive summary

Investigation of Fire Resistant Polyurea Systems: Final

Report

Brenda DiLoreto, Sam DiLoreto; DRDC Atlantic CR 2009-071; Defence R&D Canada

– Atlantic; October 2009.

Background: The demand for improved damage control materials to address blast mit-

igation has led to an interest in polyureas. Polyurea shows potential for use in retrofit

pre-existing platforms because it can be applied as a spray, has extremely fast reaction

kinetics, fast cure times and low volatile organic compounds. However, it is limited in its

use because of poor fire properties. DRDC is exploring synthetic and additive routes to

improve the polyurea flame retardancy.

A polyurea is synthesized from two components: a diisocyanate (component A) and a

diamine (component B). Elastochem Specialty Chemicals explored changing the flamma-

bility of polyurea through a synthetic route and the addition of flame retardant additives.

The first part of this work explored removing some of the organic portion of the polyurea

by changing its backbone, making the base polyurea less flammable. The second part of

this work utilized the base polyurea from Part 1 and explored the addition of flame retardant

additives.

Results: The combination of a phosphorous polyol in component A and an amine termi-

nated polymethylsiloxane in component B yielded a polyurea with improved flame retar-

dant properties. It is believed that the phosphorous and siloxane interacted to produce a

more stable char than either constituent alone.

The addition of fillers improved the flame retardancy. Treated graphite contributed to an in-

sulating layer of char which was bound to the polymer surface when combined with sodium

phosphate, ammonium polyphosphate (APP)/triisocyanurate, zeolite and melamine.

Significance of results: Although the DoD Military Specification for Standard fire and

toxicity test methods and qualification procedure for composite material systems used

in hull, machinery and structural applications (MIL-STD-2031) was not met, significant

improvements towards these targets were made. A great deal of information was discovered

regarding heteroatom substitution (both phosphorous and silicon), as well as the use of

flame retardant fillers. The organic (i.e., carbon containing) components of the polyurea

are combustible. By replacing the carbon atoms with either phosphorous or silicon, the

polymer becomes less combustible. Similarily, addition of fillers reduces the amount of

combustible material in the end product. The key is to optimize the flammability properties,

while minimizing any detrimental affects to other properties.

DRDC Atlantic CR 2009-071 iii

Future plans: Based on the success of the treated graphite, the use of aromatic polyamines

as crosslinkers will be explored. It is hoped that incorporation of the carbon rings into

the polymer backbone will help to increase the formation of the char layer, thus further

improving the polyurea flammability properties. The goal is to obtain a composite which

will mitigate blast, while not increasing the fire risk to the space where it is being used.

iv DRDC Atlantic CR 2009-071

Sommaire

Investigation of Fire Resistant Polyurea Systems: Final

Report

Brenda DiLoreto, Sam DiLoreto ; DRDC Atlantic CR 2009-071 ; R & D pour la defense

Canada – Atlantique ; octobre 2009.

Contexte : La demande pour de meilleurs materiaux pour limiter les dommages en cas

d’explosion a conduit a susciter de l’interet pour les polyurees. La polyuree presente un

potentiel d’utilisation pour la modernisation de plateformes, car elle peut etre appliquee par

pulverisation, a une cinetique de reaction extremement rapide, des temps de durcissement

courts et une faible teneur en composes organiques volatils. Toutefois, son utilisation est

limitee en raison de ses mediocres proprietes au feu. RDDC etudie des voies de synthese

et d’ajout de composes pour ameliorer les proprietes ignifuges de la polyuree.

Une polyuree a ete synthetisee a partir de deux composes : un diisocyanate (compose A)

et une diamine (compose B). Elastochem Specialty Chemicals a etudie la possibilite de

modifier l’inflammabilite de la polyuree par voie synthetique et en ajoutant des additifs

ignifuges. Dans la premiere partie du present travail, on a explore l’elimination de certaines

parties organiques de la polyuree en modifiant son squelette et rendant ainsi la polyuree de

base moins inflammable. Pour la seconde partie du travail, on a utilise la polyuree de base

ainsi obtenue et on a etudie l’addition de composes ignifuges.

Resultats : La combinaison d’un polyol renfermant du phosphore et d’un polymethyl-

siloxane a terminaisons amines a produit une polyuree aux proprietes ignifuges ameliorees.

On pense que le phosphore et le siloxane ont interagit pour produire un produit de carbon-

isation plus stable que ceux produits par les composants pris seuls.

L’addition de matieres de charge a permis d’ameliorer les proprietes ignifuges. Du graphite

traite a contribue a la formation d’une couche isolante de produit de carbonisation qui etait

liee a la surface du polymere lorsqu’il etait combine avec du phosphate de sodium, du

polyphosphate/triisocyanurate d’ammonium, une zeolite et de la melamine.

Importance des resultats : Bien que la specification militaire du MDN pour ≪ Standard

fire and toxicity test methods and qualification procedure for composite material systems

used in hull, machinery and structural applications ≫ (MIL-STD-2031) n’a pas ete satis-

faite, des ameliorations importantes pour l’atteinte de cet objectif ont ete realisees. On

a recueilli de nombreux renseignements sur la substitution d’un heteroatome (phosphore

ou silicium), ainsi que sur l’utilisation de matieres de charge ignifuges. Les composants

organiques (contenant du carbone) de la polyuree sont combustibles. En remplacant les

DRDC Atlantic CR 2009-071 v

atomes de carbone par du phosphore ou du silicium, le polymere devient moins com-

bustible. De meme, l’addition de matieres de charge reduit la quantite de matiere com-

bustible se retrouvant dans le produit final. La cle est d’optimiser les proprietes d’inflamma-

bilite tout en reduisant au minimum tout autre effet negatif sur les autres proprietes.

Recherches futures : En se basant sur le succes rencontre avec le graphite traite, on

etudiera l’utilisation de polyamines aromatiques comme agents de reticulation. On espere

que l’incorporation de noyaux carbones dans le squelette du polymere contribuera a aug-

menter la formation d’une couche de produit de carbonisation, ameliorant ainsi encore plus

les proprietes d’inflammabilite de la polyuree. L’objectif est d’obtenir un composite qui

limitera les effets d’une explosion sans accroıtre les risques dans l’espace ou il est utilise.

vi DRDC Atlantic CR 2009-071

Table of contents

Abstract . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . i

Resume . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . i

Executive summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . iii

Sommaire . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . v

Table of contents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vii

List of figures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . viii

List of tables . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . viii

1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1

2 Part 1 — Inorganic substitution of polyurea backbone . . . . . . . . . . . . . . . 3

2.1 Polyurea synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4

2.2 Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5

3 Part 2 — Fire resistant fillers . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7

3.1 Filled polyurea preparation . . . . . . . . . . . . . . . . . . . . . . . . . 7

3.2 Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

4 Conclusions and future work . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15

References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16

Annex A: MSDS & Data Sheets . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17

Annex B: ACT Labs FTIR Spectra of Base Polyureas . . . . . . . . . . . . . . . . 25

Annex C: In-house Flame Testing . . . . . . . . . . . . . . . . . . . . . . . . . . . 27

Distribution list . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31

DRDC Atlantic CR 2009-071 vii

List of figures

Figure 1: Basic polyurea synthesis. . . . . . . . . . . . . . . . . . . . . . . . . . 1

Figure 2: Cross-section images of the filled polyurea samples. All images are

the same scale. Film thicknesses are 2.1–2.5 mm, with P2P2S6 being

the thickest. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

Figure 3: Example of a sample from the benchtop burn tests. . . . . . . . . . . . 10

Figure 4: Comparison of time to ignition (s) for Part 1 and Part 2 . . . . . . . . . 10

Figure 5: Comparison of peak heat release rate (kW/m2) for Part 1 and Part 2 . . . 11

Figure 6: Comparison of average heat release rate (kW/m2) for Part 1 and Part 2 . 11

Figure 7: Comparison of smoke factor (× 103) for Part 1 and Part 2 . . . . . . . . 12

Figure 8: Comparison of mass loss rate (g/m2s) for Part 1 and Part 2 . . . . . . . 12

List of tables

Table 1: Cone calorimetry results for Part 1 . . . . . . . . . . . . . . . . . . . . 5

Table 2: DMA results for Part 1 . . . . . . . . . . . . . . . . . . . . . . . . . . 6

Table 3: Description of fire resistant fillers used in Part 2 . . . . . . . . . . . . . 7

Table 4: Formulation of samples for Part 2 . . . . . . . . . . . . . . . . . . . . . 8

Table 5: Cone calorimetry results for Part 2. . . . . . . . . . . . . . . . . . . . . 13

Table 6: DMA results for Part 2. . . . . . . . . . . . . . . . . . . . . . . . . . . 14

viii DRDC Atlantic CR 2009-071

1 Introduction

With increasing concern over the threat from improvised explosive devices (IED), interest

in materials that can be retrofitted to land vehicles and ships for increased survivability has

grown. One possible material is polyurea. The advantages of polyurea are its extremely

fast reaction kinetics, fast cure times and low volatile organic compounds (VOC).

Polyureas are synthesized using a two component system. The first component (A) is a

diisocyanate. The second component (B) is a diamine. The molecular weight, degree of

functionality and level of heteroatom substitution in these components can be chosen to

tailor the properties of the final polyurea.

The use of polyurea coatings has increased in popularity since the early 1980’s, although

their applications have been somewhat limited due to poor flame properties. Defence R&D

Canada is interested in evaluating polyurea coatings for use in enclosed spaces. The work

presented here continues from previous work [1] and further investigates synthetic methods

for improving the flammability properties of polyureas. This study has two parts. In

Part 1, a portion of the organic material of the polyurea backbone was replaced with a

phosphorous polyol and/or an amine terminated polydimethylsiloxane. The flammability

properties of the resulting polyureas were examined using cone calorimety. The optimum

polyurea formulation was then used in Part 2 to prepare a series of polyurea formulations

containing various flame retardant additives. The flame retardants included combinations

of minerals, intumescent systems, and graphite.

Fourier transform infrared spectroscopy (FTIR) was used to characterize the new poly-

mers using the phosphorous polyol and amine terminated polydimethylsiloxane precursors.

Cone calorimetry (ASTM E 1354) was used to determine the time to ignition, peak heat

release rate (HRR), smoke evolution, mass loss rate and total heat release [2]. Ideal

materials would have a long time to ignition and a reduced HRR, and the addition of a

fire retardant should not yield more smoke.

The time to ignition measures the ability to ignite a material at a specific heat flux. It

is related to the volatility of the degradation products and the time required to reach the

critical fuel concentration in the vapour over the specimen. Time to ignition gives an

indication of the time available for personnel to escape a space prior to flashover. The

Figure 1: Basic polyurea synthesis.

DRDC Atlantic CR 2009-071 1

DoD military (navy) specification (MIL-STD-2031) for minimum time to ignition with a

radiant heat of 50 kW/m2 is 150 s [3]. Peak HRR influences the rate of burning and the

rate of mass loss and determines whether the surrounding materials will ignite. The peak

HRR can be used as an indication of the degree to which a material will burn at its highest

rate of combustion [4]. The MIL-STD-2031 sets a maximum peak HRR of 65 kW/m2 as

determined using cone calorimetry with a radiant heat source of 50 kW/m2 [3,4]. Samples

of each formulation were also submitted to Defence R&D Canada — Atlantic for dynamic

mechanical analysis (DMA) and differential scanning calorimetry (DSC).

2 DRDC Atlantic CR 2009-071

2 Part 1 — Inorganic substitution of polyurea

backbone

In Part 1 of this research the focus was on the base polyurea formula. Various combinations

of inorganic material were used to replace portions of the organic backbone in an attempt

to improve the fire resistant properties of the unfilled polyurea, specifically the time to

ignition, peak heat release rate (HRR) and the total smoke released.

A review of available phosphate containing polyols and amine terminated polydimethyl-

siloxanes was performed to find suitable materials that could be used in the base formula.

The substitute in the diisocyanate portion (i.e., component A) must be a liquid at room

temperature and suitable for making a stable prepolymer with the diisocyanate. Many of

the available phosphorous polyols are solid at room temperature (e.g., Struktol R© Polydis R©

3710) or are cut with solvent (e.g., Stuctol R© VP 37452 S). These are not appropriate for this

application. These and other phosphorous polyols were also too high in molecular weight

(<500 g/mol is required) and therefore would not be incorporated into the prepolymer

properly. An approximate viscosity of 500 cps is also required so that if fillers were added,

the material could still be put through a static mixer. Exolit 550 was one possible material,

however the viscosity was too high (i.e., 3500 cps). Exolit OP 560 phosphorous polyol from

Clariant Pigments and Additives division was selected. It is a liquid at room temperature,

has a low viscosity and has a molecular weight of 250 g/mol. The supplier’s website and

sales representatives were consulted in order to determine the best available product to meet

the criteria above. The diisocyanate that was reacted with the Exolit OP 560 was Mondur

M (4,4′-methylene diphenyl isocyante) (Bayer).

Previous work used a base polyurea formula which had 15% of the organic amine in com-

ponent B replaced with a phosphorous polyol (Exolit OP 560) [1]. The cone calorimetry

showed an improvement to the peak heat release rate (from 1252 Kw/m2 for the polyurea

formula with no phosphorous polyol to 761 Kw/m2 for the polyurea with 15% phosphorous

polyol), however the total smoke increased from about 17 m2 to about 28 m2 when the

phosphorous polyol was used. That study concluded that because the reaction of the

diisocyanate with the amine is orders of magnitude faster than the reaction of isocyante with

the phosphorous polyol, there may have been unreacted phosphorous polyol that would

cause a large amount of smoke when burned and thus increase the total smoke in the cone

calorimetry testing.

In the work presented here, component A utilized the same phosphorous polyol (i.e.,

Exolit OP 5600), reacted with the diisocyanate (i.e., Mondur M) to form a prepolymer in

an attempt to ensure all of the polyol was reacted. The prepolymer was then used with the

usual component B amine (i.e., Ethacure). This was identified as P2P1S1 (P2 for project 2,

P1 for Part 1 and S1 for sample 1).


Another approach for replacing organic portions of the polyurea formulation was to replace

the polyether amine portion of component B with an amine terminated polydimethylsilox-

ane of similar molecular weight in the base formula. For replacing the polyether amine

the material must be amine terminated and have a similar molecular weight to D2000.

DMS-A15 (Gelest Inc.), an amine terminated polydimethylsiloxane, was selected. This

was identified as P2P1S2.

The third sample utilized component A of P2P1S1 (i.e., Exolit OP 560) and component B

of P2P1S2 (i.e., DMS-A15) to investigate if greater improvements to the flame retardancy

could be achieved by combining both approaches.

The three different base formulations were prepared and submitted to DRDC Atlantic for

physical testing (i.e., Cone Calorimetry, DSC, and DMA). Samples were also submitted to

Actlabs for characterization via FTIR (Annex B).

2.1 Polyurea synthesis

The three samples that were prepared were (molar percents):

P2P1S1: component A: 50% 4,4′-MDI (Pure) Mondur M

50% Exolit OP 560

component B: 30% Ethacure 100/300

70% D2000/T3000/T5000

P2P1S2: component A: 100% Rubinate 9009


70% DMS-A15

P2P1S3: component A: 50% 4,4′-MDI (Pure) Mondur M

50% Exolit OP 560


70% DMS-A15

For P2P1S1, the component A was prepared by adding 2 mols of 4,4′-MDI (Mondur M)

into a mixing vessel at 40◦C, 1 mol of Exolit OP 560 was added slowly to the vessel.

The ingredients were mixed at 60 RPM with a paddle blade mixer for 5 minutes. The

temperature rose to 80◦C and was held at this temperature for two hours by placing it in

the oven. The resin was then allowed to cool.

For component B of the polyureas, approximately 200 g of material was prepared by

weighing 60 g of the Ethacure and 140 g of the D200/T300/T500 or DMS-A14 depending

which sample (i.e., P2P1S1 or P2P1S2) was being made. The material was mixed for

1 minute using a low speed paddle mixing blade (500 RPM) at room temperature and

normal pressure.


Table 1: Cone calorimetry results (ASTM E1354) for Part 1 with a radiant heat source of

50 kW/m2. (Testing by Bodycote Testing Group)

Sample ID Time to

Ignition

(s)

Peak

Heat

Release

Rate

(kW/m2)

Average

Heat

Release

Rate

(kW/m2)

Total

Smoke

(m2)

Smoke

Factor

(× 103

kW/kg)

Peak

Mass

Loss

Rate

(g/m2s)

MIL STD 2031 150 60 n/a n/a 6.5 n/a

Base polyurea 21 1252.0 237.4 17.2 657 43.89

(no phosphorous or

polysiloxane)∗

Base polyurea 21 760.6 310.0 28.3 474 33.56

(containing 15% of

phosphorous polyol

in component B)∗

P2P1S1 11 286.3 133.0 27.2 256 21.14

P2P1S2 14 542.4 144.3 21.8 433 23.11

P2P1S3 16 351.9 69.8 9.1 245 22.95∗ data taken from previous work [1].

Components A and B were prepared separately, then 200 g of each were loaded into 200 mL

side by side cartridges and dispensed through an 18 element, 14

′′static mixing tube into

2 mm and 3 mm thickness sheet sample moulds. This was done at room temperature using

a hand held dispensing gun.

All sample sheets were post cured, in an oven, for 16 hours at 65◦C at normal atmospheric

conditions. Samples for cone calorimetry, DMA and DSC were cut from the cured sheets

using a band saw.

2.2 Discussion

Results of the cone calorimetry for Part 1 are outlined in Table 1. Shown are: Time to

Ignition, Peak Heat Release Rate (HRR), Average Heat Release Rate (HRR), Total Smoke,

Smoke Factor (which is calculated by multiplying the total smoke released at 300 s by the

peak HRR) and Peak Mass Loss Rate.

By examining the cone calorimetry results in Table 1, it can be seen that P2P1S3 (con-

tained a diisocyanate/phosphorous polyol prepolymer reacted with an amine terminated

polydimethylsiloxane) gave the best overall results. It had the longest time to ignition

(16 seconds), and the least smoke released (9.1 m2). Although P2P1S3 had a slightly higher

peak HRR than P2P1S1, its average HRR 69.8 kW/m2, was the lowest of the three samples.


Table 2: DMA results for Part 1, at 1 Hz, 25◦C. (Testing by DRDC Atlantic/Dockyard

Labortory (Atlantic))

Sample ID Young’s Modulus

(MPa)

P2P1S1 158.1

P2P1S2 181.6

P2P1S3 2539

The peak HRR for P2P1S3 was much lower than the base material of previous work [1],

which also contained phosphorous polyol, but added into component B. The difference

between these two approaches was that in the previous work, the polyol was reacted into

the polyurea during the crosslinking stage, while in the current study, it was reacted with

the diisocyanate of component A to yield a prepolymer which was subsequently reacted

to form the completed polyurea. The improved flammability performace observed in the

current work was likely due to the phosphorous polyol being completely reacted into the

polymer, at higher loading levels; increased from 7.5% in the final polymer in the previous

work [1] to 25% in the final polymer in this work. P2P1S3 was selected to be the base

formulation for Part 2 of this study.

The smoke values for P2P1S1 and P2P1S2 were 27.2 m2 and 21.8 m2 respectively. It

was believed that reacting the phosphorous polyol with the diisocyanate to produce a

prepolymer would contribute to decreasing the smoke value from previous work [1]. The

smoke value however, is still high for both samples. The smoke value for P2P1S3 was less

than half of P2P1S1 and P2P1S2. It can be concluded that phosphorous polyols produce

higher smoke values in the material whether as a reactant in component B, or reacted in

the component A prepolymer. The current work also shows a synergistic effect between

phosphorus and siloxane when they are contained in the backbone of the polymer. One

theory for this, is that during the combustion process the phosphorous and siloxane interact

to produce a more stable char than either of them individually, thus reducing the total smoke

released.

Results of the DMA testing performed at DRDC Atlantic, for Part 1 are listed in Table 2.

The FTIR spectra are shown in Annex B. The polyurea from previous work, with no

phosphorous or polysiloxane, had a storage modulus of 203.6 MPa (at 25◦C) [1]. The

samples with only one component substituted show lower moduli. When both components

are substituted, there is a drastic increase in modulus.


3 Part 2 — Fire resistant fillers

The second part of this work focused on adding fillers to the base polyurea that was selected

in Part 1 (i.e., P2P1S3 — Exolit OP 560 substituted diisocyanate and DMS-A15 substituted

polyether amine) in order to improve fire resistant characteristics. The results from previous

work showed that a combination of flame retardants was required to obtain the best results

[1]. The additives explored in the current work are listed in Table 3.

Table 3: Description of fire resistant fillers used in Part 2

Additive Description

sodium phosphate Recochem

Polybor R© disodium octaborate tetrahydrate from US Borax

ammonium sulfate Canada Colours and Chemicals

APP/triisocyanurate (3:1) internally blended

treated graphite expanded graphite flakes #1721 from Ashbury An-

thracite Industries

urea Sylvite

ammonium phosphate Rhodia

sodium bicarbonate Canada Colours and Chemicals

APP ammonium polyphosphate

Zeolite 3A Intumax AC-2

melamine 3ST Powder from Zeochem

melamine-phosphate Melapur 200 from Ciba

calcium phosphate blend 1:1 blend of calcium phosphate and ammonium phos-

phate from Canada Colours and Chemicals

talc Cantal 490 from Canada Colours and Chemicals

3.1 Filled polyurea preparation

From Part 1, P2P1S3 was selected as the base polyurea formulation for Part 2. Again values

are molar percents.

component A: 50% 4,4′-MDI (Pure) Mondur M

50% Exolit OP 560


70% DMS-A15

The base resins for components A and B were produced as outlined in §2.1. The powders

were weighted and added, according to the percentages in Table 4, to both component A

and B. For Sample P2P2S1, for example; since 200 g is used in each side of the side by

side cartridges, 5 g of sodium phosphate, 75 g of ammonium sulphate, 10 g of melamine,

10 g of calcium phosphate blend and 5 g of talc would be added to 100 g of the base resin


Table 4: Formulation of samples for Part 2

Sample ID Formulation

P2P2S1∗ 2.5% sodium phosphate, 35% ammonium sulfate, 5% melamine, 5%

calcium phosphate blend, 2.5% talc

P2P2S2 4% sodium phosphate, 4% Polybor R©, 4% ammonium sulfate, 4%

APP/triisocyanurate 3:1, 4% treated graphite, 4% urea, 4% ammonium

phosphate, 4% sodium bicarbonate, 4% APP, 4% zeolite, 4% melamine

P2P2S3 10% sodium phosphate, 10% ammonium sulfate, 10%

APP/triisocyanurate 3:1, 4% treated graphite, 2% zeolite, 4%

melamine

P2P2S4 10% sodium phosphate, 10% APP/triisocyanurate 3:1, 8% treated

graphite, 8% urea, 2% zeolite, 4% melamine

P2P2S5 10% APP/triisocyanurate 3:1, 6% treated graphite, 6% urea, 6% ammo-

nium phosphate, 6% sodium bicarbonate, 2% zeolite, 4% melamine

P2P2S6 30% sodium phosphate, 4% sodium bicarbonate, 2% zeolite, 4%

melamine

P2P2S7 10% sodium phosphate, 20% ammonium sulfate, 4% treated graphite,

4% melamine, 2% calcium phosphate blend, 2% talc

P2P2S8 10% sodium phosphate, 10% ammonium sulfate, 5%

APP/triisocyanurate 3:1, 4% treated graphite, 2% zeolite, 4%

melamine, 2.5% calcium phosphate blend, 2.5% talc∗ same filler ratios that performed the best from previous work [1].

to give the desired final concentration . The powders were added to both component A and

B so that the 1:1 ratio static mixer cartridges could be used.

The powders were mixed using a high speed shear mixer at 2500 RPM. Components A

and B were then loaded into 200 mL side by side cartridges and dispensed through 18

element, 14

′′static mixing tubes into 2 mm and 3 mm sheet sample moulds using a hand

held dispensing gun. All weighing and mixing was done at room temperature. Sample

sheets were post cured in an oven for 16 hours at 65◦C at normal atmospheric conditions.

The samples for cone calorimetry, DMA and DSC were then cut from the sample sheets

using a band saw. Figure 2 shows each of the eight samples in cross-section.

Sample pucks of polyurea containing various additive materials and combinations were

produced using the same methodology as the sheet samples. The pucks were burned at

Elastochem using a flame (1100◦F), produced by a propane torch. The flame was held

on the puck for 30 seconds and then removed. The amount of smoke, change in weight

after burning, time to ignition and the formation of the char was observed (the results were

qualitative only).


(a) P2P2S1 (b) P2P2S2

(c) P2P2S3 (d) P2P2S4

(e) P2P2S5 (f) P2P2S6

(g) P2P2S7 (h) P2P2S8

Figure 2: Cross-section images of the filled polyurea samples. All images are the same

scale. Film thicknesses are 2.1–2.5 mm, with P2P2S6 being the thickest.

3.2 Discussion

Qualitative observations from the in-house fire testing are included in Annex C. An exam-

ple of the burned pucks can be seen in Figure 3. The observations of the in-house fire testing

were used to determine which samples would be explored further using cone calorimetry.

The combinations which produced a good char (i.e.,not flakey), that was bonded to the

unburned polyurea, had very little weight loss after burning, had a slow ignition time,

extinguished quickly and had a low amount of observed smoke were selected. The cone

calorimetry results are listed in Table 5. Shown are; Time to Ignition, Peak Heat Release

Rate, Average Heat Release Rate, Total Smoke, Smoke Factor (which is calculated by

multiplying the smoke at 300s by the Peak heat release rate) and Peak Mass Loss Rate.

The data for Part 1 and Part 2 is presented in Figures 4–8.


Figure 3: Example of a sample from the benchtop burn tests.

0

5

10

15

20

P2P

1S

1

P2P

1S

2

P2P

1S

3

P2P

2S

1

P2P

2S

2

P2P

2S

3

P2P

2S

4

P2P

2S

5

P2P

2S

6

P2P

2S

7

P2P

2S

8

Tim

e to ignitio

n (

s)

Figure 4: Comparison of time to ignition (s) for Part 1 and Part 2, heat flux 50kW/m2.


0

100

200

300

400

500

P2P1S1

P2P1S2

P2P1S3

P2P2S1

P2P2S2

P2P2S3

P2P2S4

P2P2S5

P2P2S6

P2P2S7

P2P2S8

Peak Heat Release Rate (kW/m2)

Fig

ure

5:

Com

pariso

nof

peak

heat

releaserate

(kW

/m2)

for

Part

1an

dP

art2,

heat

flux

50kW

/m2.

0

50

100

150

200

250

300

P2P1S1

P2P1S2

P2P1S3

P2P2S1

P2P2S2

P2P2S3

P2P2S4

P2P2S5

P2P2S6

P2P2S7

P2P2S8

Average Heat Release Rate (kW/m2)

Fig

ure

6:

Com

pariso

nof

averag

eheat

releaserate

(kW

/m2)

(s)fo

rP

art1

and

Part

2,

heat

flux

50kW

/m2.

DR

DC

Atla

ntic

CR

20

09

-07

11

1

0

50

100

150

200

250

300

P2P1S1

P2P1S2

P2P1S3

P2P2S1

P2P2S2

P2P2S3

P2P2S4

P2P2S5

P2P2S6

P2P2S7

P2P2S8

Smoke Factor (X 103 kW/kg)

Fig

ure

7:

Com

pariso

nof

smoke

factor

for

Part

1an

dP

art2,heat

flux

50kW

/m2.

0 5

10

15

20

25

P2P1S1

P2P1S2

P2P1S3

P2P2S1

P2P2S2

P2P2S3

P2P2S4

P2P2S5

P2P2S6

P2P2S7

P2P2S8

Mass Loss Rate (g/m2s)

Fig

ure

8:

Com

pariso

nof

mass

loss

rate(g

/m2s)

for

Part

1an

dP

art2,heat

flux

50kW

/m2.

12

DR

DC

Atla

ntic

CR

20

09

-07

1

Table 5: Cone calorimetry results (ASTM E 1354) for Part 2 with a radiant heat source of

50 kW/m2. (Testing by Bodycote Testing Group)

Sample ID Time to

Ignition

(s)

Peak

Heat

Release

Rate

(kW/m2)

Average

Heat

Release

Rate

(kW/m2)

Total

Smoke

(m2)

Smoke

Factor

(× 103

kW/kg)

Peak

Mass

Loss

Rate

(g/m2s)

MIL STD 2031 150 65 n/a n/a 6.5 n/a

Base Polyurea∗ 16 351.9 69.8 9.1 245 22.95

(P2P1S3)

P2P2S1 15 301.6 102.6 18.0 135 16.87

P2P2S2 15 222.0 127.3 17.1 103 12.21

P2P2S3 12 207.9 105.7 13.4 90 12.03

P2P2S4 13 164.1 99.2 9.3 55 9.76

P2P2S5 15 202.2 118.4 12.1 76 11.21

P2P2S6 10 449.5 262.4 24.7 280 22.36

P2P2S7 11 205.2 116.8 11.9 81 12.29

P2P2S8 14 199.6 115.5 14.5 83 10.92∗ data taken from Part 1 of the current work.

From Table 5, it can be seen that P2P2S4 performed the best with a peak HRR of 164 kW/m2,

a smoke factor of 55,000 kW/kg and a mass loss rate of 9.76 g/m2s. The peak extinction

area, 498 m2/kg was about 50% less than the base polyurea (P2P1S3). The total smoke

released was 9.3 m2 which is the same (within error) as the result from the base with no

fillers.

All samples in Part 2 performed better than the base polyurea with no fillers (P2P1S3) in

terms of peak HRR except sample P2P2S6. This may be due to there being very little

carbon in the backbone of the polymer, and with no added graphite there is little carbon

present to form char. Sample P2P2S6 performed the worst with an increase in peak HRR

of 28%, a decrease of 38% for time to ignition and an increase in total smoke released of

170%. Sample P2P2S4 had the highest concentration of treated graphite (i.e., 8%), and it

is believed that this is why it gave the best result. The graphite by itself is powdery after it

is burned and creates an insulating layer that is slightly expanded away from the polyurea

surface. It is believed to be the combination of the sodium phosphate, APP/triisocyanurate,

zeolite and melamine that stabilizes this layer and keeps it attached to the polyurea surface.

The Results of the DMA testing for Part 2, which was performed by Defence R&D Canada,

are listed in Table 6. The addition of fillers up to 30 wt.% resulted in stiff, brittle samples.

The corresponding increase in storage modulus reflects this.


Table 6: DMA results for Part 2, at 1 Hz, 25◦C. (Testing by DRDC Atlantic/Dockyard

Laboratory (Atlantic))

Sample ID Young’s Modulus

(MPa)

P2P2S1 799±97

P2P2S2 592±177

P2P2S3 400±155

P2P2S4 346±6

P2P2S5 801±148

P2P2S6∗ –

P2P2S7 526±49

P2P2S8 756±219∗P2P2S6 was too brittle to test.


4 Conclusions and future work

Part 1 of the work reported here explored removing or substituting the organic back bone

of the base polyurea formulation in an effort to improve their fire retardant properties.

The sample yielding the best cone calorimetry results was P2P1S3, which resulted from

the reaction of the phosphorous polyol/diisocyanate prepolymer and the amine terminated

polydimethylsiloxane. Part 2 of this work explored the use of flame retardant fillers to

further improve the flammability properties of P2P1S3. The best results were observed

with the addition of graphite (layered carbon). In combination with synergists such as

sodium phosphate, APP/triisocyanurate, zeolite and melamine, stable chars were achieved.

All of the formulations were designed to be sprayed using a high pressure impingement

technique, that limits the viscosity of the material to less than 2000 cP. A low viscosity

limits the quantity of fillers (e.g.,treated graphite) that can be added to the formulations. If

the equipment can be modified to handle greater viscosities, the use of larger concentrations

of treated graphite can be investigated.

Future work should investigate the use of aromatic polyamines as crosslinkers. It has been

shown [5] that these organic rings increase the formation of the char layer which in turn

lowers the peak HRR.


References

[1] DiLoreto, B. and DiLoreto, S. (2008), Fire Retardant Additives: Their Effect on the

Flammability of Polyureas — Final Report, (DRDC Atlantic CR 2008-048)


[2] ASTM Standard E1354-08 (2008), Standard Test Method for Heat and Visible Smoke

Release Rates for Materials and Products Using an Oxygen Consumption

Calorimeter. ASTM International, West Conshohocken, PA.

[3] United States of America, Department of Defense (1991), Fire and toxicity test

methods and qualification procedure for composite material systems used in hull,

machinery, and structural applications inside naval submarines. Department of

Defense Test Method Standard. MIL-STD-2031.

[4] Langille, K., Nguyen, D., and Veinot, D. E. (1999), Inorganic Intumescent Coatings

for Improved Fire Protection of GRP, Fire Technology, 35, 99–110.

[5] Levchik, S. (2007), Flame Retardant Polymer Nanocomposites, New York: John

Wiley & Sons.


Product Information

MONDUR M Aromatic Diisocyanate

Descript ion

Mondur M is a high-purity-grade difunctionalisocyanate, diphenylmethane 4,4’-diisocyanate(MDI), available in three forms: flaked solid, fusedcake, and molten liquid.

Applicat ion

Mondur M diisocyanate can be used in the produc-tion of solid polyurethane elastomers, adhesives,coatings, and in intermediate polyurethane products.As with any product, use of Mondur M in a givenapplication must be tested (including but not limitedto field testing) in advance by the user to determinesuitability.

Product Specificat ions

Flaked Fused Molten

Assay, wt. % (min) 99.5 99.5 99.5

Acidity, (as HCl), % ppm 15 15 15

Color of melt, APHA (max) 200 20 20

MDI Dimer, wt. % 0.7 1.0 0.3

Hydrolyzable chloride,

ppm (max) 20 20 15

Typical Propert ies*

Flaked Fused Molten

Appearance white to colorless colorless

slightly solid liquid

yellow

Specific gravity @ 50C/15.5C 1.19 1.19 1.19

Flash point, PMCC,°C 202 202 202

Viscosity, mPa•s - - 4.1

Bulk density, lb/gal 4.6 - 5.8 10 9.93

Freezing Temperatures, ºC 39 39 39

Storage and Handling

Mondur M isocyanate must be stored in tightlyclosed containers and protected from contaminationwith moisture and foreign substances that canadversely affect processing. Contamination canresult in the formation of solids, the evolution of gas,and/or significant amounts of heat. Mondur Misocyanate will react with water to form ureas andliberate CO

2 gas, which may cause sealed contain-

ers to expand and rupture. Partially filled containersshould be blanketed with dry nitrogen.

Storage Temperatures and Shipping Conta iners

Flaked Fused Molten Bulk

Recommended 5°C 5°C 41-44°C

Storage Temperature (41°F) max** (41°F) max** (107°-111°F)

Storage Time

at Recommended 3 months 3 months 3 weeks

Temperature (max)

Shipping Containers 4-lb pails 1-lb pails Truck trailers

20-lb pails 5-lb pails 1,500-4,500

88-lb drums 55-gal drums gal

Dimer Formation. During storage, Mondur Misocyanate slowly reacts to form self-condensationproducts known as MDI dimer. Dimer is undesirablebecause it is only slightly soluble in the moltenproduct and in time will cause turbidity and/or form asolid precipitate. Dimer formation occurs in bothliquid and solid Mondur M isocyanate, and the rateof dimer formation for both is determined by thestorage temperature. Therefore, storage tempera-ture is the critical factor which determines thestorage life of both solid and liquid Mondur Misocyanate.

Page 1 of 3 — Document contains important information and must be read in its entirety.

* These items are provided as general information only. They are approximate values and are not part of the product specifications.


To avoid rapid dimer formation, and a significantshortened storage life, Mondur M isocyanate mustnot be allowed to remain at temperatures between20° and 39°C (68° and 122°F). Dimer forms in solidMondur M isocyanate at a very rapid rate somewhatbelow its melting point of 39°C (102°F). If solidMondur M isocyanate is allowed to remain at thistemperature for seveal hours, it can form enoughdimer to become unusable. This can occur, forexample, when a drum or vessel of liquid isocyanateis allowed to slowly freeze due to exposure toambient temperature.

Storage Temperature for Flaked or FusedMondur M Isocyanate. Store fused or flakedMondur M isocyanate at 5°C (41°F) or lower, whichwill provide a storage life of about three months. Attemperatures of -20°C max (-4°F max), flaked orfused Mondur M isocyanate can be stored up to sixmonths. Storage temperatures up to 15°C (59°F) arepossible, if the correspondingly shorter storage life isacceptable. Strictly avoid the storage of solid MondurM isocyanate between 20° and 39°C (68° and102°F) because the formation of dimer is very rapidat these higher temperatures.

Storage Temperature for Molten Mondur MIsocyanate. The recommended temperature rangefor storing molten Mondur M isocyanate is 42° to44°C (107° to 111°F). The reasons for this narrowrange are:

•The freezing point of Mondur M isocyanate is 39°C (103°F) and it will quickly freeze at or below this temperature. Freezing drasti cally promotes the formation of MDI dimer.

•Above 44°C (111°F) the storage life is shortened due to the formation of a solid precipitate of MDI dimer.

Even when properly stored, liquid Mondur M isocy-anate has a limited storage life of only three weeks.The storage life of molten Mondur M isocyanate isshort compared to most other bulk chemicals,requiring good planning and inventory control.

Bayer MaterialScience has extensive experience inthe design and operation of facilities for the storageand handling of molten Mondur M isocyanate. Pleasecontact your Bayer MaterialScience representativefor more information.

Melting Flaked Mondur M Isocyanate. FlakedMondur M isocyanate is especially convenient forsmaller operations, since the flaked material may beeasily transferred to the appropriate vessel withoutprior melting. It is recommended that flaked MondurM isocyanate be melted in heat jacketed vesselsequipped with an agitator. This will ensure rapidmelting and uniform heating with minimum formationof MDI dimer. Proper ventilation must be used whenmelting material.

Melting Fused Mondur M Isocyanate. Melt fusedMondur M isocyanate as quickly as posible – withoutoverheating — to minimize dimer formation. Thepreferred method for melting fused Mondur Misocyanate is to heat it in a steam cabinet whileslowly rolling the drum. This method normally takes 4to 5 hours to melt 55-gallon drums of fused MondurM isocyanate. Uneven heating without rolling willincrease the amount of MDI dimer formation and thetime needed to completely melt the material. If adrum roller is not used, some method of agitationmust be employed to thoroughly homogenize themelted product. Proper ventilation must be usedwhen melting material.

A hot room (60°C to 80°C/140° to 176°F) can alsobe used. The time needed to melt fused Mondur Misocyanate in a hot room depends on temperature,heat source, air circulation and the amount of mate-rial being melted. Times must be determined empiri-cally, based on specific equipment.

When melted, use the entire contents of the con-tainer, if possible. Otherwise, blanket the remainingMondur M isocyanate with nitrogen and store at atemperature of 42° to 44°C (107° to 111°F). Do notattempt to refreeze melted Mondur M isocyanate.

During melting, monitor the drums for abnormalities— particularly swelling — and discontinue heatingshould any be observed. Swollen drums are poten-tially dangerous and must be handled only by trainedpersonnel. Contact Bayer MaterialScience’s ProductSafety Department for guidelines on handling swollendrums. See Material Safety Data Sheet for emer-gency telephone numbers.

If no abnormalities are observed, open the drums ofmelted Mondur M in a well-ventilated area. Appro-priate personal protection equipment must be used(see Material Safety Data Sheet). Remove anymoisture from the top of the drum and open the bungslowly to relieve pressure build-up that may haveoccurred during the melting process.



If moisture contamination has occurred, do notattempt to melt the product, because the moisturewill react with the isocyanate and result in a danger-ous pressure build-up of carbon dioxide in a closedsystem.

Do not use electric heating devices or any type ofhigh temperature equipment for melting Mondur Misocyanate. High temperatures can cause decompo-sition of the isocyanate and the formation of gaseswhich can build up pressure in closed containers andcause them to rupture, possibly resulting in seriousinjury.

Filtration of Mondur M Isocyanate. It is possible tofilter small amounts of dimer from Mondur Misocyanate. This is typically done when no turbidityor particulates can be tolerated in the process.Contact your Bayer MaterialScience representativefor specific filter equipment recommendations basedon your processing needs.

Filtration cannot solve a dimer problem. WhenMondur M isocyanate has reached the end of itsstorage life — indicated by a significant formation ofsolids — the only really satisfactory solution is torapidly use the remaining product.

Health and Safety Informat ion

Appropriate literature has been assembled whichprovides information pertaining to the health andsafety concerns that must be observed when han-dling Mondur M diisocyanate. For materials men-tioned that are not Bayer products, appropriateindustrial hygiene and other safety precautionsrecommended by their manufacturer should befollowed. Before working with any product men-tioned in this publication, you must read and becomefamiliar with available information concerning itshazards, proper use, and handling. This cannot beoveremphasized. Information is available in severalforms such as material safety data sheets andproduct labels. For further information contact yourBayer MaterialScience representative or the ProductSafety and Regulatory Affairs Department in Pitts-burgh, PA.


Note: The information contained in this bulletin is current as of June 2002. Please contact BayerMaterialScience to determine whether this publication has been revised.

Bayer Materia lScience LLC

100 Bayer Road • Pittsburgh, PA 15205-9741 • Phone: 1-800-662-2927 • www.BayerMaterialScienceNAFTA.com

The manner in which you use and the purpose to which you put and utilize our products, technical assistance and information (whether verbal, written or by

way of production evaluations), including any suggested formulations and recommendations are beyond our control. Therefore, it is imperative that you testour products, technical assistance and information to determine to your own satisfaction whether they are suitable for your intended uses and applications.

This application-specific analysis must at least include testing to determine suitability from a technical as well as health, safety, and environmental

standpoint. Such testing has not necessarily been done by us. Unless we otherwise agree in writing, all products are sold strictly pursuant to the terms ofour standard conditions of sale. All information and technical assistance is given without warranty or guarantee and is subject to change without notice. It is

expressly understood and agreed that you assume and hereby expressly release us from all liability, in tort, contract or otherwise, incurred in connection with

the use of our products, technical assistance, and information. Any statement or recommendation not contained herein is unauthorized and shall not bind us.Nothing herein shall be construed as a recommendation to use any product in conflict with patents covering any material or its use. No license is implied or

in fact granted under the claims of any patent.

Sales Offices

17320 Redhill Avenue, Suite 175, Irvine, CA 92614-5660 • 1-949-833-2351 • Fax: 1-949-752-13061000 Route 9 North, Suite 103, Woodbridge, NJ 07095-1200 • 1-732-726-8988 • Fax: 1-732-726-1672

2401 Walton Boulevard, Auburn Hills, MI 48326-1957 • Phone: 1-248-475-7700 • Fax: 1-248-475-7701

6/02


GELEST, INC. 11 East Steel Rd. Morrisville, PA 19067

Phone: (215) 547-1015 MATERIAL SAFETY EMERGENCY TELEPHONE DATA SHEET CHEMTREC: 1-800-424-9300 NAME: POLY(DIMETHYLSILOXANE), AMINOPROPYL TERMINATED - DMS-A15

CHEMICAL NAME: POLY(DIMETHYLSILOXANE), AMINOPROPYL TERMINATED SYNONYMS: AMINOPROPYL TERMINATED POLYDIMETHYLSILOXANE CHEMICAL FAMILY: SILICONE HMIS CODES HEALTH: 1 FLAMMABILITY: 1 REACTIVITY: 0

INGREDIENTS

IDENTITY CAS NO. % TLV OSHA PEL POLY(DIMETHYLSILOXANE), AMINOPROPYL TERMINATED 106214-84-0 >95 not established

PHYSICAL DATA

Boiling Point: >205°C Melting Point: <-60°C Specific Gravity: 0.97 Vapor Pressure: not determined Vapor Density, air = 1: NA Solubility in water: insoluble % volatiles: <3 Evaporation rate: NA Molecular Weight: 2500-4000 Viscosity: 40-60 cSt Appearance & Color: Clear liquid

FIRE & EXPLOSION DATA Flash Point, COC: 205°C (400°F) Autoignition Temp.: not determined Flammability Limits- LEL: NA UEL: NA Extinguishing Media: Water spray or fog, foam, carbon dioxide, dry chemical. Special Fire Fighting Procedures: Avoid eye and skin contact. Do not breathe fumes or inhale vapors. Unusual Fire and Explosion Hazards: Irritating fumes and organic acid vapors may develop when material is exposed to elevated temperatures or open flame.

-1-(DMS-A15)


ENVIRONMENTAL INFORMATION Spill response: Sweep material and transfer to a suitable container for disposal. Recommended Disposal: Incinerate. Follow all chemical pollution control regulations.

HEALTH HAZARD DATA

Eye Contact: May cause immediate or delayed severe eye irritation. Skin contact: No information available. Avoid Contact. Inhalation: No information available. Avoid inhalation. Oral Toxicity: not determined Inhalation Toxicity: not determined SUGGESTED FIRST AID EYES: In case of contact, immediately flush eyes with flowing water for at least 15 minutes. Get medical attention. SKIN: Flush with water, then wash with soap and water. INHALATION: Move exposed individual to fresh air. Administer oxygen if needed. Call a physician. INGESTION: Never give fluids or induce vomiting if patient is unconscious or having convulsions. To conscious individual give one full cup of water to dilute ingested material. Get medical attention.

REACTIVITY DATA Stability: Stable Conditions to avoid: Store away from oxidizers. Hazardous decomposition products: Organic acid vapors and silicon dioxide.

SPECIAL PROTECTION INFORMATION

Ventilation: Local exhaust is recommended. Mechanical is recommended. Respiratory Protection: If exposure exceeds TLV, NIOSH approved organic vapor respirator. Eye and Face Protection: Chemical worker’s goggles. Do not wear contact lenses. Other Clothing and Equipment: Rubber, neoprene or nitrile gloves. An eyewash and emergency shower should be available. Launder clothing before reuse.

-2-(DMS-A15)


OTHER PRECAUTIONS

For research and industrial use only. Storage and Handling: Store in sealed containers.

TRANSPORTATION

DOT SHIPPING NAME: CHEMICALS, NOI DOT HAZARD CLASS: None required DOT LABEL: None required DOT ID No: None required Prepared by safety and environmental affairs ISSUE DATE DMS-A15: 3/3/03 SUPERSEDES: 7/31/02 The information contained in this document has been gathered from reference materials and/or Gelest, Inc. test data and is to the best knowledge and belief of Gelest, Inc. accurate and reliable. Such

information is offered solely for your consideration, investigation and verification. It is not suggested or guaranteed that the hazard precautions or procedures described are the only ones which exist. Gelest, Inc. makes no warranties, express or implied, with respect to the use of such information and assumes no

responsibility therefore.

-3-(DMS-A15)




Annex B: ACT Labs FTIR Spectra of Base

Polyureas

FTIR spectra for P2P1S1, Exolit OP 560 substituted diisocyanate.

FTIR spectra for P2P1S2, DMS-A15 substituted polyether amine.

””


FTIR spectra for P2P1S3, Exolit OP 560 substituted diisocyanate and DMS-A15

substituted polyether amine.


An

nex

C:

In-h

ou

se

Fla

me

Te

stin

g

mic

a(g

)

zin

cb

ora

te(g

)

sod

ium

ph

osp

hate

(g)

Poly

bor

(g)

am

mon

ium

sulf

ate

(g)

sila

zan

e(g

)

talc

(g)

AP

P/t

riis

ocy

an

ura

te3:1

(g)

trea

ted

gra

ph

ite

(g)

ure

a(g

)

zin

cst

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te(g

)

am

mon

ium

ph

osp

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(g)

AT

H(g

)

trip

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(g)

sod

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ate

(g)

AP

P(g

)

zeoli

te(g

)

mel

am

ine

(g)

Init

ial

mass

(g)

Mass

aft

erb

urn

(g)

Mass

loss

(g)

%lo

ss

Ign

itio

nti

me

(s)

Tim

eto

exti

nct

ion

(s)

Ch

ar

typ

e

Bon

ded

3v0 15.3 11.8 3.5 22.9 4 3 liquifies n

3v1 20 27.7 26.1 1.6 5.8 4 30 good y

3v2 20 27.2 25.9 1.3 4.8 5 30 powder n

3v3 20 31.0 30.1 0.9 2.9 n/a 1 spotty y

3v4 20 32.8 32.0 0.8 2.4 7 10 v. good n

3v5 20 35.9 34.9 1.0 2.8 11 3 flakey n

3v6 4 19.6 18.4 1.2 6.1 4 30 flakey y

3v7 20 27.5 26.4 1.1 4.0 4 30 powder n

3v8 20 28.9 28.7 0.2 0.7 n/a 1 excellent y

3v9 20 30.5 30.3 0.2 0.7 8 0 powder n

3v10 20 31.5 28.8 2.7 8.6 12 0 liquifies n

3v11 10 31.0 28.8 2.2 7.1 3 30 liquifies n

3v12 20 31.9 30.8 1.1 3.4 10 1 liquifies n

3v13 20 31.6 30.8 0.8 2.5 7 30 good y

3v14 20 31.8 27.9 3.9 12.3 2 3 liquifies n

3v15 20 30.7 29.5 1.2 3.9 6 3 good y

3v16 10 36.8 36.3 0.5 1.4 7 5 flakey n

3v17 20 32.5 30.9 1.6 4.9 6 30 excellent y

3v18 20 28.9 28.4 0.5 1.7 15 2 good y

Single ingredient trials, base Polyurea Rubinate 9009 + Ethacure 100/300 + D2000, 30 Second Burn at 1100◦F, 50 g sample.

DR

DC

Atla

ntic

CR

20

09

-07

12

7

mic

a(g

)

zin

cb

ora

te(g

)

sod

ium

ph

osp

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(g)

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bor

(g)

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(g)

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)

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)

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(g)

Init

ial

mass

(g)

Mass

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(g)

Mass

loss

(g)

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Ign

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me

(s)

Tim

eto

exti

nct

ion

(s)

Ch

ar

typ

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ded

3v19 5 5 5 2 32.1 31.2 0.9 2.8 6 27 spotty y

3v20 5 5 5 5 33.0 32.1 0.9 2.7 9 30 spotty y

3v21 5 5 5 5 34.9 34.1 0.8 2.3 5 20 flakey n

3v22 5 5 5 5 32.4 31.5 0.9 2.8 11 2 spotty y

3v23 5 2 5 5 25.8 24.4 1.4 5.4 5 30 excellent y

3v24 5 2 5 5 29.6 28.6 1.0 3.4 9 30 good y

3v25 5 5 2 5 27.4 25.9 1.5 5.5 4 30 good y

3v26 5 5 5 5 29.6 28.5 1.1 3.7 10 30 flakey n

3v27 5 5 2 5 29.1 28.0 1.1 3.8 2 30 excellent n

3v28 5 5 5 2 30.4 30.2 0.2 0.7 n/a 0 ash n

3v29 5 2 5 5 29.7 28.5 1.2 4.0 5 30 good y

3v30 5 5 2 5 30.1 29.5 0.6 2.0 7 11 flakey n

3v31 5 5 5 2 31.2 30.4 0.8 2.6 3 12 flakey n

3v32 5 5 5 5 35.6 34.7 0.9 2.5 11 13 flakey y

3v33 5 5 2 5 30.7 28.7 2.0 6.5 4 30 good n

3v34 5 5 5 5 33.1 32.1 1.0 3.0 28 0 spotty y

3v35 5 5 5 5 29.1 28.2 0.9 3.1 6 19 good n

3v36 5 5 5 5 30.9 30.2 0.7 2.3 10 7 flakey y

First set of combinations, base Polyurea Rubinate 9009 + Ethacure 100/300 + D2000, 30 Second Burn at 1100◦F, 50 g sample.

28

DR

DC

Atla

ntic

CR

20

09

-07

1

sod

ium

ph

osp

hate

(g)

Poly

bor

(g)

am

mon

ium

sulf

ate

(g)

sila

zan

e(g

)

AP

P/t

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ocy

an

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te3:1

(g)

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ph

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(g)

ure

a(g

)

am

mon

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(g)

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on

ate

(g)

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P(g

)

zeoli

te(g

)

mel

am

ine

(g)

Init

ial

mass

(g)

Mass

aft

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urn

(g)

Mass

loss

(g)

%lo

ss

Ign

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nti

me

(s)

Tim

eto

exti

nct

ion

(s)

Ch

ar

typ

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ded

3v37 2 2 2 2 2 2 2 2 2 2 2 35.0 34.8 0.2 0.6 n/a 0 strand y

3v38 5 5 5 2 1 2 35.0 34.8 0.2 0.7 n/a 0 strand y

3v39 5 4 4 4 1 2 30.5 30.3 0.2 2.8 n/a 0 strand y

3v40 5 4 4 4 1 2 32.7 31.8 0.9 2.1 10 2 good y

3v41 5 5 4 4 1 2 32.8 32.1 0.7 0.9 13 5 excellent y

3v42 4 3 3 3 3 1 3 32.4 32.1 0.3 2.2 n/a 0 strand y

3v43 4 3 3 3 3 2 1 1 35.6 34.8 0.8 1.0 18 1 good y

3v44 9 1 1 1 1 1 1 1 1 1 1 1 29.6 29.3 0.3 1.9 25 1 strand y

3v45 5 5 5 2 1 2 26.5 26.0 0.5 1.8 16 2 strand y

3v46 13 1 1 1 4 32.5 31.9 0.6 2.2 14 3 good slightly

3v47 5 3 3 3 3 1 2 32.0 31.3 0.7 0.3 26 0.5 good y

3v48 15 2 1 2 34.9 34.8 0.1 2.0 28 0 strand y

3v49 8 8 1 1 1 1 34.8 34.1 0.7 2.6 26 0.5 good y

3v50 7 7 2 1 1 2 34.2 33.3 0.9 2.5 16 2 good y

Second set of combinations, base Polyurea Rubinate 9009 + Ethacure 100/300 + D2000, 30 Second Burn at 1100◦F, 50 g sample.

DR

DC

Atla

ntic

CR

20

09

-07

12

9



Distribution list


Internal distribution

2 R.S. Underhill: 1CD, 1 hard copy

1 J. Hiltz

1 L.M. Cheng (H/DL(A))

3 DRDC ATLANTIC LIBRARY FILE COPIES

Total internal copies: 7

External distribution

2 Brenda DiLoreto: 1CD, 1 hard copy


37 Easton Road


1 NDHQ/DRDC/DRDKIM 3

1 Library & Archives Canada

Attention: Military Archivist, Government Records Branch

Total external copies: 4

Total copies: 11




DOCUMENT CONTROL DATA

(Security classification of title, body of abstract and indexing annotation must be entered when document is classified)

1. ORIGINATOR (The name and address of the organization preparing the

document. Organizations for whom the document was prepared, e.g. Centre

sponsoring a contractor’s report, or tasking agency, are entered in section 8.)


37 Easton Road


2. SECURITY CLASSIFICATION (Overall security

classification of the document including special

warning terms if applicable.)

UNCLASSIFIED

3. TITLE (The complete document title as indicated on the title page. Its classification should be indicated by the appropriate

abbreviation (S, C or U) in parentheses after the title.)

Investigation of Fire Resistant Polyurea Systems: Final Report

4. AUTHORS (Last name, followed by initials – ranks, titles, etc. not to be used.)

DiLoreto, B.; DiLoreto, S.

5. DATE OF PUBLICATION (Month and year of publication of

document.)

October 2009

6a. NO. OF PAGES (Total

containing information.

Include Annexes,

Appendices, etc.)

44

6b. NO. OF REFS (Total cited

in document.)

5

7. DESCRIPTIVE NOTES (The category of the document, e.g. technical report, technical note or memorandum. If appropriate, enter the type

of report, e.g. interim, progress, summary, annual or final. Give the inclusive dates when a specific reporting period is covered.)

Contract Report

8. SPONSORING ACTIVITY (The name of the department project office or laboratory sponsoring the research and development – include

address.)


PO Box 1012, Dartmouth NS B2Y 3Z7, Canada

9a. PROJECT OR GRANT NO. (If appropriate, the applicable

research and development project or grant number under which

the document was written. Please specify whether project or

grant.)

11gy05

9b. CONTRACT NO. (If appropriate, the applicable number under

which the document was written.)

W7707-088115/001/HAL

10a. ORIGINATOR’S DOCUMENT NUMBER (The official document

number by which the document is identified by the originating

activity. This number must be unique to this document.)


10b. OTHER DOCUMENT NO(s). (Any other numbers which may be

assigned this document either by the originator or by the

sponsor.)

11. DOCUMENT AVAILABILITY (Any limitations on further dissemination of the document, other than those imposed by security classification.)

( X ) Unlimited distribution

( ) Defence departments and defence contractors; further distribution only as approved

( ) Defence departments and Canadian defence contractors; further distribution only as approved

( ) Government departments and agencies; further distribution only as approved

( ) Defence departments; further distribution only as approved

( ) Other (please specify):

12. DOCUMENT ANNOUNCEMENT (Any limitation to the bibliographic announcement of this document. This will normally correspond to the

Document Availability (11). However, where further distribution (beyond the audience specified in (11)) is possible, a wider announcement

audience may be selected.)

unlimited

13. ABSTRACT (A brief and factual summary of the document. It may also appear elsewhere in the body of the document itself. It is highly desirable

that the abstract of classified documents be unclassified. Each paragraph of the abstract shall begin with an indication of the security

classification of the information in the paragraph (unless the document itself is unclassified) represented as (S), (C), or (U). It is not necessary to

include here abstracts in both official languages unless the text is bilingual.)

DRDC Atlantic is interested in evaluating polyurea coatings for use in enclosed spaces as damage

control materials. For such applications, their fire resistant properties need to be improved. The work

reported here is divided into two parts. In Part 1, three base polyurea formulations were developed

and evaluated by cone calorimetry. The goal was to replace portions of the organic polyurea backbone

to improve the flame retardancy. The first sample utilized an diisocyanate prepolymer with a portion of

its backbone made up of a phosphorous polyol, the second sample replaced a portion of the polyether

amine with an amine terminated polydimethylsiloxane and the third sample combined the phosphorous

polyol with the amine terminated polydimethylsiloxane. Cone calorimetry determined that the third

sample yielded the best results for lowering smoke production and increasing time to ignition. It is

believed that the phosphorous polyol and polydimethylsiloxane have a synergistic effect in improving

the flame properties.

In Part 2 of this work, the phosphorous polyol/ polydimethylsiloxane based polyurea was used as

the base formulation and various combinations of flame retardant additives were incorporated in an

attempt to further improve the flame properties. Cone calorimetry indicated that the best combinations

included sodium phosphate, ammonium polyphosphate (APP)/triisocyanurate 3:1, treated graphite,

urea, zeolite and melamine.

14. KEYWORDS, DESCRIPTORS or IDENTIFIERS (Technically meaningful terms or short phrases that characterize a document and could be

helpful in cataloguing the document. They should be selected so that no security classification is required. Identifiers, such as equipment model

designation, trade name, military project code name, geographic location may also be included. If possible keywords should be selected from a

published thesaurus. e.g. Thesaurus of Engineering and Scientific Terms (TEST) and that thesaurus identified. If it is not possible to select

indexing terms which are Unclassified, the classification of each should be indicated as with the title.)

fire safe materials, fire retardant materials, char, polymer, polymer degradation, polymer decomposi-

tion, polyurea


Documents

Investigation of Fire Resistant Polyurea Systemscradpdf.drdc-rddc.gc.ca/PDFS/unc101/p533664_A1b.pdf · Investigation of Fire Resistant Polyurea Systems Final Report Brenda DiLoreto