Sustainable Flame Retardant Developments for the Polyurethane Industry

Greg Symes – Global Polyurethane BU Manager Munjal Patel – Global Market Support Manager

November 11th – 13th, 2014

Outline

• Brief introduction on ICL(-IP)

• Flame Retardant (FR) Basics

• Flame Retardant Trends

• Status TDCP and TCPP

• Product Development of sustainable FRs

• Fyrol® HF-10 as TDCP-alternative in automotive foam

• E06-16 New reactive TCPP-alternative in PIR boardstock

• Conclusions

Israel Chemicals Ltd

• Leading specialty minerals company fulfilling essential needs in Agriculture, Food and Engineered Materials

• Turnover US$ 6.3 billion; 12.000 employees (2013)

ESSENTIAL NEEDS*

Agriculture 55%

Food 8%

Engineered Materials

29%

Unique minerals

K

P

S

Br

Mg

Min

ing

Ch

em

istr

y Fo

rmu

lati

on

Processing expertise

* Percentages represent share of 2013 sales

ICL-Industrial Products

• ICL-IP is the Industrial Products segment of ICL

– Leading producer of elemental Bromine • Bromine inorganics

• Bromo-organics

• Biocides

• Flame Retardants

– Phosphorus • Leading producer of P-based Flame Retardants

• Inorganics

– Magnesia Products

• Emphasis on innovation & new product development

ICL-IP

• Headquarters – Beer Sheva, Israel

• Production Sites – Israel

– France

– Germany

– The Netherlands

– USA

– China

• Sales Offices – Europe

– North America

– Brazil

– Japan

– China

– Hong Kong

– Israel

• R&D/Technical centers – Israel: Beer Sheva

Haifa

– USA: Ardsley

– Germany: Bitterfeld

– China: Shanghai

FR Basics

• Flame retardants play an important role in public fire safety

• They have a long history in polyurethane (PU) and polyisocyanurate (PIR) foam applications such as consumer products (furniture & automobile) and thermal insulation in buildings (rigid foam for building envelope)

• Why/How are they used: – FR products are carefully formulated into highly combustible raw materials to minimize their

flammability, thereby allowing the safe use of these raw materials in commercial products

– FR products help prevent fires from starting and/or dramatically slow combustion

– For economic reasons, FR products are typically used at minimal levels to prevent ignition from the most logical combustion sources (cigarette and open flame)

• Products with flame retardant additives can still burn. The addition of FR’s helps manage the combustible nature of urethanes.

• New flame retardant products are exhaustively tested and approved for intended uses by regulatory agencies in North America, Europe and Asia

FR Basics Te

mp

erat

ure

Start of fire

flash over Time

Prevent ignition ….. primary purpose

Slow down the spread of fire

Resist large fire …… not usually

FR Trends - General

• Public and governmental scrutiny of chemicals has increased over the years; FRs are no exception

• Growing concerns about chemical exposure and their migration into our environment

• Currently, most widely used FRs in PU foam are:

TDCP Furniture (US) Automotive (EU)

TCPP Furniture (EU) Insulation

FR Trends – Status TDCP

• EU: Risk approach (Risk = Hazard * Exposure) – Labelling since many years, but low exposure

• R40 = Limited evidence of a carcinogenic effect

• R51/53 = Toxic to aquatic organisms; may cause long term effect in aq. environment

– Oct, 2009: German TV (ZDF, Frontal21) measures air quality in car interiors

– Feb 24th, 2014: Ban on a.o. TDCP in toys and children’s goods

• US: Hazard approach – Oct 12th, 2011: California Proposition 65 listing => Cal. TB117 dropped

– Bills passed in states of New York, Maryland and Vermont to ban TDCP in consumer products based on structural similarity to TCEP (EPA DfE)

– Bills submitted in Illinois, Connecticut, North Carolina, Maine, Massachusetts and Washington. More are expected

• TDCP is a declarable substance according to GADSL (#128: D/FA)

• Oct 2014: TDCP included in SIN list (“NGO blacklist”)

FR Trends – Status TCPP

• Read across and structural similarity TDCP/TCEP

• US

– Ubiquitous claim: Found in breast milk, fish, household dust, indoor air and surface water

– EPA

• National Toxicology Program – Carcinogenicity study

• Negative assessment in Design for Environment study

– No bans yet, but Vermont and California are assessing

FR Trends – Status TCPP

• EU

– H302 – Harmful if swallowed

– Banned in toys and toddlers goods (not evidence based; just read-across)

– Banned in Ecolabels (based on halogen-content)

– IKEA repeatedly asking for alternatives

– How will outcomes US affect EU?

FR Trends – Results

• Push towards more sustainable reactive, polymeric and/or halogen-free new product offerings with an improved HSE profile and minimal potential for migration out of matrix

• However, new developments require R&D resources, time and investment

• ICL announced voluntary phase out of TDCP for furniture applications by Jan 1st, 2013 and for automotive applications by end of 2015

• ICL still believes TCPP to be safe in use and plans to continue producing TCPP until stopped by regulatory action or a move by the value chains to other technologies

New Product Development Criteria for Sustainable FRs for PU-foam

POLYMERIC

REACTIVE

CLEAN HSE PROFILE

REDUCED LOADING

LOW FOAM SCORCH

LOW VOC, NON-FUGITIVE GOOD STABILITY NOT PBT (PERSISTENT, BIOACCUMULATIVE, TOXIC) NOT VPVB (VERY PERSISTENT, VERY BIOACCUMULATIVE) NOT CMR (CARCINOGENIC, MUTAGENIC, REPROTOXIC) COST EFFECTIVE (TO PRODUCE AND USE) COMMERCIALLY VIABLE SYNTHETIC ROUTE

TDCP-alternative:

Fyrol® HF-10

Automotive PU FRs - History

• Fyrol® A710 (2000) – Halogen-free FR for mid-high densities

• Fyrol® PNX (2000) – Very efficient FR; scorch potential

• Fyrol® PNX-LE (2004) – Reduced volatiles

• Fyrol® HF-5 (2010) – All densities; moderate scorch potential

• Fyrol® HF-10 (2014) – Low emission product for automotive

• New development: Reactive FR

Fyrol® HF-10

• Foams with like densities, air flows, and overall foam quality were produced and tested

• Results compared to known commercial FR’s, like TDCP, Fyrol® A710 and Fyrol® PNX

– Flammability – loading levels (FR efficiency)

– Fog/VOC

– Foam physical properties

– Discoloration

Typical Properties

Property Fyrol® HF-10

Fyrol® FR-2 (TDCP) / 300TB

Fyrol® A710

Fyrol® PNX-LE

Appearance CTL CTL CTL CTL

Color (APHA) < 100 < 100 < 100 < 350

Viscosity (mPa.s @ 25°C)

1950 1800 / 1200 80 2000 - 4000

P-content (%) 12,7 7,1 / 7,1 8,4 19

Density (kg/m3) 1300 1520 / 1480 1190 1330

Acid number (mg KOH/g)

< 1,0 < 0,02 < 0,02 < 2.0

Water content (wt%)

< 0,1 < 0,1 < 0,1 < 0.1

Remark TPP content

Only for ether foam

Performance

in

PolyETHER foams

PolyETHER formulation Hand-Mix PU Formulations Used for Evaluation (24 & 29 kg/m3 density)

Ingredient Level Level

Polyether polyol, Voranol 3136 (Dow) 100.00 100.00

Flame retardant variable variable

H2O 3.85 3.35

Catalyst, Dabco BLV (Air Products) 0.25 0.25

Silicone surfactant, Niax L-620 (Momentive) 1.00 0.80

Stannous octoate, Dabco T-10 (Air Products) 0.35 0.35

TDI Index 110 110

Foam Density (pcf / kg/m3) 1.5 / 24 1.8 / 29

PolyETHER foam – FMVSS-302

0

2

4

6

8

10

12

14

16

Fyrol® PNX Fyrol® HF-10 TDCP Fyrol® A710

Pass

ing

Level

(ph

p)

24 kg/m3

29 kg/m3

Fogging and VOC

• OEMs require automotive interior parts to have excellent fogging properties, which also applies to the FR products used in the parts

• Reducing volatiles in car interiors, while at the same time providing flame retardancy to meet the FMVSS-302 flammability standard is of growing importance for automobile manufacturers worldwide

• There are many different methods for measuring the emission of volatile components from PU foams; test conditions vary widely

DIN 75201 – Results PolyETHER

No FR Foam Fyrol® PNX-LE Fyrol® HF-10 Fyrol® A710 TDCP Fyrol® PNX

1,2 1,7

4,4

5,6

8,7 9,2

Deposit (

mg

)

Fogging - Gravimetric Method

PolyETHER foam – VDA 277

VDA 277 test in µgC/g

Specs VW 50 and Audi 20

Components related with FR

Fyrol® A300TB

(TCDP-based)

3 µgC/g -> 1,3 dichloro-2-

propanol

Fyrol® A710 3 µgC/g -> Phenol

Fyrol® HF-10 4 µgC/g -> Phenol

PolyETHER foam – Compression Set

Compression set test in ether foam at 26 kg/m3 density

22 hours at 70°C – 75% compression

Fyrol® FR-2 (TDCP) 10 %

Fyrol® HF-10 15 %

Fyrol® PNX-LE 10 %

PolyETHER foam - Scorch

0,00

10,00

20,00

30,00

40,00

50,00

60,00

70,00

80,00

50,00 70,00 90,00 110,00 130,00 150,00

De

lta

E

Time (min)

Scorch Performance

Fyrol® PNX

TDCP

Fyrol® HF-10

Fyrol® A710

Performance

in

PolyESTER foams

PolyESTER formulation Desmophen 2200B 100 100 100

Water 4 4 4

Niax C-131NPF 1,1 1,1 1,1

Niax DMP 0,2 0,2 0,2

Niax Silicone L-537XF 1,3 1,3 1,3

Fyrol® A300TB 7

Fyrol® HF-10 8

Fyrol® A710 10

Index 98 98 98

Tests

Air flow [l/min] 29 44 44

Density [kg/m3] 32,1 31,7 29,7

Density [pcf] 2 2 1,9

Automotive FMVSS 302 SE NBR SE NBR SE NBR

Compression Set (%) 32,6 30,2 26

PolyESTER foam – FMVSS-302

0

2

4

6

8

10

12

Fyrol®A710

Fyrol®HF-10

Fyrol®A300TB

Fyrol®PNX/LE

pp

hp

Polyester foam 30 kg/m3

FR level forSE/NBR

PolyESTER foam – VDA 277

VDA 277 test in µgC/g

Specs VW 50 and Audi 20

Components related with FR

Fyrol® A300TB Pass -> 1,3 dichloro-2-

propanol

Fyrol® A710 Pass -> Phenol

Fyrol® HF-10 Pass -> Phenol

PolyESTER foam – Compression Set

Compression set test in ester foam at 30 kg/m3 density

22 hours at 70°C – 75% compression

Fyrol® A300TB 33 %

Fyrol® A710 26 %

Fyrol® HF-10 30 %

TCPP-alternatives: Fyrol® HF-10 (Flexible Foam)

&

E06-16 – Reactive (Rigid Foam)

Fyrol® HF-10 in BS-5852 Crib 5

0

10

20

30

40

50

60

TCPP Fyrol® HF-10 Fyrol® PNX TDCP

15 15

30

21 20 20 20 20

45 48

54 52

Flame Retardant (pphp) Melamine (pphp) Weight Loss (grams)

Foam Density = 32 kg/m3

E06-16: Reactive TCPP-alternative for use in rigid foam • PIR rigid foams were made using a discontinuous

panel manufacturing process

• Results are compared to industry control (Fyrol® PCF) to ensure a reference point is always present

• Physical Properties – Compressive strength, Closed cell content

• Insulation – R-values measured at 10°C

• Flammability

• Cone calorimeter and DIN 4102 tests - Predictive small-scale tests

• ASTM E84 Steiner tunnel test (US building code requirement) and SBI test (European building code requirement) - Large-scale fire tests

PIR Boardstock formulation

Ingredient Level (PHP)

Polyester polyol 100.00

Flame retardant 15

Surfactant 1-3

Catalyst A 0.2-0.5

Catalyst B 3-5

Catalyst C 0.2-0.5

Water 0.8-1.0

365mfc/245fa 45-50

MDI Index 270

Density (kg/m3) 32

Results E06-16 vs TCPP

Parameter Fyrol® PCF

(TCPP)

E06-16

(Reactive)

Compressive strength (kPa) 176 236

Closed cell content (%) 97,3 96,1

R-value @ 10°C (m2.K/W) 1,19 1,24

Cone THR (MJ/m2) 3,3 3,9

Cone TSR (m2/m2) 114 98

Char yield (%) 77 74

DIN 4102 (cm) 8,7 8,2

ASTM E84 Class I Class I

Single Burning Item (SBI)

• PIR boards with Fyrol® PCF and E06-16 were tested in the Single Burning Item (SBI) test, EN 13823

PIR board (FR)

FIGRA (W/s)

THR (MJ)

SMOGRA (m2/s2)

TSP (m2)

Fyrol® PCF 3572 7.5 (C) 1238 (s3) 180 (s2)

E06-16 4242 8.5 (C) 1133 (s3) 159 (s2)

• Fyrol® PCF and E06-16 PIR panels achieved a comparable fire performance and “E” classification for FIGRA and “C” classification for THR in the SBI test with naked panels

Conclusions

• Growing demand for halogen-free, reactive and/or polymeric FR products for the flexible and rigid PU-foam markets

• ICL-IP has had a long history in developing new flame retardant products and will continue to develop safe and sustainable products that respond to the challenging needs of the market

• Fyrol® HF-10 is a sustainable, halogen-free TDCP-alternative for automotive flexible foam applications (both in Polyether and Polyester)

• Fyrol® HF-10 is a sustainable, halogen-free TCPP-alternative for furniture flexible foam applications (BS-5852)

• E06-16 is a sustainable, reactive TCPP-alternative for use in PIR Rigid foam

• ICL is currently commercializing both Fyrol® HF-10 and E06-16

• Negative publicity and potential deselection of PU-foam can be avoided by choosing sustainable alternatives now

Acknowledgements

• ICL-IP America – Dr. Andrew Piotrowski

– Manny Pinzoni

– Munjal Patel

– Dr. Jeffrey Stowell

– Greg Symes

– Kali Suryadevara

– Barbara Williams

• ICL-IP Bitterfeld – Jens Leopold

– Dr. Mike Hildebrand

– Dr. Horst Fedgenhauer

– Joop Wuestenenk

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