Novel Flame Retardants Developments for the Flexible Foam Market

Dr. Mike Goode, VP Sales & Marketing, Americas

Munjal Patel, Global Technical Market Support Manager

November 6th, 2018

ICL-IP: who we are…….

Flame Retardants in Automotive Flexible Polyurethane Foam

Evaluation of FR Products in Foam

Results

Conclusions

Presentation Outline

✓ Leading global manufacturer of Specialty

Chemicals and Fertilizers

✓ Headquarters is in Israel

✓ Production facilities located across the

globe

✓ Turnover $5.4bn in 2017

✓ World’s largest Flame Retardant

Producer

✓ Largest Phosphorus based FR producer

✓ Largest Bromine producer

About ICL

ICL presence in South America

4

São Paulo

São José dos Campos

Cajati

Santa Fé

São PauloEst. 1978 (Rotem),

40th anniv. Oct.

Buenos AiresEst. 1997,

20th anniv. last year

MontevideoEst. 1994,

25th anniv. next year

Plants

Offices

5

SAFR®: Provides Reassurance In Your Choices SAFR® is a framework that provides a rigorous evaluation of specific flame retardants in their

applications, thus enabling users to choose the most sustainable product for the intended use.

SAFR® allows for the measurement of the sustainability profile of individual flame retardants based on their use. By using the latest available scientific data, SAFR® ensures the use of the appropriate flame retardant for the application in question and when needed, the replacement with an effective and more sustainable

Building on accepted hazard criteria, SAFR® assesses the extent to which hazards translate into potential risks due to possible exposure to humans and/or the environment during a product’s service life.

SAFR®: Our Story in Facts

Flame Retardants are added in Flexible Polyurethane foam

formulations to meet appropriate fire safety

standards.

There are many fire statistics documenting the first item

ignited, property loss values, death, etc. , but NO statistics on the number of fire prevented by

the use of flame retardants.

Flame Retardants in Automotive Flexible PU

Flame Retardants in Automotive Flexible PU

8

Automotive FoamNorth America Market Polyether Foam

European / S. America Market Polyester Foam

Fire Safety Standard: Primarily FMVSS-302

Stringent OEM requirements for VOC/Fog Emissions, Odor, hydrolytic stability, cost performance

Some OEM have voluntarily stopped using tris(dichloropropyl) phosphate TDCP

Growing interest in sustainable new products to replace traditionally used TDCP has become a priority for consumers and producers of flame retardant products.

Lab Evaluation of Developmental FRs in 30kg/m3

Polyester Automotive Foam

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Components

[pphp]No FR TDCP FR A FR B FR C

Polyester

Polyol

(OH 60)

100 100 100 100 100

FR loading -- Variable

Water 4.0 4.0/4.5 4.0 4.0 4.0

Catalyst 1

(Amine)1.1 1.1 1.1 1.1 1.1

Catalyst 2

(Amine)0.2 0.2 0.2 0.2 0.2

Surfactant

1(silicone)1.3 1.3 1.3 1.3 1.3

TDI 80/ TDI 65

@40/60, Index98 98 98 98 98

Polyester Foam Formulations

Various loading of Developmental FRs evaluated to find optimum fire performance

No change is made except water and FR loading in the formulation to achieve comparable density and air flow

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Fire Property Test

Lower loadings are required for FR A, B and C to meet SE rating in MVSS 302 test, when compared with TDCP

To better understand FR performance in real production line environment, where the FR in the foam must carry the burden of flame retarding the entire composite (flame laminated with textiles), the minimum passing loading levels are doubled in this polyester foam evaluation.

7

4

5

6

0 1 2 3 4 5 6 7 8

SE Passing Loading

pphp

FMVSS 302 Data for Polyester foam

FR C

FR B

FR A

TDCP

Properties No FR TDCP FR A FR B FR C

FR loadings [pphp] -- 14 8 10 12

Cream time [second] 7 7 7 7 7

End of rise time [second] 66 71 63 67 67

Density[pcf] (kg/m3) 1.8 (29.0) 1.9 (30.1) 1.9 (29.8) 1.9 (31.5) 1.9 (31.1)

Air flow [scfm] 0.8 1.1 0.8 1.0 1.0

MVSS 302 Condition at RT

(13, 9, 6 mm) Burn SE SE SE SE

MVSS 302 Dry heat aging

(13, 9, 6 mm) Burn SE SE SE SE

MVSS 302 Humid aging 3h

(13, 9, 6 mm) Burn SE SE SE SE

Foam Reactivity Profile

Developmental FRs achieve comparable density and airflow without reformulation

Meet SE requirements at 13, 9, 6 mm thicknesses before and after different aging conditions✓ Normal Aging at Room Temperature (RT)✓ Humid Aging at 105°C, 100% Relative Humidity for 3 hours✓ Dry Heat Aging at 140°C for 7 days

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0

10

20

30

40

50

60

0 30 60 90 120 150

De

lta

E

minute

Scorch Performance Data in Polyester Foam

TDCP

FR A

FR C

FR B

No FR

Scorch Test

FR A, B and C provide better thermal stability in foam, show improved scorch profile compared to TDCP

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200h Humid Aging Test

PV-3959 Humid Aging Test: 200 hours, 90°C, 100% RH, color change and the ability to recover after deformation were observed and measured.

Developmental FRs provide improved humid aging performance compared to TDCP

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Emission Tests Data for Polyester Foam Formulation

Test No FR TDCP FR A FR B FR CFR loadings [pphp] -- 14 8 10 12DIN-75201 Fogging

Gravimetric [mg]0.40 0.76 0.60 0.63 0.46

VDA 277 FR Related

[µgC/g] -- 0.86 0.00 0.78 0.73

Emission and Odor Test

Emission tests include: DIN 75201 Fogging Gravimetric Method and VDA 277 VDA 270(2016): variant C (foamed material), storage condition C (80°C, 2h) Compared to TDCP Developmental FRs showed:

✓ Lower/ No contribution to emission✓ Improved odor characteristic

VDA 270 Odor Test Data for Polyester Foam Formulation

Odor Test No FR TDCP FR A FR B FR CFR loadings [pphp] -- 14 8 10 12

Grade (1-6) 1.0 2.0 1.5 1.5 1.5

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Physical Properties of Polyester foam

Properties TDCP FR A FR B FR C

FR loadings [pphp] 14 8 10 12

90% CS (%) 13 80 16 20

90% CS (%)

Humid Aged @

105°C, 100% RH 3h

38 85 31 39

50% CS (%) 5 36 6 9

50% CS (%)

Humid Aged @

105°C, 100% RH 3h

8 34 9 10

Tensile

Strength kpa

(psi)

97.6

(14.2)

137.9

(20.0)

120.2

(17.4)

130.5

(18.9)

%

change-- +41 +23 +34

Elongati

on at

Break

%121.3

233.0 154.8 190.2

%

change-- +92 +28 +57

Tear

Strength N/m

(lbf/in)

480

(2.74)

630

(3.60)

490

(2.80)

570

(3.25)

%

change-- +31 +2 +19

CFD 50% kpa 4.0 2.9 4.4 4.1

%

change-- -28 +10 +3

Physical/Mechanical Properties

Developmental FRs show improved tensile, elongation and tear performancecompared to TDCP

FR A experienced loss in CS and CFD, while FR B and C have no/little impact.

Evaluation of Fyrol® PNX-LE, Fyrol® HF-9 and Fyrol® HF-10 in 29kg/m3 Polyether Foam

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Properties of commercial flame retardants for polyether foam

Properties TDCP Fyrol® PNX-LE Fyrol® HF-9 Fyrol® HF-10

Phosphorus

Content [%] 7.1 19.0 10.8 12.7

Chlorine

Content [%]49.0 -- -- --

Viscosity at

25°C [mPas] 1800 2000 350 1950

Density

[kg/m3]1520 1300 1200 1300

FR Properties

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1.8pcf density polyether foam formulation

Components [pphp] No FR TDCPFyrol®

PNX-LEFyrol® HF-9 Fyrol® HF-10

Polyether Polyol

(OH 54)100 100 100 100 100

FR loading -- Variable

Water 3.55 3.55 3.55 3.55 3.55

Catalyst 3 (Amine) 0.25 0.25 0.25 0.25 0.25

Catalyst 4

(Stannous Octoate)0.1 0.1 0.1 0.06 0.06

Surfactant 2(silicone) 0.8 0.8 0.8 0.8 0.8

TDI 80 110 110 110 110 110

Polyether Foam Formulations

Various loading of Developmental FRs evaluated to find optimum fire performance

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Fire Property Test

Among all three products, PNX-LE gave the best efficiency on passing the MVSS 302 test, nearly 38% lower loading than TDCP, due to its high phosphorus content (19%). HF-9 and HF-10, which contain relatively lower phosphorus, are not as efficient as PNX-LE and required higher loading to achieve the same SE performance level

8

5

12

12

0 2 4 6 8 10 12 14

SE Passing Loading

pphp

FMVSS 302 data for polyether foam

Fyrol® HF-10

Fyrol® HF-9

Fyrol® PNX-LE

TDCP

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Reactivity profile of Polyether foam formulation

Properties No FR TDCP Fyrol® PNX-LE Fyrol® HF-9 Fyrol® HF-10

FR loadings

[pphp]-- 8 5 12 12

Cream time

[second]8 9 9 10 9

End of rise

time [second] 83 108 117 144 134

Density[pcf]

(kg/m3)1.8 (29.0) 1.9 (31.4) 1.9 (30.0) 1.9 (31.4) 1.9 (31.1)

Air flow [scfm] 3.0 3.0 3.0 3.6 3.0

90%

Compression

Set

4 4 6 5 6

Foam Reactivity Profile

Comparable density and airflow in all foams

All three products had longer end of rise time

90% CS are within the same range with TDCP

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0.00

10.00

20.00

30.00

40.00

50.00

60.00

70.00

80.00

30 60 90 120

De

lta

E

minute

Scorch Performance Data in Polyether Foam

FR-2

PNX-LE

HF-9

HF-10

No FR

Scorch and Emission Test

Fyrol HF-10 is very stable and therefore had the lowest propensity to discolor

Scorch Resistance: HF-10 > HF-9 > PNX-LE

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Emission Tests

Emission Tests Data for Polyether Foam Formulation

Test No FR TDCP Fyrol® PNX-LE Fyrol® HF-9 Fyrol® HF-10

FR loadings

[pphp]-- 8 5 12 12

DIN-75201

Fogging

Gravimetric

[mg]

0.11 0.90 0.21 0.80 0.16

VDA 277 FR

Related [µgC/g] -- 0.47 29.88 0.47 1.54

VDA 278

VOC/FOG

[ µg/g ]

388/693 614/2379 338/652 367/3228 389/733

All three products have less contribution to fogging values compared with TDCP PNX-LE and HF-10 provide excellent performance in reducing fogging. PNX-LE is specially

designed to pass the VDA 278. HF-10 has better scorch and emission profile (both VDA 277 and VDA 278) HF-9 is suitable to meet DIN-75201 and VDA 277 requirements

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Next generation of non-halogenated FRs developed by ICL-IP America are viable TDCP alternatives in flexible polyurethane foam for automotive applications.

Developmental FR A, B and C in this study are found to be:

✓Easy to formulate with

✓Very efficient and so cost effective in comparison to TDCP

✓Improved resistance to foam hydrolysis and discoloration

✓No or low contribution to emission

✓No odor issue

✓Improved mechanical and physical properties

Commercial products:

✓Fyrol® PNX-LE provides excellent efficiency in flammability, has low fogging and low VDA 278 values.

✓Fyrol® HF-10 offers ideal FR solution where low scorch, low fogging and VOC are essential.

✓Fyrol® HF-9 is suitable for most commercial production system where low viscosity is required.

Conclusions and Summary

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Dr. Jeff Stowell, Applications Group Manager

Zhihao Chen, Application Chemist

ICL Tarrytown and IMI R&D Team

Acknowledgements

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Thank You For Your Kind AttentionQuestions?