The Dow Chemical Company

• Norms and requirements

• Polyolefin elastomers

• Flame retardants and co-agents

• Development of optimized formulations

®™ Trademark of The Dow Chemical Company

Halogen -free Elastomer Solutionsaddressing most stringent Fire Standards

SGF Annual Conference, April 14 th 2016 S. Ultsch, T. ClayfieldC. Li Pi Shan, V. Thakur

Fire performance

The discussion is changing

IgnitabilityFlamespreadFuel load Smoke density

ToxicitySustainabilityRecycling

Polyolefin elastomers offer an excellent polymer base

Fire performance standards – example of infrastructu re

• Trend: Euro-Class B compounds• Demanding for halogen-free polyolefin compounds

Laboratory scale System Tests

Euro-class

Small burner SBI (EN 13823) OtherGermany DIN 4102

UK France Nordic

A1EN 1182 EN 1716

Non-combustible

Non-combustible

Non-combustible

A2Figra0,2 MJ=<120 Ws THR600s=< 7.5 MJ

EN 1182 EN 1716

A2Limited

combustabilityM0/M1

BEN 11925-2 (30s/30s)

Figra0,2 MJ=<120 Ws THR600s=< 7.5 MJ

BS7837 B1 Class B-s2-d0 M1 Class 1

CEN 11925-2 (30s/30s)

Figra0,4 MJ=<250 Ws THR600s=< 15 MJ

B1 Class 1 M2 Class 2

DEN 11925-2 (30s/30s)

Figra0,4 MJ=<750 Ws B2

ENV 1187 t1Class 3

ENV 1187 t4M3/M4

ENV 1187 t3Class 3

ENV 1187 t2

E EN 11925-2 (15s/20s)

B2 ENV 1187 t1

M4 not allowed

F B3

Radiation

Air flow

Fuel load

Olefinic roofing membrane

State of the art: ENV 1187 B roof t1 –t4 system tests

System test Broof t3

• 35 to 50% Al(OH)3 or Mg(OH)2

• Flexible Formulations from Dow Elastomers

EN 45545-2 transportation: new fire standards comin g up

• Small burner and cone calorimeter for fast development • Smoke-density and toxicity: defined by the formulation

Application Categories Parameter Requirements for Haz ard Level HL3

Walls, Ceilings... R1 Ignitabiity [-] pass

Flooring R10 Heat release MARHE [kW/m2] 50 to 90

Sealants, tubes R23 Flame spread CFE [kW/m2] 13 to 40

.... Smoke density DS(4) [-] 150 to 240

Smoke toxicity CIT(4 or 8 min) [-] 0.75 to 1.5

Dow performance plastics

LLDPE

E-m

odul

us LDPE

Mg(OH)2

Al(OH)3

CaCO3

TiO2

AO

…...

-EA

-MAH

PBE

EPE

ULDPE

EPDM

OBC

POE

DOWLEX™

ATTANE™

ENGAGE™

INFUSE™

NORDELTM

AMPLIFY™

VERSIFY™

PE

PP

PP

ELITE TM

®™ Trademark of The Dow Chemical Company 6

AGILITY™

Meeting Customers’ Needs Around the World

DOW CONFIDENTIAL - Do not share without permission

SpainAFFINITY GA™ENGAGE™VERSIFY™ Thailand

ENGAGE™

FreeportAFFINITY GA™INFUSE™ENGAGE™

PlaquemineENGAGE™NORDEL™

SeadriftVLDPE

Japan

China

Switzerland

Texas

• Global solution trains and R&D labs on 3 continents

• World’s largest POE capacity…and Growing!

Investing Globally to Meet Your Growing Needs

U.S. Gulf Coast InvestmentsNext-Generation NORDEL ™ EPDM – Bringing world’s preferred EPDM technology to high-value segmentsStartup: 2017

High Melt Index Elastomers – Building on proprietary AFFINTY™ GA for use in high-growth, hot melt adhesives marketsStartup: 2017

Propane Dehydrogenation Unit – Making propylene on purpose for use in copolymer production & specialty chemicalsStarted: 2015

Sadara Chemical CompanyENGAGE™ & AFFINITY™

Polyolefin Elastomers• Serving Consumer Durables,

Transportation and Infrastructure in high growth emerging economies

• Feedstock advantage

• Startup: 2016-2017

Dow Advances in Catalyst Technology

9

Ziegler-Natta MetalloceneAdvanced

Post-Metallocene

• Low efficiency• De-ashing needed• Low reactor temp

• High efficiency• No de-ashing required• High-temperature stability• Homogeneous composition

• High efficiency• Ultra-high MW capability• Ultra-high long chain

branching capability

Constrained Geometry Catalyst

TMTrademark of The Dow Chemical Company (“Dow”) or an affiliated company of Dow.

1990’s-present1960’s-present 2000 and beyond

Molecular Weight

• Ultimate properties

• Filler retention

• Compression set

Processability

Low High

Design Parameters for EPDM:• Molecular Weight

Distribution/Processing-Property

• C2 Composition/Crystallinity

• Long Chain Branching/Rheology

• ENB Composition/Cure Rate

EPDM by Design

Long ChainBranching

Wei

ght F

ract

ion

ENB Composition

C2 Composition

Expanding the NORDEL TM EPDM Product Offering

TMTrademark of The Dow Chemical Company (“Dow”) or an affiliated company of Dow.

FasterCuring

Higher Mooney,More Filler

Oil-Extended

Ultra-High Mooney

Sponge

EasyMixing New Features:

� Complete Product Portfolio� Optimize grades for key

market segments

Ethylene Based Olefin Block Copolymers

Crystalline hard-blocksInterlinking soft blocks

Advantages: Flexibility and temperature resistance High filler take up without property lossLow glass transition temperatureAdvantages of polyethylene

High filler levels without significant loss in physical performance

®™ Trademark of The Dow Chemical Company

20

40

60

80

100

120

140

1 10 100Flexural modulus [MPa]

DSC melting temperature [ºC]

INFUSE™ Block Copolymers

Random Copolymers

Heat resistance and flexibility

®™ Trademark of The Dow Chemical Company

Ext

rusi

on g

rade

with

exc

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nt p

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MFI 190/2.16 g/10 min

ISO 1133 0.5 5 30 0.55 4 0.5 5 30 < 0.5 2 (230/2.16) 25 (230/2.16)

MOONEY viscosity D1646 33 8 2 74 72 25

Shore A º D 2240 77 83 78 70 66 84 88 71 72 86 94

Shore D º D 2240 60.5 20 17 26 31 30 42

Tensile modulus MPa ASTM D638 3.4 3.8 4 650 5.2 4.1

Secant modulus (2%) MPa ASTM 882 14 11 31 44

Flexural modulus MPa ASTM D 790 39 116

Tensile strength MPa ASTM D638 > 13 7.4 5 30 25 9.5 5.7 8.5 3.7 16.6 12.7 11 14

Break elongation % ASTM D638 > 750 >1000 > 850 780 680 > 600 >600 >600 200 238 247 >500 >500

Glas transition temperature OC DSC -62 < -60 <- 60 -52 -53 -47 -46 -27 -23

DSC melting point OC DSC 122 122 122 127 55 59 80 99 na na

= vulcanizate properties

LLDPELinear Low Density

Polyethylene

EPDM PBEPOEOBC

Olefin Block Copolymers Polyolefin Elastomers Hydrocarbon Rubber Propylene Based

Elastomers

not applicable

Selecting the right polymer

Formulation toolbox

LLDPE

PBE

ULDPE

OBC

POE

DOWLEX™

ATTANE™

ENGAGE™

INFUSE™

NORDEL™

VERSIFY™

Infrastructure

Transportation

Industrial

....

EPDM

• Blends from two to three polymers• Platform for various applications

EPEELITE™

Flame retardant 30 – 75 % Fillers 0 – 30 %

Process stabilizer 0.5 – 1 %Longterm stabilizer 0 – 2 %Colorants 0.5 – 4%

Processing aids, crosslink agents...

®™ Trademark of The Dow Chemical Company

Sample production: Dow Europe direct extrusion line

16

• 25 mm 40 L/D co-rotating twin screw extruder• 5 to 25 kg/h• Gravimetric feeders

Dow Europe direct extrusion line

• 300 mm die• 0.1 to 2 mm • Three stack calander• Film and fabric feeder

Production of 1 x 300 mm sample rolls

Halogen-free flame retardants for outdoor applicati ons

Al(OH)3

Mg(OH)2

Diagram: Courtesy of Martinswerke/Albemarle, Bergheim Germany

Thermogravimetric Analysis (TGA)

mas

s lo

ss [%

]

temperature [oC]0 100 200 5000 200 400 600 800

Mas

s lo

ss [%

]

- 40

0

Temperature [oC]

Mg(OH)2

Al(OH)3

• Magnesium dihydroxide or Aluminum trihydroxide

• Parameters : particle size and distribution coating purity – precipitated or ground

Co-agents to improve fire performance

Diagram: Courtesy of Martinswerke/Albemarle, Bergheim Germany

• Manifold substances and mechanisms – the fire triangle

• Options: Improvement of fire performance Reduction of filler load

• Side effects: processing aidsurface propertiesimproved physicals….

SilicateCyanuratesCalcined clayAminesCopolymerizate…..

Systematic evaluation as recommended by the producers

POLYMERS FLAME RETARDANTS COAGENTS

INFUSETM MDH Coarse Silica

INFUSETM/ENGAGETM MDH fine Cyanurate

INFUSETM/AMPLIFYTM MDH fine, coating 1 Amines

INFUSETM/VERSIFYTM MDH fine, coating 2

TERPOLYMERS MDH fine, coating 3 Fibrous FR

COPOLYMERS ATH fine, coated Nanoclay

... ... ...

The material base - how to study so many options?

• Screening design of experiments• Fine-tuning by multilevel mixture designs

Screening design of experiment (DOE)

Four functions

Each function at three levels

Fixed concentrations

Trial average: effect per component

• Fire performance

• Processing• Flexibility• Physical performance• Heat resistance• Cold temperature impact• Compression set• Tear resistance• Weathering• Drinking water• Surface properties• Recycling, sustainability…

Fire performance is only one aspect

Norms and certifications

23

Screening experiment – evaluation of key parameters

Die Pres

sure [b

ar]

Time t

o 150 m

m [s]

Time b

urning dro

plets [-]

Total heat

releas

e [MJ/m

2 ]

Peak h

eat re

lease [

MJ/m2 ]

MARHE [kW/m

2 ]

Modulus [MPa]

Tensil

e Stre

ngth [M

Pa]

Break

elongation [%

]

Goal < 120 > 60 >40 <100 <60 >8 >500

Average 117 56 45 87 172 115 59 9 514

Polymer OBC1 46 59 52 92 152 106 60 7.2 707

OBC2 102 69 52 86 172 116 43 9.2 538

OBC polar 203 40 30 83 193 121 73 10.5 298

Flame MgOH coarse 74 63 24 77 179 120 60 10.0 570

Retardant ATH high end 128 44 57 88 179 113 48 6.8 435

MgOH fine 149 60 53 97 158 110 68 10.1 537

Co-agent Coagent 1 149 35 30 77 181 120 69 7.2 600

Coagent 2 84 56 44 90 168 114 49 11.0 502

Coagent 3 119 75 60 94 168 109 58 8.7 440

Filler Function 1 115 39 45 86 180 120 64 7.7 485

Function 2 101 58 54 86 177 115 55 9.9 553

MgOH coarse 135 69 35 90 160 109 57 9.3 504

Processing Edge Cone Physicals

Winning combinations ?..

24

• A lot of information• What fits the end use?• Re-discussion with suppliers

Case study: passing SBI with polyolefinic formulatio ns

Textile architecture membrane

• Target: SBI classification: B-s2, d0

• 0.6 mm, vertical installation• Design: flexibility, strength, printability• Halogen and plasticizer-free • Sustainability, re-cycling, re-purposing

25

EN 12823: Single Burning Item Test (SBI)

Simulation of waste paper basket in room corner

Parameters

• Fire growth rate FIGRA [W/s]

• Total heat release THR [MJ]

• Smoke rate SMOGRA [m2/s2]

• Burned area TSP [m2]

• Burning droplets

Required classification: B-s2, d0

• Fire class• Smoke density/class• Dripping behavior

26

Lab-Simulation of SBI-test by cone-calorimetry

Photograph: Courtesy of Martinswerke/Albemarle, Bergheim Germany

Parameters:

• Fire Growth Rate FIGRA [W/s]

• Total Heat Release THR [MJ]

• Smoke Density SMOGRA [m2/s2]

• Total Smoke Production TSP [m2]

• Burning Droplets

27

0

50

100

150

200

250

0 200 400 600 800 10001200140016001800

[ kW/m² ]

Zeit [s]

Heat Release Rate

4050607072

Cone-Calorimetry – effect of MDH content

Mg(OH)2THR FIGRA[wt%] [MJ/m2] [kW/m2/s]

80.6 1.22773.8 0.96855.4 0.66846.9 0.3838 0.325

Potential for SBI: B-s1, d0

Measurements: Martinswerke/Albemarle, Bergheim

28

Passing the SBI-test

Parameter Result Limit FIGRA [W/s] 82 120THR [MJ] 0.7 7.5SMOGRA [m2/s2] 0 180TSP [m2] 37 200Burning Droplets none none

Classification B-s1-d0:

• A clear pass at 65 wt% MDH

• First time for a polyolefinic solution

29DOW RESTRICTED

Simplex design to finetune the flame retardant

40 %

ATH 50 %

Fire performance co-agent 10 %

0 % 0 %

Processing aid 10 %

1

2 3

4 5

6

7

• INFUSE® matrix• Extrusion of 1 mm membranes• Testing of: processing, mechanicals, fire performance

30

Cone-Calorimetry at 35 kW/m 2 addressing EN 45545H

eat r

elea

se r

ate

[kW

/m2 ]

300

0

0 1400Time [s]

50 % ATH, no co-agent: THR = 88 kW/m2

MARHE = 159 kW/m2

40 % ATH, 10 % co-agent

THR = 84 kW/m2

MARHE = 105 kW/m2

Significant improvement at reduced flame retardant

32

Fire Performing formulations - status

• Formulation database

• Halogen-free solutions addressing class B, SBI, EN 45545

• 40 to 60 wt% filler level - flame retardants and co-agents

• Excellent processing• Flexible• Physical strength• ..... Weldable, dirt repellent, longevity...

25 26

UV/no dirt

UV/ dirt

no UV/ dirt

Summary

www.dowelastomers.com

• DOW Elastomers - flexible formulations with excellent fire performance• Infrastructure, building envelopes, transportation, wire and cable….

• Formulation and processing know-how • Support from pellet to end-use• Cooperation with technology leaders

33DOW RESTRICTED

Dow Performance Plastics and Elastomers Grades

AFFINITY™ Polyolefin Plastomers

AGILITY™ Performance Low Density Polyethylene Resins

AMPLIFY™ Functional Polymers

ATTANE™ Ultra Low Density Polyethylene Resins

DOWLEX™ Linear Low Density Polyethylene Resins

ELITE™ Enhanced Polyethylene Resins

ENGAGE™ Polyolefin Elastomers

INFUSE™ Olefin Block Copolymers

NORDEL™ IP Hydrocarbon Rubber

VERSIFY™ Plastomers and Elastomers

®™ Trademark of The Dow Chemical Company34