SURFACE TREATMENTS TO OPTIMIZE DISPERSION OF HALOGEN FREE FLAME

RETARDANT MINERALS

Intro to Water-based Coatings

Agenda

Motivation

-Hazards

-Regulatory Influence

-Technology Shift

Mineral Dispersion

-Introduction

-Relevant Chemistries

Technical Results

-Functionality Selection

-Charging Method

-Correlating Ductility with Dispersion

Summary & Conclusions

2 Cray Valley HSC

Motivation – Hazards & Regulation

Increase in synthetic content in homes produces hotter and more toxic fires and has dropped escape time from 17 to 3 minutes (1975)

Increasingly stringent fire codes and flammability requirements in Building Materials & Construction (BM&C) products

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Motivation – Hazards & Regulation

Restriction of Hazardous Substances Directive (RoHS)-Adopted in EU 2006, China & South Korea in 2007

-Restricts six hazardous materials in electronic/electrical applications

- Lead, mercury, cadmium, hexavalent chromium, polybrominated biphenyls, polybrominated diphenyl ether

- Skin disorders, nervous and immune system effects, liver, kidney and thyroid malfunctions, and possible carcinogen

Waste Electrical and Electronic Equipment Directive (WEEE)-Legislative initiative to solve the problem of toxic e-waste

-Targets for collection, recycling and recovery of electrical goods

-Responsibility for disposal of e-waste imposed on manufacturer

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Technology

Flame retardant plastics have become more critical than ever before

$827 million FR market segmented*:-Halogenated: 36%

-Non-halogenated: 64%

Plastics industry lagging-Halogenated FR remain dominant

Aluminum trihydrate (ATH) projected as largest volume flame retardant through 2011 -Comprising 45% of demand

-Growing inline with the market (3%/yr)

Brominated Phosphorous Mineral Antimony Other

* Freedonia Market Study # FW35019

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Introduction

Surveyed W&C industry to identify outstanding difficulties transitioning to non-halogenated flame retardants

Matching FR performance on halogenated compounds required greater than 60% by weight mineral filler

Elevated loadings of additive caused:-Poor ductility

-Low tensile strength

-Significant change in flow

Objectives:-Improve elongation via dispersion

-Identify surface treatment options relevant to specific mineral systems

-Investigate methods to coat filler

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Introduction to Dispersion

Dispersants promote homogeneity and prevent defect sites via agglomeration

Coupling agents are bi-functional and effectively immobilize filler and polymer chains through A—B—C structure:

-Anchor --- Buffer/Bridge --- Couplant

*Courtesy of Phantom Plastics

Property Dispersant Coupling Agent

Flow (MFI/MFR) ↑↑ ↑↑ or ↓↓

Modulus = =

Yield Strength = ↑↑

HDT = ↑↑

Impact resistance ↑ ↓

Elongation to break ↑ ↓↓

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Effective Dispersant Chemistry

Vast majority of surface treated minerals leverage silane chemistry

Cray Valley chemistry can fill the void beyond silane surface chemistry

Filler Type Best Dispersant

2nd Best 3rd Best

Calcium carbonate Anhydride Carboxylic acid

Primary amine

Dolomite Sulfonic acid Carboxylic acid

Anhydride

Magnesium hydroxide

Anhydride Silane Carboxylic acid

Mica Primary amine Silane Sulfonic acid

Talc Silane --- ---

Silica Silane Sulfonic acid Anhydride

Wollastonite Primary amine Anhydride Carboxylic acid

Titanium dioxide Anhydride Carboxylic acid

Silane

*Courtesy of Phantom Plastics

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Alternative Chemistry

Functionality SMA®

Ricon®

Maleic anhydride

Carboxylic acid

Epoxy

Imide

Sulfonated

Hydrogenated

Acrylated

Amine

Brominated

Siloxy

Commercially Available

Developmental

Chemistry and processes are core competencies for Cray Valley; Alternative functionalities are routinely explored

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Maleated Polymers

Material Class

StructureAnhydri

de Range

Tg Rang

e

Molecular

Weight

Styrene Maleic Anhydride (SMA®) Copolymer

10.5 to 42% by weight

110°C to

155°C5k to 24k

Liquid Functional Polybutadiene (Ricon®)

3 to 20% by weight

-86°C to -

30°C5k to 10k

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Literature Evidence

Maleated Polybutadiene (MBPD) historically used as mineral surface treatment

-Calcium carbonate – water soluble variants to ‘pre-treat’ minerals with dispersant

-Aluminum trihydrate – formation of carboxylate salt to cover mineral surface by ‘loopy’ adsorption

-Clays, talcs, etc…

-Rothon, R. Particulate Filled Polymer Composites. 2nd edition, Shrewsbury, UK: Rapra Technology Limited, 2003.

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Dispersing ATH

Experimental composition:

-60% ATH (1 & 50 mm)

-36% EVA (28% vinyl acetate)

-4% Additive

Additives were based on functional liquid polybutadienes (LPBD):

Additive Mn(g/mol)

Functionality (type/%)

Vinyl(%)

Ricon® 156 1,400 - 70

Ricon® 131 4,500 - 28

Ricon® 156MA17

2,500 Anhydride/ 17% 70

Ricon® 131MA17

5,500 Anhydride/ 17% 28

Ricon® 131MA5 4,700 Anhydride/ 5% 28

PRO-5052 (developmental)

4,500 Epoxy* / 5% 28

NXT-6715 (developmental)

5,000 Amine** / 5% 28

Poly bd® R45 2,700 Hydroxyl*** 20* Internally epoxidized** Tertiary amine grafted*** Terminal hydroxyl

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Introduction - Materials

Method 1• PBD dispersed

onto porous silica

• Approximately 70% PBD content

Method 2• ATH pre-

charged with PBD

• Eliminates ‘extra’ mineral content

Method 3• ATH treated

with H2O based dispersion of PBD

• Ease of introduction

Pre-treated ATH tended to aerate less (EH&S)

Material process improvements: torque & throughput (Productivity)

Reduced dilution of EVA matrix (formulation)

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Dispersing Large Diameter ATH

Neat Ricon® 156

Ricon® 131

Ricon® 156MA17

Ricon® 131MA17

3

3.5

4

4.5

5

5.5

6

6.5

Tens

ile S

tren

gth

(MPa

)

Neat Ricon® 156 Ricon® 131 Ricon® 156MA17

Ricon® 131MA17

0

10

20

30

40

50

60

70

80

90

100

Elon

gatio

n (%

)

Tensile strength was reduced in filled systems; anhydride functionalized systems to a lesser extent

Elongation increased 200 – 350%

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Alternate Chemistry

Neat Ricon® 131MA5

PRO-5052 NTX-67153

3.5

4

4.5

5

5.5

6

6.5

Tens

ile S

tren

gth

(MPa

)

Neat Ricon® 131MA5

PRO-5052 NTX-67150

20

40

60

80

100

120

140

160

Elon

gatio

n (%

)

Low anhydride, amine or epoxy functionality LPBD increased elongation 500 – 700%

Less variation in data with LPBDs over base filled material

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Dispersing Small Diameter ATH

Neat Ricon® 131MA5

Poly bd® R453

4

5

6

7

8

9

10

11

12

13

Tens

ile S

tren

gth

@ B

reak

(MPa

)

Neat Ricon® 131MA5

Poly bd® R45100

150

200

250

300

350

Elon

gatio

n (%

)Ricon® 131MA5 met target for tensile strength and elongation

Average elongation for neat material met requirement, but was highly variable

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Filled Summary

Plasticization effect apparent in filled systems

-Unfunctionalized LPBD significantly reduced tensile strength

-Anhydride functionalized analogues helped disperse the ATH by polar interactions with the EVA and mineral surface

Ductility of EVA regained by improved dispersion of ATH

-Believed that surface wettout dispersed the ATH and prevented re-agglomeration during molding

-Reducing the average particle size of the ATH lessened the likelihood of providing a defect site during void formation while under strain

-Owing to the low molecular weight and high functional loading (17%) LBPD-3 likely enveloped the ATH

versus

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Surface Treatment Method

Mechanical coating and wet coating were equally viable methods

Integration of functional polybutadiene can coincide with mineral surface treatment

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Base Mechanical Starve Coated Flood Coated0

100

200

300

400

500

600

Elon

gatio

n (%

)

Improving Dispersion

Base Starve CoatedMechanical

Fewer instance of large aggregate in coated samples and relative aggregate size reduction

Dispersion efficiency of functional LBPD was comparable between mechanical and wet coating methods

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Influence on Flammability

Base Mechanical Starve Coated30

31

32

33

34

35

36

37

38

39

LOI (

%)

UL94 V-2 UL94 V-0 UL94 V-2

Pre-coating ATH with LPBD dispersant not only maintained the flammability performance, but also improved it

Dispersing augments the ‘self-extinguishing’ nature of the filled polymer

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Heat & Smoke Generation

Heat release rate (HRR) improved by introduction of LPBD coating

Rate of smoke release (RSR) was lowest in composition prepared using starve coating Method 3

LPBD coatings in general imparted better HRR and RSR to EVA/ATH composite

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0 100 2000

50

100

150

200

250BaseMechan-icalStarve

Time (s)

HRR

[kW

/m2]

0 20 40 60 80 1001201401601802000.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5Base

Mechanical

Starve

Time (s)

RSR

[(m

2/s)

/m2]

Summary

Pre-dispersing a functionalized liquid polybutadiene on ATH is an effective way to promote ductility through dispersion

-Mechanical and wet coating methods proved adequate

Molecular weight, functionality and functional loading are leading factors when selecting an appropriate dispersant

Appropriate functionalities vary by surface chemistry of the mineral

-Judicious selection maximizes dispersion potential

Flammability performance likely linked to improved dispersion of water containing minerals

22 Cray Valley HSC

Cray Valley HSC

Leading global supplier of hydrocarbon resins, diene-based resins, and specialty monomers

- Wingtack® and Norsolene® (C5 & C9 tackifiers)

- Poly bd®, KrasolTM, and Ricon® (low molecular weight liquid polybutadiene resins)

- SMA® (styrene-maleic anhydride copolymer resins)

- DymalinkTM (metal centered monomers)

Annual sales over $350 million and has more than 340 employees worldwide

Company’s more than 250 products are manufactured at 9 sites in 4 countries

23 Cray Valley HSC

Cray Valley HSCA Division of Total SA

Upstream Downstream Chemicals

Focus

• Oil & gas exploration• Production• Gas & power • Alternative energy

• Trading & shipping• Refining & marketing• Commodity & specialty fluids

• Base chemicals• Industrial & consumer market specialty chemicals

Sales (billion)

$24.6 $163.4 $23.2

Employees

17,192 32,631 41,658

Total, a partner in your challenges

24 Cray Valley HSC

Cray Valley HSCFocus Markets

Ru

bb

er

• Performance additives

• Tire & hose applications

• Co-curing agents

Ad

hesi

ves

• Pressure sensitive

• Reactive adhesives

• IGS

Gro

wth

Mark

ets

• Printed circuit boards

• Electronics

• Thermoplastic additives

25 Cray Valley HSC

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Cray ValleyGlobal Presence

Research

Regional HQ

Sales Office

Global HQ

Manufacturing

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Distribution Network

26 Cray Valley HSC

Cray Valley HSC

For additional information about Cray Valley, its products or its work in Hydrocarbon Specialty Chemicals,

visit www.CVPolymerAdditives.com.