This presentation by Cray Valley talks about surface treatments for optimizing dispersion of halogen-free, flame retardant minerals. It highlights water-based coatings and the reasons behind investigating fire-resistant plastics. This slideshow reveals Cray Valley's investigation into relevant surface treatments for specific mineral systems, methods to coat filler and elongating dispersion.

1. SURFACE TREATMENTS TO OPTIMIZE
DISPERSION OF HALOGEN FREE FLAME
RETARDANT MINERALS
Intro to Water-based Coatings

2. Agenda
Motivation
-Hazards
-Regulatory Influence
-Technology Shift
Mineral Dispersion
-Introduction
-Relevant Chemistries
Technical Results
-Functionality Selection
-Charging Method
-Correlating Ductility with Dispersion
Summary & Conclusions
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3. 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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4. 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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5. 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 Brominated Phosphorous Mineral Antimony Other
as largest volume flame retardant
through 2011 * Freedonia Market Study # FW35019
-Comprising 45% of demand
-Growing inline with the market (3%/yr)
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6. 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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7. Introduction to Dispersion
Property Dispersant Coupling Agent
Flow (MFI/MFR) ↑↑ ↑↑ or ↓↓
Modulus = =
Yield Strength = ↑↑
HDT = ↑↑
Impact resistance ↑ ↓
Elongation to break ↑ ↓↓
*Courtesy of Phantom Plastics
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
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8. Effective Dispersant 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
Vast majority of surface treated minerals leverage silane
chemistry
Cray Valley chemistry can fill the void beyond silane surface
chemistry
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9. Alternative Chemistry
Functionality SMA® Ricon® Commercially Available
Maleic anhydride  
Carboxylic acid 
Epoxy 
Imide  
Sulfonated 
Hydrogenated 
Acrylated  
Amine  
Brominated 
Developmental
Siloxy 
Chemistry and processes are core competencies for Cray
Valley; Alternative functionalities are routinely explored
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10. Maleated Polymers
Material Anhydride Tg Molecular
Structure
Class Range Range Weight
Styrene
Maleic 110°C
10.5 to 42%
Anhydride to 5k to 24k
by weight
(SMA®) 155°C
Copolymer
Liquid
-86°C
Functional 3 to 20%
to - 5k to 10k
Polybutadiene by weight
30°C
(Ricon®)
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11. 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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12. Dispersing ATH
Experimental composition: Mn Functionality Vinyl
Additive
(g/mol) (type/%) (%)
-60% ATH (1 & 50 m) Ricon® 156 1,400 - 70
-36% EVA (28% vinyl acetate) Ricon® 131 4,500 - 28
-4% Additive Ricon® 156MA17 2,500 Anhydride/ 17% 70
Ricon® 131MA17 5,500 Anhydride/ 17% 28
Additives were based on Ricon® 131MA5 4,700 Anhydride/ 5% 28
functional liquid PRO-5052 4,500 Epoxy* / 5% 28
polybutadienes (LPBD): (developmental)
NXT-6715 5,000 Amine** / 5% 28
(developmental)
Poly bd® R45 2,700 Hydroxyl*** 20
* Internally epoxidized
** Tertiary amine grafted
*** Terminal hydroxyl
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13. Introduction - Materials
Method 1 Method 2 Method 3
• PBD dispersed • ATH pre-charged • ATH treated with
onto porous with PBD H2O based
silica • Eliminates ‘extra’ dispersion of
• Approximately mineral content PBD
70% PBD • Ease of
content 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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14. Dispersing Large Diameter ATH
100
6.5
90
6 80
Tensile Strength (MPa)
5.5 70
Elongation (%)
60
5
50
4.5 40
4 30
20
3.5
10
3 0
Neat Ricon® Ricon® Ricon® Ricon® Neat Ricon® Ricon® Ricon® Ricon®
156 131 156MA17 131MA17 156 131 156MA17 131MA17
Tensile strength was reduced in filled systems; anhydride
functionalized systems to a lesser extent
Elongation increased 200 – 350%
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15. Alternate Chemistry
6.5 160
140
6
120
Tensile Strength (MPa)
5.5
Elongation (%)
100
5
80
4.5
60
4 40
3.5 20
3 0
Neat Ricon® PRO-5052 NTX-6715 Neat Ricon® PRO-5052 NTX-6715
131MA5 131MA5
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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16. Dispersing Small Diameter ATH
13 350
12
Tensile Strength @ Break (MPa)
11 300
10
Elongation (%)
9 250
8
7 200
6
5 150
4
3 100
Neat Ricon® 131MA5 Poly bd® R45 Neat Ricon® 131MA5 Poly bd® R45
Ricon® 131MA5 met target for tensile strength and elongation
Average elongation for neat material met requirement, but
was highly variable
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17. 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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18. Surface Treatment Method
600
500
Elongation (%)
400
300
200
100
0
Base Mechanical Starve Coated Flood Coated
Mechanical coating and wet coating were equally viable
methods
Integration of functional polybutadiene can coincide with
mineral surface treatment
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19. Improving Dispersion
Base Mechanical Starve Coated
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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20. Influence on Flammability
39
38
37
36
LOI (%)
35
34
33
32
31
30
Base Mechanical Starve Coated
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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21. Heat & Smoke Generation
4.5
250
Base
Base 4.0
Mechanical Mechanical
200 3.5
Starve Starve
RSR [(m2/s)/m2]
3.0
HRR [kW/m2]
150 2.5
2.0
100
1.5
1.0
50
0.5
0 0.0
0 100 200 0 50 100 150 200
Time (s) Time (s)
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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22. 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
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23. 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
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24. Cray Valley HSC
A Division of Total SA
Upstream Downstream Chemicals
• Oil & gas exploration • Trading & shipping • Base chemicals
• Production • Refining & marketing • Industrial & consumer
Focus
• Gas & power • Commodity & specialty market specialty
• Alternative energy fluids chemicals
Sales $24.6 $163.4 $23.2
(billion)
Employees 17,192 32,631 41,658
Total, a partner in your challenges
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25. Cray Valley HSC
Focus Markets
• Performance • Pressure • Printed circuit
Growth Markets
additives sensitive boards
Adhesives
• Tire & hose • Reactive • Electronics
Rubber
applications adhesives
• Thermoplastic
• Co-curing • IGS additives
agents
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26. Cray Valley
Global Presence
vv
vvv v
v v v
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v
Global HQ
v Regional HQ
v
v Sales Office
v Research
v Manufacturing
Distribution Network
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27. Cray Valley HSC
For additional information about Cray Valley, its products
or its work in Hydrocarbon Specialty Chemicals,
visit www.CVPolymerAdditives.com.