Cray Valley's ongoing study of polymer modification is presented, in part, in this slideshow. It specifically focuses on dissecting the differentiating commodity minerals with unique surface treatments. Topics covered include dispersing technology, the effect of dispersion in CaCO3-filled PP, and the analogue in PA6.

1. Differentiating Commodity Minerals
with Unique Surface Treatments
Minerals in Compounding

2. Overview
• Dispersing Technology
• Effect of Dispersion in CaCO3-filled PP
- Chemistry review
- Optimization
• Analogue in PA6
• Summary
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3. Dispersants: A Review
• Dispersants must bond strongly to the filler surface only
• Coupling agents bond strongly to filler AND surrounding
polymer matrix
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4. Dispersants: A Review
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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5. Dispersants: A Review
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
• Cray Valley chemistry can fill the void beyond silane
surface chemistry
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6. 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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7. Portfolio of Chemistry
Functionality SMA® Ricon® Commercially Available
Maleic anhydride  
Carboxylic acid 
Epoxy 
Imide  
Sulfonated 
Hydrogenated 
Acrylated  
Amine  
Brominated 
Siloxy  Developmental
• Chemistry and processes are core competencies for
Cray Valley; alternative functionalities are routinely
explored
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8. Dispersion Evaluation
Model Formulation Dispersant Options
↗ 30% CaCO3 (Omyacarb F) •SMA® 3000P
↗ 68.5% PP (Hival 2420) ↗ 24% anhydride
↗ 1.5% Dispersant ↗ 3,050 Mn
↗ Solid powder
↗ H2O dispersion
• Ricon® 131MA5
Evaluation Criteria
↗ 5% anhydride
↗ 4,700 Mn
↗ Cost
↗ High viscosity liquid
↗ Charpy impact resistance
↗ H2O dispersion
↗ Ductility
↗ MFR
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9. Dispersion Results
Cost
300%
250%
MFR 200% Modulus
150%
100%
50%
0%
Izod Yield
Ricon
SMA
Ductility Strength Baseline
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10. Optimization
Objective
Leverage dispersants to maintain mechanical properties
while reducing the cost of highly filled CaCO3 composites
Parameters Optimization Criteria
↗ 30 to 55% CaCO3 ↗ Minimize cost
↗ 0 to 3% SMA 3000P ↗ Maximize ductility, flow
↗ Baseline w/stearic acid & impact
↗ Maintain balance
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11. Optimization Results
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12. Optimization Results
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13. Cost-Benefit Analysis
55% Filled
Modulus, +33% Modulus, +11%
Yield, -47% Yield, -13%
Strength, -7% Strength, -7%
Ductility, -85% Ductility, -12%
Impact, -59% Impact, -16%
CaCO3 Loading
MFR, -43% MFR, -10%
Cost, -26% Cost, -19%
Stearic Acid
Modulus = 0.9 Gpa Modulus, 0% Modulus, 0%
Yield = 29.4 MPa Yield, -6% Yield, -5%
Strength = 22.1 MPa Strength, -14% Strength, 0%
Ductility = 38.4% Ductility, +12% Ductility, +10%
30% Filled
Impact = 3.7 kJ/m2 Impact, -3% Impact, +8%
MFR = 15.2 g/10min MFR, +25% MFR, +4%
Cost = $0.76 Cost, 0% Cost, +9%
0% Dispersant SMA Loading 3% Dispersant
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14. Future Work
• Pre-treated CaCO3 for application in polyamides
• Cost-benefit analysis considering embrittling effect
• H2O dispersions to fully coat mineral surface
• Similar methodology and analysis criteria
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15. Summary
• Anhydride functional additives validated as appropriate
in CaCO3 systems
- Rigid SMA ® provided robust property improvement
- Ductile Ricon® emphasized ductility & impact
• Mechanical properties maintained while increasing
CaCO3 & decreasing cost by leveraging dispersant
• Optimization indicated that increasing dispersant as a
function of CaCO3 loading will balance properties
• SMA outperformed stearic acid in property retention &
generation while increasing filler loading
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16. 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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17. 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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18. Cray Valley HSC
Focus Markets
• Performance • Pressure • Printed
Growth Markets
additives sensitive circuit
boards
Adhesives
• Tire & hose • Reactive
Rubber
applications adhesives • Pigment
Dispersants
• Co-curing • Insulated
agents Glass • Mineral
Sealants Dispersants
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19. Cray Valley HSC
Global Presence
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• For additional information about Cray Valley, its products
or its work in Hydrocarbon Specialty Chemicals,
visit www.CVPolymerAdditives.com
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