Differentiating Commodity Minerals with Unique Surface Treatments

Minerals in Compounding

Cray Valley HSC2

Overview

• Dispersing Technology

• Effect of Dispersion in CaCO3-filled PP

- Chemistry review- Optimization

• Analogue in PA6• Summary

Cray Valley HSC3

Dispersants: A Review

• Dispersants must bond strongly to the filler surface only• Coupling agents bond strongly to filler AND surrounding

polymer matrix

Cray Valley HSC4

Dispersants: A Review

• 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 ↑ ↓↓

Cray Valley HSC5

Dispersants: A Review

• 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

Cray Valley HSC6

Maleated Polymers

Material Class

Structure Anhydride Range

Tg Range

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

Cray Valley HSC7

Portfolio of Chemistry

Commercially Available

Developmental

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

Functionality SMA® Ricon®

Maleic anhydride

Carboxylic acid

Epoxy

Imide

Sulfonated

Hydrogenated

Acrylated

Amine

Brominated

Siloxy

Cray Valley HSC8

Dispersion Evaluation

Model Formulation

↗ 30% CaCO3 (Omyacarb F)↗ 68.5% PP (Hival 2420)↗ 1.5% Dispersant

Evaluation Criteria

↗ Cost ↗ Charpy impact resistance↗ Ductility↗ MFR

Dispersant Options

•SMA® 3000P↗ 24% anhydride↗ 3,050 Mn

↗ Solid powder↗ H2O dispersion

• Ricon® 131MA5↗ 5% anhydride ↗ 4,700 Mn

↗ High viscosity liquid↗ H2O dispersion

Cray Valley HSC9

Dispersion Results

Cost

Modulus

Yield

StrengthDuctility

Izod

MFR

0%

200%

400%

Ricon

SMA

Baseline

Cray Valley HSC10

Optimization

ObjectiveLeverage dispersants to maintain mechanical properties while reducing the cost of highly filled CaCO3 composites

Parameters

↗ 30 to 55% CaCO3

↗ 0 to 3% SMA 3000P↗ Baseline w/stearic acid

Optimization Criteria

↗ Minimize cost↗ Maximize ductility, flow & impact↗ Maintain balance

Cray Valley HSC11

Optimization Results

Cray Valley HSC12

Optimization Results

Cray Valley HSC13

Cost-Benefit Analysis

Modulus, +33%Yield, -47%Strength, -7%Ductility, -85%Impact, -59%MFR, -43%Cost, -26%

Modulus = 0.9 GpaYield = 29.4 MPaStrength = 22.1 MPaDuctility = 38.4%Impact = 3.7 kJ/m2

MFR = 15.2 g/10minCost = $0.76

Modulus, 0%Yield, -5%Strength, 0%Ductility, +10%Impact, +8%MFR, +4%Cost, +9%

Modulus, +11%Yield, -13%Strength, -7%Ductility, -12%Impact, -16%MFR, -10%Cost, -19%

Modulus, 0%Yield, -6%Strength, -14%Ductility, +12%Impact, -3%MFR, +25%Cost, 0%

SMA Loading

CaC

O3

Load

ing

Stearic Acid

30%

Fill

ed55

% F

illed

0% Dispersant 3% Dispersant

Cray Valley HSC14

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

Cray Valley HSC15

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

Cray Valley HSC16

• 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

Cray Valley HSC

Cray Valley HSC17

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

Cray Valley HSCA Division of Total SA

Cray Valley HSC18

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• Performance additives

• Tire & hose applications

• Co-curing agents A

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• Pressure sensitive

• Reactive adhesives

• Insulated Glass Sealants

Gro

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Mark

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• Printed circuit boards

• Pigment Dispersants

• Mineral Dispersants

Cray Valley HSCFocus Markets

Cray Valley HSC19

Cray Valley HSCGlobal Presence

Cray Valley HSC20

Cray Valley HSC

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

visit www.CVPolymerAdditives.com