Dispersants & Coupling Agents: New Chemistry for a Mature Industry

DISPERSANTS & COUPLING AGENTS: NEW CHEMISTRY FOR A MATURE INDUSTRY

Dispersants for Filled Polymers

Agenda

Dispersants & Coupling Agents

Effective Chemistry

The ‘Additive Toolbox’

Applications

-

Classical Formulations

-

Emerging Materials

Summary

2 Cray Valley HSC

Interfacial Technology

Dispersants must bond strongly to the filler surface only

Coupling agents bond strongly to filler AND surrounding polymer matrix

DispersantDispersant Coupling AgentCoupling Agent

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Measurable Property Improvements

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

PropertyProperty DispersantDispersant Coupling AgentCoupling AgentFlow (MFI/MFR) ↑↑ ↑↑

or ↓↓Modulus = =Yield Strength = ↑↑HDT = ↑↑Impact resistance ↑ ↓Elongation to break ↑ ↓↓

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Effective Dispersant Chemistry

Cray Valley chemistry can fill the void beyond silane surface chemistry

Filler TypeFiller Type Best DispersantBest Dispersant 22ndnd BestBest 33rdrd BestBestCalcium carbonate Anhydride Carboxylic acid Primary amineDolomite Sulfonic

acid Carboxylic acid AnhydrideMagnesium hydroxide Anhydride Silane Carboxylic acidMica Primary amine Silane Sulfonic

acidTalc Silane --- ---Silica Silane Sulfonic

acid AnhydrideWollastonite Primary amine Anhydride Carboxylic acidTitanium dioxide Anhydride Carboxylic acid Silane

*Courtesy of Phantom Plastics

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Maleated

Polymers

Material Material ClassClass StructureStructure Anhydride Anhydride

Range Range TTgg

RangeRangeMolecular Molecular

WeightWeight

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°C

5k to 10k

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Additive Toolbox

SMA®SMASMA®®

Ricon®RiconRicon®®

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Alternative ChemistryCommercially Available

Developmental

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

FunctionalityFunctionality SMASMA®® RiconRicon®®

Maleic

anhydride

Carboxylic acid

Epoxy

Imide

Sulfonated

Hydrogenated

Acrylated

Amine

Brominated

Siloxy

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Application

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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Application

Literature survey demonstrates applicability of SMA®

-

Dispersing & coupling of PMMA core-shell impact modifiers in PA6 and PA6/6 composites

-

Paul, D.R., et al. Polymer, 34(9), p.1874-1885, 1993.

-

Interfacial adhesion promotion and surface coverage between glass fiber and polystyrene using oligomeric

styrene-co-maleic

anhydride

-

Devaux, E., et al., Polymer Testing, 21(7), p. 773-779, 2002.

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Dispersing ATH

AdditiveAdditive MnMn(g/mol)(g/mol)

Functionality Functionality (type/%)(type/%)

VinylVinyl(%)(%)

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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Dispersing ATH -

Data

Experimental Composition I:-

60% ATH (50 mm)

-

36% EVA (15% vinyl acetate)

- 4% Additive

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Experimental Composition II:-

60% ATH (1 mm)

-

36% EVA (28% vinyl acetate)

- 4% Additive

•

Additives were based on functional liquid polybutadienes

(LPBD):

Dispersing Large Diameter ATH

3

3.5

4

4.5

5

5.5

6

6.5

7

Neat Ricon® 156

Ricon® 131

Ricon® 156MA17

Ricon® 131MA17

Tens

ile S

treng

th (M

Pa)

0

10

20

30

40

50

60

70

80

90

100

Neat Ricon® 156

Ricon® 131

Ricon® 156MA17

Ricon® 131MA17

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

3

3.5

4

4.5

5

5.5

6

6.5

7

Neat Ricon® 131MA5

PRO-5052 NTX-6715

Tens

ile S

treng

th (M

Pa)

0

20

40

60

80

100

120

140

160

Neat Ricon® 131MA5

PRO-5052 NTX-6715

Elon

gatio

n (%

)Low anhydride, amine or epoxy functionalized LPBS increased elongation 500 –

750%

Less variation in data with LPBDs

over based filled material

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3

4

5

6

7

8

9

10

11

12

13

Neat Ricon® 131MA5 Poly bd® R45

Tens

ile S

treng

th @

Bre

ak (M

Pa)

100

150

200

250

300

350

Neat Ricon® 131MA5

Poly bd® R45

Elon

gatio

n (%

)

Dispersing Small Diameter ATH

Ricon®

131MA5 met target for tensile strength and elongation

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

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Dispersing Dragonite®

HNT

Crystallization induced property improvements in PP with HNT-

Marginal loadings ~1%; literature supported

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Dispersing Dragonite®

HNT

Promote property changes through dispersion

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Summary & Conclusion

Identify application needs on basis of:-

Coupling versus dispersion

-

Appropriate functionality for filler

-

Identify appropriate oligomeric

backbone

-

Contact Cray Valley for all non-silane

needs!

Functional liquid polybutadienes

were effective in EVA/ATH formulations to restore lost ductility in NHFR transition

Emerging fillers can take advantage of the ‘ToolBox’ approach to select appropriate additives or surface

treatments

18 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

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Cray Valley HSC A Division of Total SA

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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

Polymer Modification

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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

Cray Valley HSC

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