Additives In Innovation & Product Engineering of Poly Olefins

Swapan Dhara

Regional Technical Head-Africa, India & Middle East

LyondellBasell Industries

Fine Organics & Jayvee Org. Endowment Lecture , New Delhi

Agenda

• Role of Additives

• Additives - Classifications

• Additives - Process

• Additives - Products

• Environment & Additives

• Conclusion

Definition

Materials used as components to Protect & Modify

the end product properties , enable better Plastic

products with enhanced Performance , long Service

life and new Applications & Markets.

Extending Beyond Polymer Protection

Additives can provide additional properties or effects beyond stabilisation

Phenolic AOs

Plasticisers

Organophosphites

UV AbsorbersAntifogging Stabilizers

Optical BrightenersSlip Agents

Light Stabilizers

AntimicrobialsAntistats

Colorants

Polymer Property Retention

Polymer Property Extension

End use Product Property Protection / Enhancement

Types of Additives

• Process Chemicals

• Product Additives

Process Chemicals

• Catalysts & Donors

• Process Support Chemicals, eg, Anti Static Agents

Product Additives• Stabilizers • Lubricants• Plasticizers• Slip Additives• Fillers• Process Aids• Pigments• Speciality additives

- Dispersion & wetting agents- Polymers- Anti scratch - Oxygen absorbers- Vis breaking Agents- Nucleating & Clarifying agents- Blowing Agent

Catalysts

The internal donor determines the performance of the catalyst and the properties of the polyolefin

The internal donor determines the performance of the catalyst and the properties of the polyolefin

The external donor is used to fine tune the catalyst performance

The external donor is used to fine tune the catalyst performance

Catalyst Manufacturer

PP Manufacturer

Manufacture and use of catalysts

Polypropylene

Avant ZNCatalyst

InternalDonor

TiCl4

SupportExternalDonorTEAL

Propylene

ZN - catalyst families Internal Donors

O OR

O OR O

O

R

R

R O

O

R

R

Ethyl Benzoate

O

OR

RO

OR

R

RR

Succinate

Phthalate

DietherCatalyst yieldMW distributionSelectivity rangeHydrogen responseOligomer contentMicro-tacticity

Effect of catalyst internal donor

Commodity Specialty

Narrow MWD(Fibres, cast film, etc.)

Phthalate Diether

Broad MWD(BOPP, Pipe etc.)

Ethyl Benzoate Succinate

Polymerisation processCatalyst yieldHydrogen responseSelectivity range

Performance PropertiesMWDMicro-tacticityOligomer content

ZN phthalate - applications

PP homopolymerGood control of MW and MWDGood processability

PP random copolymerVery good transparencyVery good glossGood mechanical property balance

PP impact copolymerHigh impactGood mechanicalproperty balance

ZN diether - spunbond applications

Features

Narrow MWD

Excellent spinnability

Excellent drawdown performance

Reduced smoke generation

Fine denier

Higher tenacity

ZN diether - impact copolymers

FeaturesVery high melt fluidity MFR 100Reactor Narrow MWDOdourless (No peroxide)Excellent stiffness- impactEasy processingLess warpage

ApplicationsAuto compound BumperInterior panelsThin wall injection mouldingImproved cycle time

ZN succinate - general characteristics

Internal donor : SuccinateHigh iso-tacticityCapable of producing very broad MWDCan expand product capabilities of single stage reactors towards a bimodal rangeImproved stiffness/impact balance for copolymers

ApplicationsBOPPPipesInjection moulding

ZN succinate - applications

High stiffness PP homopolymerThermoforming

Cast PP film

Injection moulding

High stiffness PP impact copolymerImproved balance of impact and stiffness

ZN succinate - high stiffness Homo Polymer

FeaturesHigher Stiffness

Higher HDT

Better barrier properties

Easy processing

Applications - ThermoformingHigher stiffness : down-gauging

Higher HDT : hot fill applications

HIPS replacement

ZN succinate - high stiffness Homo Polymer

Metallised CPP

Appliances

Cast PP filmStiffer lamination filmPackaging speed on FFS machine can be increasedMetallised film : Higher stiffness and better dyne retentionBetter barrier properties

Injection mouldingHigh stiffness without fillerHigh surface glossGood scratch resistance

Adstif copolymer with succinate catalysts

FeaturesExcellent stiffness with good impactGood glossEasy processingFood contact

ApplicationsFurniture Can replace ternary blends of Homo + Copolymer + fillerImproved surface aestheticsBetter scratch resistanceAppliancesElectrical plugs etc.

High Melt Strength PP as Additive : Examples

Thermoformed Foam PP

Anti Static Agents

Anti static Agents : Process & Product Additive

• Reduces static electricity generation when in – process dry polyolefinpowder transported pneumatically

• Used during polymerization / post polymerization – technology specific & dependant

• Used in Product formulation to impart antistatic / internal lubrication.

Antistatic Agents : Mechanism Minimization of electrostatic charge and increasing surface conductivity

Basic Building Block• An additive layer

starts building up on the surface

• The anti static agent will attract moisture

• A conductive layer is established

• The antistatic performance is obtained when the additive concentration reaches a certain level

Antistatic Agents - Examples Minimization of electrostatic charge and increasing surface conductivity

Short term antistatic effect Long term antistatic effect

Nucleating & Clarifying Agents

Nucleating & Clarifying Agents

• Nucleating Agents are generic materials - Homogeneous nucleation - Heterogeneous nucleation

• Clarifying Agents- Organic nucleating agents which are soluble in the

polymer matrix

Nucleation/ Clarifying Mechanism- An Illustration

Polymer meltPartially Crystallised

Fully Crystallised

Non - Nucleated

Nucleated

Clarified

Clarifying Agents

Ist Generation : Dibenzylidene Sorbitol ( DBS)2nd Generation : p-Methyl Dibenziline Sorbitol ( MDBS )3rd Generation : 3,4-dimethyl dibenzilidine sorbitol ( 3,4-DMDBS)4th Generation : 1,2,3-trideoxy-4,6.5,7-bis-O- 4-(propyl phenyl)methylene –nonitol –

a di benzylidine nonitol

Generation Product Max Use Temp.

Advantages Drawbacks

1G DBS 225 DegC Food contact Poor Clarity, Heat Stability

2G MDBS 250 DegC Clarity, Nucleation Taste Odor

3G Millad®3988i

285 DegC Clarity, Nucleation, Food Contact, Heat Stability

Suitable for ALL applications

Slip & Antiblock Agents

Slip Additives Reduction of coefficient of friction ( COF )

Examples

Basic Building Block

Slip Additives - Examples

• Oleamide

• Erucamide

• Strearamide

• Behenamide

• Oleamide & Erucamide - unsaturated fatty amides and

predominatly used as slip additives

• Stearamide & Behenamide - saturated fatty amides and

provides both slip & antiblock properties

Antiblocking Agents - Mechanism Prevention of Blocking in Films

Prevention of Blocking in Films

Basic Building Block

Silica induces surface roughness, air enters between film layers and makes openability easier

Anti block Additives- Examples

• Silica

• Talc

• Microfined Coated Calcium Carbonate

Stabilisers

Auto Oxidation Cycle for Polyolefins

Cycle II Cycle IRO. + .OHROO.R.

+ ROOH

R-H(Polymer)

Energy, Shear Melt ProcessingCatalyst Residues

R. Alkyl RadicalRO. Alkoxy RadicalHO. Hydroxy RadicalROO. Peroxy RadicalROOH Hydroperoxide

Traditional Inhibited Auto Oxidation for Polyolefins

Cycle II Cycle IRO. + .OH ROO.R.

+ ROOH

R-H(Polymer)

Energy, Shear Melt ProcessingCatalyst Residues

Phenolic AOs react with free radicals to give inactive product, ROH & H2O

Phosphites react with Hydroperoxides to give inactive product, ROH

Phenolic AOs react with oxygen centered radicals

“Phenol Free” Inhibited Auto Oxidation for Polyolefins

Cycle II Cycle IRO. + .OH ROO.R.

+ ROOH

R-H(Polymer)

Energy, Shear Melt ProcessingCatalyst Residues

Hydroxylamine / Hindered Amines react with free radicals to give inactive product, ROH & H2O

Phosphites react with Hydroperoxides to give inactive product, ROH

Hydroxylamines react with oxygen centered radicals

Nitrones react with carbon centered radicals

Primary Stabilisers – Phenolic AOs : Examples

Basic Building Block

AO 3114 (anti gas Fading for fibres)

Long Term Stabilisers – Thioether Synergists

Basic Building Block

Thioethers & Dithiols: Examples

DLTDP

DSTDP

Melt Stabilisers – Peroxide Decomposers

Basic Building Block

Melt Stabilisers – Peroxide Decomposers : Examples

Metal Deactivators – Inhibits degradation by metal ions (catalyst residues)

Reaction Scheme of degradation in presence of Metal

Basic Building Block

Metal Deactivators – Inhibits degradation by metal ions (catalyst residues) : Examples

UV Stabilisers : Examples

Acknowledgement – CIBA GIEGY

Tinuvin 622

Chimasorb 119

Vis- Breaking Additives

Vis –Breaking Additives : Non woven & Melt blown

• Conventional Vis-breaking with Peroxide

• Peroxide free visbreaking

Vis Breaking – New Technology

Acknowledgement – CIBA GIEGY

Melt Blown Non Wovens : Scanning Electron Microscopy

Acknowledgement – CIBA GIEGY

Anti Scratch Agents

Anti Sctatch Additives

• Enables broader use of PP/TPO vs more expensive polymer

• Performs well in combination with light stabiliser & Colourants

• No exudation & Stickiness on parts surface

• Can be directly dosed during Injection Moulding

Acknowledgement – CIBA GIEGY

Oxygen Scavengers

Oxygen Absorbers

• To reduce and / or eleminate oxygen inside the package

• Enhances passive barrier performance

• Improves Product Shelf life

Foaming / Blowing Agents

Blowing Agents

• Chemical Blowing Agents

• Physical Blowing Agents

High Melt Strength(HMS) PP +Blowing Agent :PP FoamFeatures of PP Foam• Cost savings due to lower material cost

and faster processability• Excellent impact propertieseven at lower

temperatures• Wide temp window (-40 Deg C to +120

DegC)• Microwave able retorting• Hot filling, Stretilisation possible• No restrictions with fatty food

compliance• Excellent humidity barrier• Smooth surface “Pleasant Touch”

Acknowledgement – Lyondell Basell Industries

Wetting / Dispersion Agents

Wetting Agents & Dispersion Agents Pigment Wetting

No Wetting

• No Effect on agglomerate cohesion• No Stabilisation• Phase seggregation and chalking• No Improvement of dispersability

• Weakening of agglomerate cohesion

• Stabilisation of primary parts

• Optimum dispersability

• No weakening of agglomerate cohesion

• Part stabilisation of primary parts

• Improves dispersability

Complete penetration

Only outside wetting

Wetting

Wax / Polymer

• Viscosity• Polarity

Pigment Agglomeration

• Capillary Forces• Particle &

Agglomerate Size• Particle Size

distribution• Surface Tension• Polarity

Dispersion Additives - Examples

Description Acid Value Melting point

Ethoxylated alkylamine

- Liquid

Ethoxylated alkylamine

- 85 – 100 Degt C

Fatty Acid Esters 5 60 – 70 DegC

Fatty Acid Esters 5 Liquid

Alkane sulfonate 220 – 230 DegC

Process Aids

Why Use Process Aids (PPA ) ?

Eliminate Melt Fracture

Reduce die build up Reduce gels and optical defects

Reduce change over time

Reduce die pressure & extrusion temperature

Applications of Process Aids

PE Films BOPP / OPP Films

HDPE Blow Molding

Cables Pipes

Sheets

Monofilaments & Fibres

Process Aid - Examples

• Fluoro polymers

• Multi functional Complex Oleo-Chemical derivatives( Melt Flow Promoter +Ext. Lubricant +Dispersion Agent )

Fillers

Fillers – Performance modifying Agents

• Types- Mostly inorganics- Organic

• Examples- Calcium Carbonate , Talc , Nano Clays- Fibrous org., eg. Wood Flour

Characterization of CaCO3

Particle Structures of Natural CaCO3 after grinding

influence the product properties

CaCO3 – Most Important Properties

• Surface Treatment– Composition– Surface Coverage– Surface Tension

• Purity– Colour– Metal – “free”– Insolubles

• Particle Size– Particle Size distribution– Top Cut– Median PS– Specific Surface

Nano Additives - Examples

• Organo treated Clays for Polymer Composites

• Speciality Zinc Oxide as anti microbials

• Photo catalytic Titanium dioxide

• Carbon nanotubes as additives nano nucleators based on silica.

Nano Clay as filler

• Concept :The incorporation of single digit percentages of high surface area nano clays into host polymer systems improves the performance of the specific polymer matrix without significant deterioration of properties

• Benefits :- Reinforcement- Increased dimensional Stability & HDT- Lower Density- Increased melt strength- Thermoplastic Recyclable

Nano Clays : Types

• Bentonite– A rock– A mixture of several minerals

(one is smectite)– Billions of tons worldwide

• Smectite– Component of bentonite– Known as a 2:1 layered clay– Clays in the smectite family

• Montmorillonite (di-octahedral)• Hectorite (tri-octahedral)• Others

10 microns

SEM of Unrefined Bentonite

TEM of Refined Montmorillonite

Impala Side Moulding with nano composite : Example

Global Additives Market

Global Market – Polymer Additives by Volume

Global Additive Market ~ 21.8 billion lbs

22%

11%

21%

23%

23%North America

Europe

China

Asia Pacific

Other (India, SA, ME,East Eur. Africa)

Global Market – Additives Segments by Type

Highest Consumption- Plasticizers followed by Property Extenders

58%24%

11%

7%Plasticisers

Modifiers (Nucl., Clarifying, Coupling agents,Imp. Modifiers, Processing Aids)

Property Extenders (AO, Antistat, Biocides,Heat & Light Stab, Flame Retardants)

Processing Aids (Antiblocks, Lubricants,Slips)

PVC – The single Large consumer of Additives beside Polyolefins

Major Additive consumption by Type

- Plasticizers

- Stabilizer

- Lubricants

Plasticizer - PVC : The Trend

• Phthalates, DEHP (DOP) are under environmental pressure but continue to remain as building block.

• Commercially available alternates, eg, adipates, benzoates,citrates & specialities( ESO,Polyesters) still expensive in comparison.

• New Development - Plasticizers from renewable sources , eg, isosorbide diesters- a sorbitol derivative ( DOP alike)

Stabilizer – The Trend

• Enviornmental concerns changing PVC heat stabilizer market dynamics

• PVC applications are under pressure to replace heavy metal based stabilizersMixes metal stabilizers,eg Ca-Zn, tin stabilisers & organic alkyl phosphit stabilisers gradually replacing heavy metal stabilisers

• Organic compound based stabilizers will be trend setter – Reduction of inorganic component & proportionate increase of organic component to minimise the -ve impact.

• Future Trend – Development of organic stabilizers from organic renewable resources

Conclusion : Trend & driving forces within polymer additive industry

• Global Majors focussing on niche products• Patent Expiry leading to newer players• One pack & customised additive formulations• Higher environmental awareness : Driving innovations

Technology Support and Partnership of

Poymer-Additive Mfg. leading Innovations

Acknowledgements

• Fine Organics

• Jayvee Organics Pvt. Ltd.

• Indian Plastics Institute

• Polymer additive Manufactures

Thank you for your attention