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

End use Product Property Antimicrobials

Protection / Enhancement Antistats

UV Absorbers Colorants
Polymer Property Antifogging Stabilizers
Extension Optical Brighteners
Slip Agents
Light Stabilizers

Plasticisers
Polymer Property
Retention

Phenolic AOs Organophosphites

Additives can provide additional properties or

effects beyond stabilisation
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
Manufacture and use of catalysts

Catalyst PP Manufacturer
Manufacturer
External
Support Donor
TEAL
Internal
Donor

TiCl4

Avant ZN Propylene
Catalyst

The Polypropylene
Theinternal
internaldonor
donor
determines The
Theexternal
externaldonor
donorisis
determinesthetheperformance
performance
of used
usedtotofine
finetune
tunethe
ofthe
thecatalyst
catalystand
andthe
the the
properties catalyst
catalystperformance
propertiesof
ofthe
thepolyolefin
polyolefin performance
ZN - catalyst families
Internal Donors

Ethyl Benzoate Phthalate

O O O O
R R O

O
R
Catalyst yield
MW distribution Succinate Diether
Selectivity range
O R
Hydrogen response
R R R O
Oligomer content R O
Micro-tacticity R O
R R R O
O R
Effect of catalyst internal donor

Polymerisation process Performance Properties

Catalyst yield MWD
Hydrogen response Micro-tacticity
Selectivity range Oligomer content

Commodity Specialty

Narrow MWD Phthalate Diether

(Fibres, cast film, etc.)

Broad MWD Ethyl Benzoate Succinate

(BOPP, Pipe etc.)
 ZN phthalate - applications

PP homopolymer
Good control of MW and MWD
Good processability
PP random copolymer
Very good transparency
Very good gloss
Good mechanical
property balance
PP impact copolymer
High impact
Good mechanical
property balance
ZN diether - spunbond applications

Features

Narrow MWD

Excellent spinnability

Excellent drawdown performance

Reduced smoke generation

Fine denier

Higher tenacity
ZN diether - impact copolymers

Features
Very high melt fluidity MFR 100
Reactor Narrow MWD
Odourless (No peroxide)
Excellent stiffness- impact
Easy processing
Less warpage

Applications
Auto compound
Bumper
Interior panels
Thin wall injection moulding
Improved cycle time
ZN succinate - general characteristics

Internal donor : Succinate

High iso-tacticity
Capable of producing very broad
MWD
Can expand product capabilities of
single stage reactors towards a
bimodal range
Improved stiffness/impact
balance for copolymers

Applications
BOPP
Pipes
Injection moulding
ZN succinate - applications

High stiffness PP homopolymer

Thermoforming

Cast PP film

Injection moulding

High stiffness PP impact copolymer

Improved balance of impact and stiffness
ZN succinate - high stiffness Homo Polymer

Features
Higher Stiffness
Higher HDT
Better barrier properties
Easy processing

Applications - Thermoforming
Higher stiffness : down-gauging
Higher HDT : hot fill applications
HIPS replacement
ZN succinate - high stiffness Homo Polymer

Cast PP film Metallised CPP

Stiffer lamination film

Packaging speed on FFS machine
can be increased
Metallised film : Higher stiffness and
better dyne retention
Better barrier properties
Appliances
Injection moulding
High stiffness without filler
High surface gloss
Good scratch resistance
Adstif copolymer with succinate catalysts

Features
Excellent stiffness with good
impact
Good gloss
Easy processing
Food contact

Applications
Furniture
Can replace ternary blends of
Homo + Copolymer + filler
Improved surface aesthetics
Better scratch resistance
Appliances
Electrical 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 polyolefin
powder 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 The antistatic

An additive layer
starts building up on performance is
the surface obtained when the
additive
The anti static agent concentration
will attract moisture reaches a certain
level
A conductive layer
is established
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

Partially Fully
Polymer melt Crystallised Crystallised

Non -
Nucleated

Nucleated

Clarified
Clarifying Agents

Generation Product Max Use Advantages Drawbacks

Temp.
1G DBS 225 DegC Food contact Poor Clarity, Heat
Stability
2G MDBS 250 DegC Clarity, Nucleation Taste Odor

3G Millad 285 DegC Clarity, Suitable for ALL

3988i Nucleation, Food applications
Contact, Heat
Stability

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
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

R. Alkyl Radical
Energy, Shear RO. Alkoxy Radical
Melt Processing HO. Hydroxy Radical
R-H Catalyst Residues ROO. Peroxy Radical
(Polymer) ROOH Hydroperoxide

R.
Cycle II Cycle I ROO.
RO. + .OH +
ROOH
Traditional Inhibited Auto Oxidation for Polyolefins

Energy, Shear
R-H
Melt Processing
(Polymer)
Catalyst Residues

R.
RO. + .OH Cycle II Cycle I ROO.
+
ROOH

Phenolic AOs react with

free radicals to give
Phosphites react with
inactive product, ROH & Phenolic AOs react with
Hydroperoxides to give
H2O oxygen centered radicals
inactive product, ROH
Phenol Free Inhibited Auto Oxidation for Polyolefins

Energy, Shear Nitrones react with carbon

R-H
Melt Processing centered radicals
(Polymer)
Catalyst Residues

R.
RO. + .OH Cycle II + Cycle I ROO.
ROOH

Hydroxylamine / Hindered
Amines react with free
radicals to give inactive
product, ROH & H2O
Phosphites react with
Hydroperoxides to give Hydroxylamines react with
oxygen centered radicals
inactive product, ROH
Primary Stabilisers Phenolic AOs : Examples
Basic Building Block

AO 3114 (anti gas Fading for fibres)

Long Term Stabilisers Thioether Synergists

Thioethers & Dithiols: Examples

DLTDP

DSTDP
Basic Building Block
Melt Stabilisers Peroxide Decomposers

Basic Building Block

Melt Stabilisers Peroxide Decomposers :
Examples
Metal Deactivators Inhibits degradation by metal
ions (catalyst residues)

Basic Building Block

Reaction Scheme of degradation in presence of Metal

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

Tinuvin 622

Chimasorb 119

Acknowledgement CIBA GIEGY

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 Foam
Features 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 Effect on agglomerate cohesion

Wax / Polymer No Stabilisation
Phase seggregation and chalking
No Improvement of dispersability
Viscosity No Wetting
Polarity Weakening of
agglomerate cohesion
Stabilisation of primary
parts
Optimum dispersability
Complete penetration

Pigment Agglomeration
No weakening of
agglomerate cohesion
Part stabilisation of
Capillary Forces Wetting primary parts
Particle & Improves dispersability
Agglomerate Size
Particle Size Only outside wetting
distribution
Surface Tension
Polarity
Dispersion Additives - Examples

Description Acid Value Melting point

Ethoxylated - Liquid
alkylamine
Ethoxylated - 85 100 Degt C
alkylamine
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 Reduce die build up Reduce gels and optical

Fracture defects

Reduce change Reduce die pressure &

over time extrusion temperature
Applications of Process Aids

PE Films BOPP / OPP HDPE Blow Sheets

Films Molding

Cables Pipes 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
SEM of Unrefined Bentonite
Bentonite
A rock
A mixture of several minerals
(one is smectite) 10 microns
Billions of tons worldwide
TEM of Refined Montmorillonite
Smectite
Component of bentonite
Known as a 2:1 layered clay
Clays in the smectite family
Montmorillonite (di-octahedral)
Hectorite (tri-octahedral)
Others
Impala Side Moulding with nano composite :
Example
Global Additives Market
Global Market Polymer Additives by Volume

23% 22%
North America

Europe

China

11% Asia Pacific

Other (India, SA, ME,

23% East Eur. Africa)

21%

Global Additive Market ~ 21.8 billion lbs

Global Market Additives Segments by Type

7%
Plasticisers
11%

Modifiers (Nucl., Clarifying, Coupling agents,

Imp. Modifiers, Processing Aids)

Property Extenders (AO, Antistat, Biocides,

58% Heat & Light Stab, Flame Retardants)
24%

Processing Aids (Antiblocks, Lubricants,

Slips)

Highest Consumption- Plasticizers followed by Property Extenders

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

stabilizers
Mixes 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