GET Induction Presentation_21 08 12_1

RIL – Confidential (for internal sharing only)

RTG Hazira

Overview of Polypropylene & PP Catalyst Technology

Development


Outline of presentation

Overview of polymers – general aspects

Polypropylene - Versatile Polymer

Polypropylene value chain

Monomer

Catalyst technology

Polymerization Technology

Polymer Processing

RTG Hazira overview


Polymers

Chemical Industry- Products pattern

Polymers constitute 20 % of Mega Chemical Industry


Polymers

POLYMERS

BIO-POLYMERS

Proteins, Nucleic

acid

NATURAL

POLYMERS

Rubber, Starch,

Cellulose

SYNTHETIC

POLYMERS

Polyethylene

Nylon,PVC

Elastomers &

Plastics

Thermosets &

Thermoplastics


Polymers

Thermoplastics can be softened or melted by heat

and reformed (molded) into another shape.

Most addition polymers are thermoplastics.

The polymer chains are held together by weak

interactions (noncovalent bonds) such as :

van der Waal’s forces,

London dispersion forces and

Dipole-dipole attractions.

These interactions are disrupted by heating, allowing

the chains to become independent of each other.

Heating and reforming can be repeated indefinitely (if

degradation doesn’t occur). This allows recycling.

Thermoplastic Polymers


Polymers

Thermoset plastics melt initially, but on further

heating they become permanently hardened.

Once formed, thermoset plastics cannot be

remolded, and they cannot be recycled.

On heating, thermoset plastics become cross-linked

(covalent bonds form between the chains). The

cross-linked chains form a rigid network

cross-linked linear

Thermoset Plastic


Polymers

HIGH-DENSITY POLYMERS

LOW-DENSITY POLYMERS

Linear polymers with chains that can pack closely

together. These polymers are often quite rigid.

Branched-chain polymers that cannot pack together

as closely.

These polymers are often more flexible than high-

density polymers.


Polymers

Mode of formation

• Addition Polymerization - Polyethylene,

Polypropylene

• Condensation Polymerization - PET, Nylon 66

Mechanism of formation

• Free radical - LDPE, PVC

• Co-ordination - PP,PBR

• Ionic - Cationic, Anionic- Poly acrylonitrile

Polymers based on formation


Polymers

CH2 CH2 CH2 CH2polyethylene

CH2 CH

CH3

polypropylene CH2 CH

CH3

polystyrene CH2 CH CH2 CH

CH2 CH

Cl

polyvinyl chloride CH2 CH

Cl

Teflon CF2 CF2 CF2 CF2

(PVC)

most common polymer

bags, wire insulation,

squeeze bottles

fibers, bottles,

indoor-outdoor carpet

styrofoam,

inexpensive molded

objects: household items,

toys

synthetic leather, clear

bottles, floor coverings,

water pipe

Addition Polymers


Polymers

Addition Polymers

Block

Random

Graft


Polymers- Finger prints

Catalyst & Process controlled Reflected in

Regioselectivity Melting point

Cis/Trans Isomerism Crystallization temp.

Stereoselectivity Glass Transition

temp.

Mol. Wt distributuion Modulus

Polydispersity Crystallinity

Viscosity

Morpohology

Hardness

Stiffness

Transparency

Catalysts & process dictate the property of polymer


Polypropylene – Versatile Polymer

13

PE

PP

PS

PEEK

ABS

PC

PET

PES

Biopolymer

High Capacity

TP

Engineering

TP

Specialty

TP

Polypropylene Can Cover Area Of Other Polymers Source : Polyolefin Conf

PVC

RIL – Confidential (for internal sharing only) 14

• Global Polymer market – 175 MMT

• Global PP market ~ 42.6 MMT (29 %)

• Global PP Growth ~ 6.4 % (mainly

driven by Asia , Africa and other

developing country)

• Indian PP , PE , PVC Consumption ~ 4.6

MMT

•

• Indian PP market ~ 1.5 MMT (34 %)

• PP Growth in India ~ 15 % (2006-07)

• RIL PP Capacity ~ 2.7 MMT

Global Demand - PO+PVC (2006)

PP 42.6 29%

HDPE 29.3 21%LLDPE 18.6 13%

LDPE 18 13%

PVC 33.5 24%

PP HDPE LLDPE LDPE PVC

India Demand - PO+PVC (2006)

PP 1530 33%

HDPE 990 21%LLDPE 650 14%

LDPE 260 6%

PVC 1220 26%

PP HDPE LLDPE LDPE PVC

Polypropylene occupy largest chunk of Market demand

*Source : A. Report 06-07



• Propylene

• Isotactic- CH3 on one side of polymer chain (isolated). Commercial PP is 90% to 95% Isotactic



16

•Atactic- CH3 in a random order (A- without; Tactic- order) Rubbery

and of limited commercial value.

•Syndiotactic- CH3 in a alternating order (Syndio- ; Tactic- order)



• Differences between PP and PE are

– Density: PP = 0.90; PE = 0.941 to 0.965

– Melt Temperature: PP = 176 C; PE = 110 C

– Service Temperature: PP has higher service

temperature

– Hardness: PP is harder, more rigid, and higher

brittle point

– Stress Cracking: PP is more resistant to

environmental stress cracking



Polypropylene Value Chain

18

Monomer

Technology

Catalyst

Technology

Polymerization

Process

Polypropylene

Product

Application

Front End

Back End


Monomer Technology

Naphtha Cracking

Gas Cracking

FCC – Gas Oil Cracking

Propane Dehydrogenation


Discovered that a combination of certain transition

metal compounds and organo metallic compounds

polymerize ethylene in 1953

Discovered the synthesis of

stereo regular polymers in

1954

The Nobel Prize in Chemistry 1963

TiCl3 / AlEt2Cl (Natta) 1st Gen

2nd Gen

3rd Gen

4th Gen

5th Gen

TiCl3 / AlCl3 / isoamylether / AlEt2Cl

TiCl4 / MgCl2 / Alkyl Benzoate & Ext. Donors

TiCl4 / MgCl2 / Alkyl Phthalate & External Donors

TiCl4 / MgCl2 / 1,3-diethers as Internal Donors

Low activity, Deashing required

Low activity, Deashing required

Medium activity, Actactic removal not required

High activity, No additional process required

High activity, No External donor required

Karl Ziegler

Giulio Natta

Catalyst Technology

21

Z-N Catalyst System accounts for ~95 % of Polypropylene Production globally

Zr/HfX3

Me

Me

Catalyst Technology

RIL – Confidential (for internal sharing only) 22

Support

TiCl4 Solvents

Catalyst

Internal

Donor

Titanation

RCT

Aluminum

Alkyl (Co- Catalyst) Propylene and/or

Ethylene Activation/

Polymerzn.

PP

Product

Catalyst External

Donor

• Multiple & Complex

Chemical , Physical reactions

• Active site incorporation on

support with intenral donor

• Activation of Active Species

by Alkylation

• Monomer polymerization for

polymeric product

Magnesium Aloxide

Alcoholated MgCl2

Magnesium Carboxlate

Ethyl Benzoate

Di-isoalkyl Phthalates

Monoester Catalyst

Diester Catalyst

Ether based Catalyst

O,P,N based Donor

Silane based Donors

COOR1

OR2

X

Y

X

Y

OCH 3SiH3CO

Catalyst Technology

• Catalytic cycle for polymerization of Olefin - Cossee-Arlman mechanism

• Direct insertion of olefin across M-alkyl bond

Catalyst Technology


1. Replacement of one Cl by alkyl group of Al alkyl

2. Bonding of Propylene to a vacant site

3. Insertion of propylene into Metal-alkyl bond- Initiation

4. Creation of vacant site for propylene adsorption

5. Repetition of steps 2,3 & 4 leading to chain growth/propagation

6. Catalyst configuration decides the configuration of added

propylene

7. Termination of polymer chain with hydrogen- Termination

Catalyst Technology



• Conventional Slurry Process

• Bulk Processes – Spheripol

– Hypol

– Atofina

• Gas Phase Fluidised Bed Processes – Unipol

– Novolen

– Innovene

– Chisso

– Sumitomo

• New Generation Processes – Borstar

– MZCR (Spherizone)


• Polymerisation in CSTR / 60-80°C / 5-15 bar

• Hydrocarbon diluent (butane, hexane, heptane or iso-octane)

• Polymer formed as suspension

• Slurry flashed to recover monomer

• Residual catalyst deactivation and atactic removal

• Polymer powder separated in centrifuge, dried, compounded and pelletised

Drawbacks

• Purification and recycle of diluent expensive

• Catalyst deactivation & atactic removal steps involved

• Products range limited


Conventional Slurry Process



Conventional Slurry Process



• Similar to Slurry process

• Liquid propylene as reaction medium

• High monomer concentration, hence higher reaction rate

& yield

• Upto 50-60% suspension in liquid monomer

• Impact copolymer in Gas Phase reactor

Bulk process



• Maximum number of plants worldwide

• High Yield High Stereospecific (HYHS) MgCl2 supported

Z.N. catalyst originally developed by Montedison and Mitsui

• No catalyst removal stage

• Two stage process - single or twin bulk loop configuration

with Gas Phase reactor in series

• Polymerisation at 60-80°C & 30-40 bar

• Very wide MFI range : 0.1 to >1500

• Spherical polymer grains with no pelletisation - Adipol

Bulk process



Bulk process



Unipol – Dow (UCC)

Novolen - NTH : ABB Lummus + Equistar (BASF)

Innovene – BP (Amoco)

Chisso

Sumitomo

Gas phase process



• Combines fluid bed reactor technology of Union Carbide and

supported Z.N., Super High Activity Catalyst (SHAC) of Shell

• No deashing and atactic removal steps

• Polymerisation at 60-80°C & 35 bar

• All types - Homo, Random and Impact Copolymer produced

using identical Gas Phase reactors

• MFI of 0.6 - 30 can be produced in reactor with improvement

in catalyst by Dow

• New grades (IMPPAX) with good high impact/stiffness

balance & rubber contents up to 35%

Gas phase process _ Unipol



Gas phase process _ Unipol



• Originally developed by BASF

• Mechanically agitated reactors to maintain fluidised bed for

Homo, Random and Impact Copolymers

• Silica supported Z.N.catalyst originally used

• Polymerisation at 60-105°C & 20-35 bar

• Unique extruder design with catalyst deactivation by

addition of water to extruder

• Stiff and tough Homopolymer grades

• Process can make super high Impact Copolymers

• Wide range of reactor MFI (0.3 to >100)

• Use of Metallocene allows high MFI grades (upto 1200) for

Nonwoven application

Gas phase process _ Novolene



Gas phase process _ Novolene



Gas phase process _ BP Innovene



• Borstar - Borealis

• MZCR - Spherizone - Basell

New Polymerization process



• Borstar PE technology extended to PP

• Dual reactor system - Slurry loop followed by Gas Phase

reactor

• Liquid Propylene diluent

• MgCl2 supported Z.N.catalyst

• Process operating at 70-80°C

• High ethylene (10%) random copolymers

• High stiffness & improved randomness in copolymer grades

• High MFI reactor grades

• Very narrow to very broad MWD capability

• Better creep resistance, higher melt strength and improved

processability

New Polymerization process _ Borstar PE



New Polymerization process _ Borstar PE



Latest process invented by Basell

Process technology derived from catalytic

cracking

Two separate zones within one reactor, separated

by a layer of barrier fluid

High productivity per unit volume of the reactor

Very broad or very narrow MWD possible

Flexural modulus upto 2,500 MPa,

Extremely high melt strength

Low seal initiation temperatures

New Polymerization process _ Spherizone Basell



New Polymerization process _ Spherizone Basell



Polymerization process _Distribution (2004)


Polypropylene

Packaging

Infrastructure

Agriculture

Consumer Goods

Health Care

Conservation of

Resources


44

Mechanical Properties of PP

Mechanical Properties of PolypropylenePolypropylene LDPE

(For Comparison)

HDPE

(For Comparison)

Density 0.90 0.91- 0.925 0.959-0.965

Crystallinity 30% to 50% 30% to 50% 80% to 91%

Molecular Weight 200K to 600K 10K to 30K 250K to 1.5M

Molecular Weight

Dispersity MWD

(Mw/Mn)

Range of

MWD for

processing

Range of MWD

for processing

Range of MWD

for processing

Tensile Strength,

psi

4,500 – 5,500 600 - 2,300 5,000 – 6,000

Tensile Modulus,

psi

165K – 225K 25K – 41K 150K – 158 K

Tensile

Elongation, %

100% - 600% 100% - 650% 10% - 1300%

Impact Strengthft-lb/in

0.4 – 1.2 No break 0.4 – 4.0

Hardness, Shore R80 - 102 D44 – D50 D66 – D73


45

Physical Properties of PP

Physical Properties of Polypropylene

Polypropylene LDPE HDPE

Optical Transparent to

opaque

Transparent to

opaque

Transparent to opaque

Tmelt 175 C 98 – 115 C 130 –137 C

Tg -20 C -100 C -100 C

H20

Absorption

0.01 – 0.03 Low < 0.01 Low < 0.01

Oxidation

Resistance

Low, oxides

readily

Low, oxides

readily

Low, oxides readily

UV Resistance Low, Crazes

readily

Low, Crazes

readily

Low, Crazes readily

Solvent

Resistance

Resistant

below 80C

Resistant below

60C

Resistant below 60C

Alkaline

Resistance

Resistant Resistant Resistant

Acid

Resistance

Oxidizing

Acids

Oxidizing Acids Oxidizing Acids


46

Processing Properties of Polyethylene

Processing Properties

Polypropylene LDPE HDPE

Tmelt 175 C 98 – 115 C 130 –137 C

Recommended Temp

Range

(I:Injection, E:Extrusion)

I: 400F – 550F

E: 400F – 500F

I: 300F – 450F

E: 250F – 450F

I: 350F – 500F

E: 350F – 525F

Molding Pressure 10 -20 psi 5 – 15 psi 12– 15 psi

Mold (linear) shrinkage

(in/in)

0.010 – 0.025 0.015 – 0.050 0.015 – 0.040


Polymer Processing

EXTRUSION

SINGLE SCREW

EXTRUDER

TWIN SCREW

EXTRUDER

• FILM

• TAPES

• PIPES

• FILAMENTS

• INJECTION MOULDING

• BLOW MOULDING

COMPOUNDING WITH

FILLERS / PIGMENTS.

REGID PVC PIPES


Polymer Processing

BIAXIALLY ORIENTED PP(BOPP) FILM:

Process : Double bubble (Blown film), Tenter

frame (Cast film).

Two directional stretching.

Applications : Print Paper lamination, Adhesive

tapes, synthetic paper, Confectionery and

Cigarette wrappings.

Tubular Quenched PP(TQPP) film:

Process : Inverse bubble, water quenching

Applications : Textile pkg., Confectionery items

pkg., Auto spare parts pkg. etc.


Polymer Processing

RAFFIA & MONOFILAMENTS: (Extrusion)

Machine : (Screw Dia, Oven/Hotplate)

DIE Width, Spinneret

Process : Stretch Ratio, Line Speed.

Materials : HDPE & PP

Products:

Raffia : Bags for cement/fertilizer/food

grains, sugar/polymer Pkg. & Tarpaulin

appln.

MF : Mosquito & Fishing nets, Ropes,

Geo- textiles


Polymer Processing

RAFFIA & MONOFILAMENTS


INJECTION MOULDING :

Machine (tonnage / shot wt.)

Mould (cavity , punch)

IM process / cycle

Products:

HDPE : Crates, Luggages, caps & closures, Buckets, Household articles, Ice trays etc.

PP/PPCP :Furniture, Crates, Luggage, Automotive components, Tooth brush, Industrial products, Textile components, Household articles etc.

PPRCP : Transparent containers, Medical products.

LD/LLD : Caps & closures.

PVC : Pipe fittings, footwears.

Polymer Processing


Polymer Processing

– BLOW MOULDING : (Extrusion-Small vol.) • Machine (Volume, Station)

• Die/Punch & Mould

• BM Process / Cycle

– Products :

HDPE : Containers for Lube oil, Vegetable oil, Cosmetics, Pesticides, Pharmaceuticals, Healthcare.

PP : Pharmaceutical & cosmetic bottles.

LD/LLD : Toys, IV bottles, Flexible containers.

PVC : Storage containers.


RTG Hazira

IN

Technology

& Products

Organometallic/

Inorganic

Chemistry

Organic

Chemistry

Polymer

Science

Polymerization

Science

Catalyst &

Chemical

Process

Catalysis

&

Material

Science Analytical

Science

Patents ,Trademark

Publications &

Classified documents

RTG-Hz: FBIV Process

Out

FOCUS

BRILLIENCE

INNOVATION

VALUE

http://images.google.co.in/imgres?imgurl=http://www.msm.cam.ac.uk/polymer/members/pmh29/4.gif&imgrefurl=http://www.msm.cam.ac.uk/polymer/members/pmh29/simulation.html&h=154&w=189&sz=6&tbnid=oyWlM2k3casJ:&tbnh=79&tbnw=97&start=2&prev=/images%3Fq%3Dpolymer%2Bmolecule%26svnum%3D30%26hl%3Den%26lr%3Dlang_en%7Clang_ru%26newwindow%3D1

http://images.google.co.in/imgres?imgurl=http://www.almatin.com/images/products_all4.jpg&imgrefurl=http://www.almatin.com/polypropylene_txt.html&h=300&w=450&sz=23&tbnid=My4ylU9LVi8J:&tbnh=82&tbnw=123&start=4&prev=/images%3Fq%3Draffia%2Bbags%26svnum%3D30%26hl%3Den%26lr%3Dlang_en%7Clang_ru%26newwindow%3D1

R&D Facilities

RTG-Hz: Facilities


(100)

C

O OC2H5

C

O OC2H5

MgCl2 Matrix

~85 mol%

Titanium chloride fragments

~10 mol%

(100)(100)

C

O OC2H5

C

O OC2H5

(100)

C

O OC2H5

C

O OC2H5

MgCl2 Matrix

~85 mol%

Titanium chloride fragments

~10 mol%

(100)

Morphology controlled

Precursor

Precursor

Pro-catalyst

Polyolefin Catalyst Technologies

Procatalyst Cocatalyst External Donor

Morphology controlled

Procatalyst

Mg(s) + Alcohol

Controlled

morphology

Mg(alkoxide)

TiCl4(excess) + Lewis Base

Controlled morphologyActive MgCl2

Supported catalystMg(s) + Alcohol

Controlled

morphology

Mg(alkoxide)

TiCl4(excess) + Lewis Base

Controlled morphologyActive MgCl2

Supported catalyst

Mg(s) + Alcohol

Controlled

morphology

Mg(alkoxide)Mg(s) + Alcohol

Controlled

morphology

Mg(alkoxide)

IP- WO

2009/1300707A2,

IN/916/MUM/2008,

IN/1691/MUM/2009

Advance Donor

Technology

External Donor

HomoRandomICP

COOR1

OR2

X

Y

X

Y

Catalyst Technology Advancement

OCH 3SiH3CO

TiCl3 Technology

Supported Titanium

Technology

Advance Donor Technology

V

a

l

u

e

E

n

h

a

n

c

e

m

e

n

t

Single SiteTechnology

Specialty PP

HomoRandomICP

COOR1

OR2

X

Y

X

Y


OCH 3SiH3CO

TiCl3 Technology

Supported Titanium

Technology


V

a

l

u

e

E

n

h

a

n

c

e

m

e

n

t


Specialty PP

HomoRandomICP

COOR1

OR2

X

Y

X

Y


OCH 3SiH3CO

TiCl3 Technology

Supported Titanium

Technology


V

a

l

u

e

E

n

h

a

n

c

e

m

e

n

t


Specialty PP

HomoRandomICP

COOR1

OR2

X

Y

X

Y


OCH 3SiH3CO

TiCl3 Technology

Supported Titanium

Technology


V

a

l

u

e

E

n

h

a

n

c

e

m

e

n

t


Specialty PP

Combination of

ester and

ethers donors

IP - IN/539/MUM/2008

IN/540/MUM/2008

IN/541/MUM/2008

IN/1074/MUM/2008

WO 2009/ 116056 A2, WO

2009/16057A2 ,WO 2009/

141831

In-house Technology Development


IP

• Indonesia Patent No:

WOO.2002.01688 / 26 Jul 2002

• - Korea Patent No- KR533442 / 26 Jul

2002

• - Philippines Patent No- 1-2002-

000064 / 30 Jan 2002

• - Australia Patent No- AU3221501A /

25 Nov 2000

• - Australia Patent No.

AU2003241147A1

• - EP - 008873482.5

• - European Patent No.

2.283048(A2)/16 Feb 2011

1. 1691/MUM/2009 / 22 July 2009

2. 1981/MUM/2010) / 12 Jul 2010

3. 2844/MUM/2010) / 12 Oct 2010

4. 762/MUM/2011 / 17 Mar 2011

5. 1123/MUMNP/2005

6. 1744/MUMNP/2006 / 24 Jun

2006-

7. 1894/MUM/2009 / 18 Aug 2010

8. 539/MUM/2008 / 18 Mar 2008

9. 541/MUM/2008 / 17 Mar 2008

10. 1074/MUM/2008 / 21 May 2008

11. 540/MUM/2008 / 14 Mar 2008

12. 468/MUM/2011 / 13 May 2011

13. 1706/MUM/2011 - 10 June 2011

14. 1424/MUM/2011 / 09 May 2011

15. 916/MUM/2008 / 25 Apr 2008

16. 1691/MUM/2009 / 22 July 2009

• PCT No WO/2009/116056A2 / 24

Sept 2009

• PCT No WO/2009/1418314 . 25

Aug 2008

• PCT No WO/2009/116057 A2 / 24

Sept 2009

• PCT No. WO 2009/128087/A2 / 22

Oct 2009

• PCT No WO/2009/130707 A2 / 29

Oct 2009

• PCT Application -

PCT/IN2010/000809

• PCT Application -

PCT/IN2010/000809

• PCT : WO 2002/44220 A1 / 06

Jun 2002

• PCT No. WO 2004/089998 A1 /

21 Oct 2004

• PCT No. -WO 2005/077990 A1 /

25 Aug 2005

• PCT/IN2011/000028 / 14 Jan 2011

• PCT/IN2011/000029 / / 14 Jan

2011

• US Patent No 2011/0003952 A1 06 Jan 2011

• US Patent No 2011/0046326 / 24 Feb 2011

• US Patent No 2011/0015355 A1 / 20 Jan

2011

• US Patent No. US6841633 B2 / 11 Jan 2005

• US Patent No. US7265074 B2 / 04 Sept

2007

• US Patent No. - US20070260099 A1 / 08

Nov 2007

• US patent 2011/0054129 A1 / 03 Mar 2011

>51 Patents/Applications

PCT India

Europe/Austalia/Korea/ Indonesia

USA


Awards & Recognitions

In-house Technology Development

ICC - 2010

Indian Science Congress - 2005 Golden Peacock - 2008 ICC Acharya PC Ray - 2008

Indira Innovation - 2009 FICCI - 2009 R&D Lab of Year, USA - 2009

Arch of Excellence - 2009 FGI - 2009

National Technology Award 2011 Vasvik Research Award - 2011

Rashtriya Rattan - 2009

Special Mention Lab of Year Award

Reliance Technology Group Hazira : Polymer R&D


Thank You!

“From IP user to IP

Creator & From

licensing technology

to

developing

technology”

RELCATT

M

RELDTM

Innovation is way of Life Growth is Life

RELSTM

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GET Induction Presentation_21 08 12_1