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Ldpe and LLdpe

Ldpe and LLdpe


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SPE Polyolefins Conference 2005 Low Density and Linear Low Density Polyethylene Presentation

Presented by J. Bayley
NOVA Chemicals Corporation
Note: The content of this presentation is intended for basic learning, the content may not describe or encompass all aspects of materials and processes

© 2005 NOVA Chemicals Corporation

Overview of Presentation Topics
• Feedstock for the Manufacture of Polyethylene • Polyethylene Basics Unit 1 - LDPE • Manufacturing Processes • Properties • Applications • Future for LDPE Unit 2 - LLDPE • Molecular Information • Comonomer Information • Properties • Catalyst vs Properties • Manufacturing Processes • Applications • Future of LLDPE

© 2005 NOVA Chemicals Corporation

Natural Gas to Ethane to Ethylene….

© 2005 NOVA Chemicals Corporation

Ethane Supply System
Gas Field Gas Plant

Reprocessing Plant


Petrochemical Industry

Residue Natural Gas

Energy Markets

© 2005 NOVA Chemicals Corporation

Natural Gas Components
C1 C2 C3 C4 C5+ H20 H2S CO2 Methane Ethane Propane Butane Pentane plus Water Sulphur Carbon dioxide Pipeline System Post Gas Plant 90 – 100% 3 – 10% < 1% 0 0 2% Export Post Straddle Plant > 98% < 2% 0

< 2%

© 2005 NOVA Chemicals Corporation

Gas Plant - Separate Components
Methane / Ethane / Carbon Dioxide Nitrogen / Propane / Butane Ethane / Propane Butane / Pentanes


Methane Butane Pentanes
Natural Gas Field

Ethane Propane Water Nitrogen

Carbon Dioxide
Contains many components in varying proportions
© 2005 NOVA Chemicals Corporation

Pentanes Natural Gas Pipeline Liquids Pipeline Reinjected underground

De-p ropa nize r

De h yd ra tor der

Turb o-ex pan

De-e than izer


Ethane & C02 Propane Butane

Natural Gas

Pentane Plus

Natural Gas to Fuel Markets
© 2005 NOVA Chemicals Corporation


De-b utan izer

Pipeline Straddle Plant Extraction and Fractionation

etha nize r


Ethylene Manufacturing from Ethane
800° C then fractionate -160° C


H H2 Co-products H



Ethane (C2 H6)
• • • •

Ethylene (C2 H4) hydrogen

In simple terms Ethane is converted into Ethylene (thermal decomposition) at high temperature in a steam furnace or cracker Refrigeration is used to separate the various components, co-products, etc. The furnace and auxiliary components are designed to efficiently produce as much Ethylene as possible and as few co-products as possible Co-Products such as Hydrogen, CO2 etc. can be sold for other uses

© 2005 NOVA Chemicals Corporation

Brief History of Polyethylene
• PE synthesis discovered accidentally in 1932 by Imperial Chemical Company (ICI) Scientists • First High Pressure LDPE plant built in 1939 • In 1953, large advancements were made by Scientist Carl Ziegler, inventor of a new catalyst system. A scientist named Giulio Natta also shares credit for this catalyst development • Known today as the Ziegler-Natta Catalyst (Z/N), this catalyst facilitated polymer synthesis at lower temperatures and pressures High Density Polyethylene (HDPE) materials were introduced soon after • In the late 1970’s LLDPE materials were introduced to the market • Significant Catalyst advances since that time with the advent of single-site catalysts

© 2005 NOVA Chemicals Corporation

Polyethylene is ...
• A polymer of ETHYLENE or a copolymer of ethylene and a comonomer • ETHYLENE - a gas composed of two carbons and four hydrogen molecules. Formula: C2H4 The monomer unit for polyethylene forms the backbone of the compound: H2C=CH2

© 2005 NOVA Chemicals Corporation

© 2005 NOVA Chemicals Corporation

Some Basic Definitions
• Monomer - A chemical compound that can undergo
polymerization. The basic building block of a polymer

• Comonomer - One of the constituents of a copolymer • Copolymer - A product of copolymerization • Copolymerization - Polymerization of two different

• Homopolymer - Manufactured with no comonomer, with
ethylene only

© 2005 NOVA Chemicals Corporation

Practical Illustration of Polyethylene Designations
(0.917 to 0.935 g/cc)

(0.955 to 0.970 g/cc)

(0.905 to 0.955 g/cc)

© 2005 NOVA Chemicals Corporation

Polyethylene Designations
Polyethylene is classified by density ranges, as defined by ASTM: • LDPE Type I 0.910 - 0.925 g/cc • MDPE Type II 0.926 - 0.940 g/cc • HDPE Type III 0.941 - 0.960 g/cc (Copolymer) • HDPE Type IV >0.961 g/cc (Homopolymer)

© 2005 NOVA Chemicals Corporation

Unit 1 PE Introduction and LDPE Overview

© 2005 NOVA Chemicals Corporation

• Molecular Structure LDPE - Long Chain Branching (LCB) results in unique polymer properties

© 2005 NOVA Chemicals Corporation

LDPE Manufacturing Processes
Two main LDPE manufacturing processes in use: • • High Pressure Tubular Reactors High Pressure Autoclave Reactors

© 2005 NOVA Chemicals Corporation

LDPE Tubular Reactors (Simplified)
• A tubular LDPE Reactor is a long heat exchanger • Free Radical polymerization uses Peroxide initiators or Oxygen to promote polymerization reactions • Ethylene is circulated through a compressor - the main pressurization of the feed stream is accomplished by a hyper compressor • Initiators are introduced at various points along the length of the tube - Zone temperatures are accurately controlled • No backmixing takes place in the tubular system, residence time is limited/short • The exothermic heat of reaction is removed via water jackets on the outside walls of the tube • Upon exiting the reactor the material passes through medium pressure and low pressure separators (separates Ethylene from PE), PE moves to the extruder
© 2005 NOVA Chemicals Corporation

Resin Manufacturing
High Pressure Tubular
Primary Compressor Secondary Compressor






Wax Drum

Knockout Pots


To Disposal

To Finishing

Gear Pump and Pelletizer

© 2005 NOVA Chemicals Corporation

LDPE Autoclave Reactors (Simplified)
• Free radical type of polymerization uses Peroxide initiators typically • System utilizes a stirred cylindrical vessel • Ethylene feed gas and Peroxide are introduced to a compressor and then pumped with Peroxide initiator into the stirred autoclave vessel • Proprietary designs baffle or partition the reactor into discreet zones enabling control of molecular species and amount of LCB of polymer in these zones • Backmixing does take place in the autoclave system • Walls of the autoclave unit are thick to accommodate high pressure Heat of reaction is removed by the introduction of fresh feed • Upon exiting the reactor the material passes through medium pressure and low pressure separators (separates Ethylene from LDPE polymer) • Polymer enters the pelletization process to be pelletized
© 2005 NOVA Chemicals Corporation

Resin Manufacturing
High Pressure Autoclave
Telogen VA Monomer MA Monomer Voluntary Purge

Primary Compressor

Secondary Compressor




Methane to Flare RAW PRODUCT SILO

< C3

Hourly Hold-Up Hoppers

C 2 S P L I T T E R D E M E T H A N I Z E R D E P R O P A N I Z E R

To Finishing

Gear Pump and Pelletizer Ethane to Flare


Solvent/Monomer Removal

© 2005 NOVA Chemicals Corporation

Comparison of High Pressure Autoclave and Tubular LDPE Manufacturing Processes Information Length Internal Diameter Rx Temperature Range (°F) Pressure within Rx (PSI) Initiator Types Typical Polymer Conversion Ranges per pass Back Mixing Capability General Observation Autoclave 20 ft 3 ft 350-500 15000-30000 Organic Peroxide Approx. 22% (varies with product mix) Yes More precise tailoring of MW, MWD and Long chain branching (LCB) Comb-like LCB structure Tubular Up to 1 mile 1-3 inches ID 350-600 20000-50000 Organic Peroxide or Oxygen Approx. 35% (varies with product mix) No Less capable of molecular tailoring and less uniform long chain branching (LCB) Root-like LCB structure

General Observation

(Note: This table provides general information. Technology may exist that is not encompassed by or include in this table. The information is intended for basic learning purposes only.)
© 2005 NOVA Chemicals Corporation

Properties of LDPE Materials Softness Permeability Clarity Processing Equipment Needs Melt Strength Other Pros Suitability as a Blend Resin

LDPE Materials Softer and more pliable than other PE types Higher, due to long chain branching and lower % crystallinity Available in high clarity for film applications - Improves clarity of LLDPE when blended with LDPE in low amounts Shear thins in extrusion - processes easily at lower amps and pressures relative to LLDPE or HDPE Screw/Die designed for LDPE required if extruding 100% LDPE Much higher than LLDPE due to presence of long chain side branched molecules - (Important for film blowing, foam etc.) Less prone to melt fracture than LLDPE or HDPE Good, commonly used, can be detrimental to physical propertiesLDPE is generally blended to improve ease of extrusion, increase melt strength or improve clarity of the end product Possesses desirable biaxial shrink properties for shrink film Absolute physical properties lowest in class - extensional limitations or drawdown limitations exist - LLDPE and HDPE can be drawn much thinner in blown or cast film processes

Shrink Properties Limitations

© 2005 NOVA Chemicals Corporation

LDPE Applications
• LDPE is still an important PE type • The unique attributes of LDPE due to LCB provide desirable properties for some specific product applications • LDPE is used at 100% in some applications such as conventional Shrink Film, Extrusion Coating, Wire and Cable Jacketing, LDPE Foam etc. • LDPE is used as a property modifier in film and sheeting applications and is often blended with LLDPE (to improve clarity, processability, output rates, etc.)

© 2005 NOVA Chemicals Corporation

2002 APC-LDPE Volume by End Use Process (based on Amercian Plastics Council 2002 Data)
Blow Molding Sheet (greater than 12 1% m il) Injection Molding 1% 6% Other Extruded Products 9%

Extrusion Coating 16%

Film (less than 12 m il) 44%

Other (Resellers, Com pounders) 23%

© 2005 NOVA Chemicals Corporation

LDPE Common Applications
• Film Applications - Garment Films, Industrial Liner, Lamination films, Coextruded Food Packaging, Bakery Films, Film Blends (with LLDPE) for food packaging, Shrink Overwrap, Kitchen Cling Film, etc. • Extrusion Coating Applications - Paper Board Coating, Package Coating, Coating of other substrates (Examples foil coating, drink box coating, etc.) • Injection Molding - Lids, Caps and Closures • Other Examples - Wire and Cable applications, PE Foam, Pipe and Conduit, Non-abrasive films, Blow Molded squeeze bottles, etc.

© 2005 NOVA Chemicals Corporation

The Future of LDPE
• Conventional LDPE has existed for many years and was predicted to be replaced by LLDPE • LDPE future capacity growth is likely to be less than for LLDPE, though demand continues to be strong for LDPE • LDPE is valued as performance modifier for extrusion processing or to obtain desired physical properties such as clarity • Manufacturers can be expected to push the boundaries of their processes and exploit existing technology, but significant advances in resin morphology are not widely expected to occur in this class of materials

© 2005 NOVA Chemicals Corporation

Unit 2

Introduction to LLDPE

© 2005 NOVA Chemicals Corporation

LLDPE - General Information
• Linear Low Density Polyethylene (LLDPE) is made by the copolymerization of ethylene and a comonomer
- (Example: Ethylene and Octene copolymerized - can be described as an Ethylene-Octene Copolymer)

• LLDPE is composed of long linear molecules, the main polymer chain is composed of long strings of repeating Ethylene units - Short side chains (from comonomer) link onto the main polymer chains • LLDPE typically has no long chain branching (LCB) • LLDPE materials are typically copolymers but terpolymers and quatropolymers have also been made • LLDPE typically has a narrow distribution of main chain molecule lengths (LDPE and HDPE tend to be broader)
© 2005 NOVA Chemicals Corporation

LLDPE - Molecular Diagram
• LLDPE consists of long linear molecules with short side chain branches (SCB) • SCB length is a function of comonomer type employed

© 2005 NOVA Chemicals Corporation

Polyethylene Comonomers Commonly Used
• Butene - A four carbon long molecule Formula: C4H8 H2C=CH-CH2-CH3 • Hexene - A six carbon long molecule Formula: C6H12 H2C=CH-CH2-CH2-CH2-CH3 • Octene - An eight carbon long molecule Formula: C8H16 H2C=CH-CH2-CH2-CH2-CH2-CH2-CH3
© 2005 NOVA Chemicals Corporation

Comonomer Type - Product Properties
• • • • Short side chain branching type influences product toughness (Example: Butene, Hexene, Octene) Short side chains, like those made with butene comonomer are less effective at disrupting chain folding Longer side chains, like those formed with hexene and octene are longer and result in superior physical properties Z/N catalysts tend to have more difficulty than single-site catalysts in placing comonomer on the longer chain (higher molecular weight) portion of the polymer thus more comonomer ends up on the shorter chains Comonomer addition levels are used to control resin density - (Example: Increased comomomer content increases short chain branch content
and results in reduced resin density)

© 2005 NOVA Chemicals Corporation

Effect of Comonomer Type on Physical Properties
Melt Index Density Comonomer Type Dart Impact (grams/mil) Low Friction Puncture (J/mm) Elmendorf Tear Strength MD (grams/mil Elmendorf Tear Strength TD (grams/mil) Tensile Strength MD (psi) Tensile Strength TD (psi) 1.0 0.919 butene 100 34 100 300 4800 3700 1.0 0.918 hexene 200 50 300 650 5300 4500 1.0 0.920 octene 335 56 400 710 6800 6400

© 2005 NOVA Chemicals Corporation

Properties of LLDPE Materials Softness Permeability Clarity Processing Equipment Needs Melt Strength Suitability as a Blend Resin Shrink Properties

LLDPE Materials
Softer relative to HDPE but not as soft and pliable as LDPE Higher % crystallinity relative to LDPE-Barrier Properties dependant on part thickness and resin density to a large degree Clarity not as good as for LDPE in most cases- LDPE can be blended to improve clarity Stiff in shear during extrusion- Narrow molecular weight distribution, processes at higher amps and head pressures relative to LDPE Screw/Die designed for LLDPE required if extruding-Extruders, Screws, Dies and Air Rings need to be designed for LLDPE Much lower than LDPE due to NO long chain side branched molecules, only short chain branching generally Can be blended into LDPE where desired- Eg: Can be blended into shrink film to modify shrinkage properties Long linear molecules tend to orient highly in the machine directionshrinkage as a result is more imbalanced relative to LDPE High physical properties possible depending on comonomer used, catalyst used and molecular architecture- Very good elongational ability, can be drawn down thinner as a film than LDPE, higher strength than LDPE permits downgaging Prone to surface melt fracture in blown film and sheet extrusion-Process Conditions and Process aid additives are used to off-set this problem

Strengths of LLDPE

Limitations of LLDPE
© 2005 NOVA Chemicals Corporation

Catalyst Information
• Metal based catalysts facilitate the reactions required to polymerize and convert Ethylene to PE • Z/N catalyst is in common use today though modifications and improvements have been made • Next generation catalysts known as single-site catalysts and Metallocene catalysts also exist and are used in the production of mLLDPE, sLLDPE and HDPE
*Note: Metallocene catalysts fall into the single-site catalyst family

© 2005 NOVA Chemicals Corporation

Catalyst Influence on LLDPE Properties
• A conventional Z/N catalyst has a variety of active reaction sites producing varied polymer molecules • The result is a heterogeneous distribution of molecules having: – broader distribution of molecular weight (molecular lengths) – varied comonomer incorporation levels across the molecular weight distribution (MWD)

© 2005 NOVA Chemicals Corporation

Catalyst Influence on LLDPE Properties
• New advanced Z/N catalysts improve comonomer placement comonomer is more uniformly distributed, less bias for the low molecular weight (MW) range • Improved comonomer placement results in improved physical properties • MWD of LLDPE is often narrow to maximize finished physical properties • Narrowing the MWD can make the polymer challenging to process (less shear thinning) therefore MWD is an important consideration in resin design

© 2005 NOVA Chemicals Corporation

Properties for Products Manufactured using Advanced Ziegler-Natta Catalyst
Dart Impact *

Hexene Gas Phase Z/N

Hexene Gas Octene Octene Phase Solution Z/N Solution Advanced Z/N Advanced Z/N

*These are typical values – advances in technology have significant improvements to product properties.
© 2005 NOVA Chemicals Corporation

Properties for Products Manufactured using Advanced Ziegler-Natta Catalyst
MD Elmendorf Tear Stength *

Hexene Gas Hexene Gas Octene Octene Phase Z/N Phase Solution Z/N Solution Advanced Z/N Advanced Z/N
*These are typical values – advances in technology have significant improvements to product properties.
© 2005 NOVA Chemicals Corporation

Properties for Products Manufactured using Advanced Ziegler-Natta Catalyst
Melt Index Density Comonomer Type Process Catalyst Type Dart Impact (grams/mil) Elmendorf Tear Strength MD (grams/mil) Elmendorf Tear Strength TD (grams/mil) Tensile Strength MD (psi) 1.0 1.0 0.918 0.920 Hexene Octene Gas Phase Solution Z/N Z/N 200 335 300 400 650 710 5300 6800 0.8 0.6 0.916 0.916 Super hexene Octene Gas Phase Solution Advanced Z/N Advanced Z/N 500 620 400 450 600 750 6100 7400

© 2005 NOVA Chemicals Corporation

Single-Site Catalyst (SSC) Information
• Every catalyst reaction site is the same, thus the molecules produced are more uniform • Every polymer molecule contains the same amount of comonomer (can result in improved properties) • Reduction in low molecular weight polymer component historically resulted in extrusion challenges largely addressed now by resin design and extrusion equipment improvements • Metallocene catalysts are a subset of the broader single-site family • Single-site catalyzed materials tend to have reduced low molecular weight grease levels

© 2005 NOVA Chemicals Corporation

Molecular Weight Distribution by GPC Z/N versus SSC

SSC polymer MI=1.9 PD=2.3

Z/N polymer MI=5.0 PD=5.8








0 2 2.5 3 3.5 4 4.5 5 5.5 6 6.5 7

© 2005 NOVA Chemicals Corporation

Physical and Optical Properties for Materials Made Using Single-Site Catalyst
Comonomer Type Melt Index (grams/10 minutes) Density Melt Flow Ratio (I21/I2) Amps Volts Pressure (psi) Specific Power (lbs/hr./amp) Dart Impact (grams) Frictionless Puncture (J/mm) Elmendorf Tear MD (grams) Elmendorf Tear TD (grams) Haze (%) 45 Gloss (%) Hexane Extractables (%) Seal Initiation Temperature (C) Supplier A octene 0.97 0.9171 22.3 34 156 2925 1.19 990 118 255 325 2 88 0.3 103 Supplier A octene 0.94 0.9172 27.5 32 144 2640 1.26 1050 93 265 370 2 87 0.4 103 Supplier B hexene 1.14 0.9168 16 39 142 3070 1.04 1200 114 190 330 3 87 0.4 99 Supplier C hexene 1.08 0.9193 16.2 36.5 137 3120 1.09 920 91 235 320 7 57 0.5 103 Z/N octene 0.95 0.9203 27.2 31.1 143 2810 1.29 180 45 430 730 15 40 1.1 111

© 2005 NOVA Chemicals Corporation

Resin Manufacturing Processes
• LLDPE Processes: – Gas Phase – Solvent Based / Solution – Slurry Loop • Most LLDPE is produced in single reactor systems, but some processes used to manufacture LLDPE do use multiple reactors

© 2005 NOVA Chemicals Corporation

Gas Phase Process (Simplified)
• Feed gases such as Ethylene, Butene or Hexene, Hydrogen etc. are introduced to the fluidized bed in the base of the gas phase reactor • Catalyst is introduced to the reactor • The exothermic heat of reaction is controlled by the fresh feed gas circulation • High Rx throughput rates and low conversion rates per pass are typically achieved - feed gases recycle through the reactor entering at the base and exiting at the top • Granular PE product is produced in the reactor and intermittently discharged out of the reactor into a purge bin, hydrocarbons are removed, granular materials conveyed to pelletization followed by pellet conveying to finishing area

© 2005 NOVA Chemicals Corporation

Example of Gas Phase Process (Simplified)
Compressor Comonomer Recovery Unit Flare Cooling Water Exchanger


Catalyst Preparation

Product Discharge System



Butene Railcar

Degassing and Drying

Degassing and Drying

Hexene Railcar

Nitrogen Hydrogen Isopentane Co-Catalyst

© 2005 NOVA Chemicals Corporation

Solution Polymerization Process (Simplified)
• All aspects of reaction take place in solution • All raw ingredients including, Ethylene feed, Hydrogen, etc. are dissolved into a solvent resulting in a solution composed of the raw ingredients required • Catalyst is introduced to the reactor/s • Solution is introduced into one or more stirred autoclave reactors temperature, residence time and mixing are controlled • Polymer solution exits the reactor/s, solvent is flashed off in a separator and returns to distillation • Polymer passes through a low pressure separator into an extruder • A devolatization extuder is used in some cases to remove residual hydrocarbons while stripping vessels (post-extrusion) may also be used in some processes to accomplish this task
© 2005 NOVA Chemicals Corporation

Low Pressure Solution Process (Simplified)
Recycle Stream Ethylene Hydrogen Comonomer Catalyst Catalyst


5 3

2 4
4. Pelletizer 5. Compressor

Pelletized Product

1. Stirred Autoclave Reactors 2. Separator 3. Separator
© 2005 NOVA Chemicals Corporation

Slurry Process Description (Simplified)
• Description is simplified but based on the Phillips Slurry loop design that can produce LLDPE, MDPE, HDPE, mLLDPE • The reactor is a circulation loop, water jacketed to remove heat • A hydocarbon carrier circulates the reactive ingredients around the loop reactor • The reaction of Ethylene, Comonomer, Hydrogen, etc. results in polymer particles forming, suspended on the carrier • Polymer settles out and is removed from the reactor into a flash vessel that separates granular polymer from residual hydrocarbon • Polymer granules exit the flash vessel into a purge vessel where hydrocarbons are removed • Additives are incorporated, granular material is extruded and pelletized
© 2005 NOVA Chemicals Corporation

Low Pressure Slurry Process (Simplified)
Circulating Pump

Operating Conditions 200 - 250 o F 500 - 600 psi
Ethylene Hydrogen Comonomer


Flash Tank

Vapors DRYER

Granular Polyethylene RECYCLE STREAM

© 2005 NOVA Chemicals Corporation

2002 APC-LLDPE Volume by End Use Process (based on Amercian Plastics Council 2002 Data)
Sheet (greater than 12 mil) Other Extruded Products 1% Pipe and Conduit 3% 1% Injection Molding 7% Film (less than 12 mil) 65%

All Other Uses 23%

© 2005 NOVA Chemicals Corporation

LLDPE by Market in N.A.
• 65% Film (12 mils or less) • 7% Injection Molding • The remainder is spread out over a variety of production processes such as: – Pipe and Conduit – Sheeting – Blow Molding – Compounding

Source: APC Resin Statistics
© 2005 NOVA Chemicals Corporation

Typical Applications
• LLDPE – Grocery sacks – Garbage bags – Stretch wrap film – Agricultural film and tubing – Milk pouches – Wire and cable coatings – Housewares – Large outdoor toys – Chemical storage tanks – Landfill covers
© 2005 NOVA Chemicals Corporation

Future Development/Outlook
• The PE Industry is continuously improving product performance by: – New Catalyst developments – New reactor configurations and manufacturing process improvements – Technology Licensing - existing technologies licensed to operate on new technology platforms => could result in novel Polyethylene materials

– Polyethylene is evolving Stay Tuned!
© 2005 NOVA Chemicals Corporation

References and Acknowledgements • • • • • • • • NOVA Chemicals Internal Literature Kirk Othmer Encyclopedia of Chemical Technology American Plastics Council Chem Systems (2003) Commodity Thermoplastics (JP Arlie) Judy Webb-Barrett (NOVA Chemicals) Lan Nguyen (NOVA Chemicals) Chris Foy (NOVA Chemicals)

© 2005 NOVA Chemicals Corporation


© 2005 NOVA Chemicals Corporation

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