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1 1 Introduction to Polyolefins Introduction to Polyolefins Polyethylene and Polypropylene Polyethylene and Polypropylene 20 20 10 10 El El ő ő ad ad ó ó : Csernyik Istv : Csernyik Istv á á n n

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Page 1: Introduction to Polyolefins - mol.hu³l_roviden/egyetemi... · 2 Content Synthetic polymers Classification Global production Polyolefins Polyolefins family PE classification PP structures

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Introduction to PolyolefinsIntroduction to Polyolefins

Polyethylene and PolypropylenePolyethylene and Polypropylene20201010

ElElőőadadóó: Csernyik Istv: Csernyik Istváánn

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ContentContent

Synthetic polymersSynthetic polymersClassificationClassificationGlobal productionGlobal production

PolyolefinsPolyolefinsPolyolefinsPolyolefins familyfamilyPE classificationPE classificationPP structuresPP structuresKey propertiesKey propertiesAdditivationAdditivationApplicationApplicationGlobal consumptionGlobal consumptionDomestic production and consumptionDomestic production and consumptionInvestment and operating costs of Investment and operating costs of polyolefinspolyolefins plantsplants

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Synthetic Polymers Classification Synthetic Polymers Classification by Plastics Europeby Plastics Europe

Standard PlasticsStandard Plastics PEPE, , PPPP, PVC, PS, EPS, PET (Bottle grade), PVC, PS, EPS, PET (Bottle grade)

Engineering PlasticsEngineering Plastics ABS, SAN, PA, PC, PBT, POM, PMMA, Other High ABS, SAN, PA, PC, PBT, POM, PMMA, Other High Performance PolymersPerformance Polymers

PURPUR PolyurethanesPolyurethanes

ThermoplasticsThermoplastics Standard PlasticsStandard Plastics + Engineering Plastics+ Engineering Plastics

Plastic MaterialsPlastic Materials Standard PlasticsStandard Plastics + Engineering Plastics + PUR+ Engineering Plastics + PUR

PlasticsPlastics Plastic MaterialsPlastic Materials + Others (+ Others (ThermosetsThermosets, , Adhesives, Coatings, Sealants)Adhesives, Coatings, Sealants)

ElastomersElastomers Synthetic Synthetic ElastomersElastomers (SBR, IR, IIR, BR, NBR, CR, (SBR, IR, IIR, BR, NBR, CR, Others)Others)

FibresFibres PA, Polyester, Acrylic, Other Synthetic FibresPA, Polyester, Acrylic, Other Synthetic Fibres

Synthetic PolymersSynthetic Polymers Plastic MaterialsPlastic Materials + Fibres + + Fibres + ElastomersElastomers + Others + Others ((ThermosetsThermosets, Adhesives, Coatings, Sealants), Adhesives, Coatings, Sealants)

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World Synthetic Polymers Production World Synthetic Polymers Production 20072007

Synthetic Polymers Synthetic Polymers production in 2007 production in 2007 approximatelyapproximately315 million t315 million t globallyglobally

PE+PPPE+PP represents represents 114 million t114 million t oror36%36% of global of global Synthetic PolymersSynthetic Polymersproductionproduction

PUR PolyurethanesThermoplastics Standard Plastics+ Engineering PlasticsOthers Thermosets, Adhesives, Coatings, SealantsElastomers Synthetic Elastomers (SBR, IR, IIR, BR, NBR, CR, Others)Fibres PA, Polyester, Acrylic, Other Synthetic Fibres

Elastomers4%

Others14%

Fibres13%

PUR4%

Thermoplastics65%

Polyolefins (PE+PP)36%

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World Plastics ProductionWorld Plastics Production 1950 1950 -- 20020088

0

50

100

150

200

250

300

1950 1960 1970 1980 1990 2000 2010

Mill

ion

t

Includes Thermoplastics, Polyurethanes, Thermosets, Elastomers, Adhesives,Coatings and Sealants and PP-Fibres. Not included PET-, PA- and Polyacryl -FibresSource: PlasticsEurope

1977: 50

1950: 1,5

1989: 100

2002: 200

2007: 270

2008: 245

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PolyolefinsPolyolefinsPE and PPPE and PP

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The Polyolefins Family The Polyolefins Family

Polyethylene Polyethylene -- PEPELDPELDPEHDPEHDPE/MDPE/MDPELLDPELLDPE

Polypropylene Polypropylene -- PPPPHomopolymersHomopolymersRandom copolymersRandom copolymersImpact copolymers (heterophasic copolymers, Impact copolymers (heterophasic copolymers, block copolymers)block copolymers)

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PE Classification by DensityPE Classification by Density

HDPE

MDPE

LLDPE

LDPE

Schematic representation of various PE structures

DENSITY COMONOMER PE GRADE0,926-0,970 –/alfa-Olefins HDPE0,926-0,940 alfa-Olefins MDPE0,915-0,935 –/Acrylates/VA LDPE0,915-0,926 alfa-Olefins LLDPE

PE grades by density

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PP StructuresPP Structures

Block copolymerBlock copolymer, , HeterophasicHeterophasic copolymercopolymer -- HECOHECO

PPPPPPPPPPPPEEEEEEEEEEPPPPPPPPPPPPPPPPEEEEEEEEPPPPPPPPPP

Random copolymerRandom copolymer -- RACORACO

PPPPPPPPPPEEPPPPEEPPEEPPPPPPPPPPPPEEPPPPPPEEPPPPPPPP

Isotactic homopolymer Atactic homopolymer

Syndiotactic homopolymer

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Key PropertiesKey Properties

Molecular weightMolecular weightMolecular weight distributionMolecular weight distributionMelt indexMelt indexDensityDensityMechanicalMechanicalESCRESCR

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Molecular Molecular wweighteight

Number averageNumber average

Weight averageWeight average

Polydispersity Polydispersity –– measure of molecular weight measure of molecular weight distributiondistribution

P=MP=M ww //MM nn

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Molecular weight distributionMolecular weight distribution

number averagemolecular weight weight average

molecular weight Mn Mw

molecular weight

number of molecules

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Bimodal PolymerBimodal Polymer Molecular structure vs. propertiesMolecular structure vs. properties

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Melt IndexMelt IndexMelt index Melt index –– measure of ease of flowmeasure of ease of flow

One kind of viscosityOne kind of viscosityInstead of determination of molecular weightInstead of determination of molecular weightFast standard method toFast standard method to

control qualitycontrol qualitycompare productscompare products

Melt index and molecular weightMelt index and molecular weightHigh melt index=low viscosity=low molecular weightHigh melt index=low viscosity=low molecular weightLow melt index=high viscosity=high molecular weightLow melt index=high viscosity=high molecular weight

Non Newtonian behaviourNon Newtonian behaviourMelt index (viscosity) depends on loadMelt index (viscosity) depends on loadMelt indices measured at different loads give indication on Melt indices measured at different loads give indication on molecular weight distributionmolecular weight distribution

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DensityDensity (D)(D)Depends on Depends on comonomercomonomer content (SCB=short chain content (SCB=short chain branching): more SCB = lower Dbranching): more SCB = lower DLonger Longer comonomercomonomer chain = lower Dchain = lower DComonomersComonomers tend to incorporate into lower Mtend to incorporate into lower Mw w molecules deteriorating molecules deteriorating organolepticorganoleptic propertiespropertiesStrong influence on important PE propertiesStrong influence on important PE properties

tie molecules

Crystalinelayers

Crystaline layers: Stiffness

Tie Molecules: ESCR, Impact Strength

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Mechanical PropertiesMechanical Properties 11Tensile strength (TS)Tensile strength (TS)

Higher crystallinity results on higher TSHigher crystallinity results on higher TSTSTSPPPP>TS>TSHDPEHDPE>TS>TSLDPELDPE

TS measured on both machine (MD) and transversal direction (TD) TS measured on both machine (MD) and transversal direction (TD) on filmon film

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Mechanical PropertiesMechanical Properties 22Impact strength (IS)Impact strength (IS)

Ability to withstand shock loadingAbility to withstand shock loadingHigher MHigher Mw w = higher IS= higher ISLower D = higher ISLower D = higher ISDart drop: special impact test for film gradesDart drop: special impact test for film grades

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Mechanical PropertiesMechanical Properties 22Flexural modulus (FM)Flexural modulus (FM)

Measure of stiffness Measure of stiffness –– higher FM means higher stiffnesshigher FM means higher stiffnessHigher D = higher FMHigher D = higher FMFMFMPPHOMOPPHOMO>FM>FMPPHECOPPHECO>FM>FMPPRACOPPRACO

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ESCR ESCR –– Environmental Stress Environmental Stress Cracking ResistanceCracking Resistance

Ability to withstand cracking under load in Ability to withstand cracking under load in chemicalschemicalsMainly used for PE Mainly used for PE -- very important for blow very important for blow moulding and pipe gradesmoulding and pipe gradesLower D = higher ESCRLower D = higher ESCRHigher MHigher MWW = higher ESCR= higher ESCRRole of Role of comonomercomonomer distribution distribution ––comonomerscomonomers built into high Mbuilt into high MWW molecules molecules give very good ESCR give very good ESCR

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AdditivationAdditivationPolyolefinsPolyolefins mainly PP and HDPE need different additives to mainly PP and HDPE need different additives to meet end use requirements. Typical concentration: some meet end use requirements. Typical concentration: some hundreds through some thousands hundreds through some thousands ppmppm (1 (1 ppmppm=1 g/t)=1 g/t)Typical Typical polyolefinspolyolefins additivesadditives

Stabilizers Stabilizers –– to protect polymer from oxidative degradation to protect polymer from oxidative degradation duringduring

Processing Processing –– melt stabilization (high temperature, short time + oxygen)melt stabilization (high temperature, short time + oxygen)Long term useLong term use

thermal stabilization (low temperature, long time + oxygen)thermal stabilization (low temperature, long time + oxygen)UV stabilization UV stabilization –– ( low temperature, long time, UV light + oxygen)( low temperature, long time, UV light + oxygen)

Processing aids and property modifiersProcessing aids and property modifiersSlip agents Slip agents –– to reduce friction during processingto reduce friction during processingAntistatic agent Antistatic agent –– to prevent build up of electrostatic chargingto prevent build up of electrostatic chargingAntiblockingAntiblocking agent agent –– to avoid sticking of film layersto avoid sticking of film layersNucleating agents Nucleating agents –– to improve stiffnessto improve stiffnessClarifying agents Clarifying agents –– to increase product transparencyto increase product transparency

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ApplicationApplication

0%

20%

40%

60%

80%

100%

PP LDPE LLDPE HDPE

Other

Pipe

Extrusion coating

Injection moulding

Blow moulding

Fiber

Film

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Global Global ConsumptionConsumption

0

10

20

30

40

50

60

70

Mill

ion

T/a

1975 1978 1981 1984 1987 1990 1993 1996 1999 2002 2005 2008

PE PP

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Domestic Production and Domestic Production and ConsumptionConsumption

0

50

100

150

200

250

300

350

400

450

500

KT/a

2001 2002 2003 2004 2005 2006 2007 2008 2009

PE production

PE consumption

PP production

PP consumption

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Development of Plant CapacitiesDevelopment of Plant Capacities

0

100

200

300

400

500

600

1970 1975 1980 1985 1990 1995 2000 2005 2010

kt/y

ear

PP HDPE/LLDPE LDPE

Typical single line plant capacity

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Evolution of Extruder Capacities

0

100

200

300

400

500

600

700

1980 1985 1990 1995 2000 2005 2010

kt/y

ear

PolypropylenePolyethylene

6

12,515

25 26

40

34

56

50

75

t/hr

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Investment CostsInvestment CostsBasis: USGC 2008Q1; 400 Basis: USGC 2008Q1; 400 ktkt/year capacity/year capacityTotal investment costs of polyolefin plants Total investment costs of polyolefin plants without licence feewithout licence fee

300300--400 million USD400 million USDCost breakdownCost breakdown

Source: Nexant

33%

32%

35%ISBLOSBLOther costs

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Operating CostsOperating Costs

BasisBasis: USGC 2008Q1; 400 : USGC 2008Q1; 400 ktkt//yearyear plantplantTypicalTypical operatingoperating cash cash costcost of of polyolefinpolyolefinplantsplants 14301430--1530 USD/t1530 USD/tCostCost breakdownbreakdown

Source: Nexant

95,3

2,62,1

80%

85%

90%

95%

100%

Fix costsUtilitiesRaw materials

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AppendixAppendix Typical investment cost elementsTypical investment cost elements

ISBL ISBL –– Inside battery limitInside battery limitFrom raw material feed through pelletizing (civil work, foundatiFrom raw material feed through pelletizing (civil work, foundations, ons, equipment, piping, instrumentation, equipment, piping, instrumentation, electricalselectricals, control room, MCC, , control room, MCC, painting and insulation, construction, supervision, etc.)painting and insulation, construction, supervision, etc.)

OSBL OSBL –– Outside battery limitOutside battery limitPellet blending, storage and packagingPellet blending, storage and packagingUtilities (e.g. power supply, steam boiler, cooling water systemUtilities (e.g. power supply, steam boiler, cooling water system), flare, ), flare, feedstock storage, pollution control, buildings, spare parts, etfeedstock storage, pollution control, buildings, spare parts, etc.c.

Other project costsOther project costsStartStart--up (Services, training programs, operating manuals, modificationup (Services, training programs, operating manuals, modifications s and maintenance during startand maintenance during start--up, etc.)up, etc.)Miscellaneous ownerMiscellaneous owner’’s costs (e.g. long distance pipeline, insurance, s costs (e.g. long distance pipeline, insurance, various studies, travel and living, engineering, transport of eqvarious studies, travel and living, engineering, transport of equipment, uipment, etc.)etc.)Working capitalWorking capital