11
Introduction to PolyolefinsIntroduction to Polyolefins
Polyethylene and PolypropylenePolyethylene and Polypropylene20201010
ElElőőadadóó: Csernyik Istv: Csernyik Istváánn
22
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
33
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)
44
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%
55
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
66
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)
88
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
99
PP StructuresPP Structures
Block copolymerBlock copolymer, , HeterophasicHeterophasic copolymercopolymer -- HECOHECO
PPPPPPPPPPPPEEEEEEEEEEPPPPPPPPPPPPPPPPEEEEEEEEPPPPPPPPPP
Random copolymerRandom copolymer -- RACORACO
PPPPPPPPPPEEPPPPEEPPEEPPPPPPPPPPPPEEPPPPPPEEPPPPPPPP
Isotactic homopolymer Atactic homopolymer
Syndiotactic homopolymer
1010
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
1212
Molecular weight distributionMolecular weight distribution
number averagemolecular weight weight average
molecular weight Mn Mw
molecular weight
number of molecules
1313
Bimodal PolymerBimodal Polymer Molecular structure vs. propertiesMolecular structure vs. properties
1414
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
1515
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
1616
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
1717
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
1818
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
1919
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
2020
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
2121
ApplicationApplication
0%
20%
40%
60%
80%
100%
PP LDPE LLDPE HDPE
Other
Pipe
Extrusion coating
Injection moulding
Blow moulding
Fiber
Film
2222
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
2323
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
2424
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
2525
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
2626
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
2727
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
2828
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