Pre Vl1 Intro

7/27/2019 Pre Vl1 Intro

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Polymerisationstechnik


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Polymer Reaction Engineering


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Polymers - the 10.000$ idea

1863: Micheal Phelan alternative for ivory

1869: J.W. Hyatt celluloid (nit

rocellulose and camphor)

1872: commercial exploitation of celluloid starts

Today: phenol resin


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Polymers a brief market overview Introduction to polymerization processes Coordination polymerization Free radical polymerization Suspension polymerization Emulsion polymerization Step-growth polymerization Control of polymerization reactors


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Synthetic Polymersproduction grew by 5 % in

2006 vs. 2005 toapproximately 300 Mio t

globally

Plastic Materialsconsists of Thermoplasticsand Polyurethanes which

count for about 70 % of this

market

WorldSynthetic Polymers Production 2006

PUR Polyurethanes

Thermoplastics Standard Plastics + Engineering Plastics

Others Thermosets, Adhesives, Coatings, Sealants

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

Fibres PA, Polyester, Acrylic, Other Synthetic Fibres

Source: PlasticsEurope Market Research Group (PEMRG)

Elastomers

4%

Thermoplastics

65%

Others

14%

Polyurethanes

(incl. TPU)

4%

Fibers

13%


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Plastics are a globalsuccess story

Continuous growthfor more than 50 years

Plastics productionramped upfrom 1.5 Mio t in 1950to 245 Mio t in 2006

Compound Annual GrowthRate (CAGR)is about 9.5 %


WorldPlastics Production 1950 - 2006

Mio t

Includes Thermoplastics, Polyurethanes, Thermosets, Elastomers, Adhesives,

Coatings and Sealants and PP-Fibers. Not included PET-, PA- and Polyacryl-Fibers

0

50

100

150

200

250

1950 1960 1970 1980 1990 2000

1950: 1.5

Europe(WE + CE)

1976: 50

1989: 100

2002: 200

2006: 245

World


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WorldBenchmarking Plastics vs. Crude Steel

Plasticsin 1989,passed steelproduction by volume

Production worldwide 2006:

Plastics:245 Mio t = 245 billion litre

Steel:1,240 Mio t = 155 billion litre

Calculation Model:1 kg plastics = 1 litre8 kg steel = 1 litre

billion litre

Source: *Stahl-Zentrum/International Iron and Steel Institute (IISI)

50

100

150

200

250

1950 1960 1970 1980 1990 2000

Plastics

Steel*

Plastics production

> Steel production


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Standard Plastics Engineering Plastics

World

Thermoplastics Demand by Resin Types 2006

175 Mio t < 20 Mio t

* PET Bottle grade** PET Injection grade


HDPE17%

LDPE, LLDPE

21%

PP 25%

PVC

20%

PS, EPS 9%PET* 8%

Blends7%

PBT, PET**

5%

Others 3% ABS, SAN41%

PA 15%PC 15%

PMMA 9%

POM 5%


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World

Plastic MaterialsPer Capita Demand* (kg/Capita)

1980 2005 2010eTotal World

4.2 %

Per capita demand* isgrowing at 4 % which is 1%lower than global demanddue to population growth

Despite high growth ratesin Asia and Central Europe -

per capita consumption isstill significantly below thelevel of mature industrial

regions

Consequently there is plentyof room for future growth

Mature industrial regionswill see growth slightly

above GDP

3831

10

13103

Middle East

Africa5.4 %

118

99

40

Western Europe3.6 %

2434

8,5

Central Europe& CIS

7.2 %

26217.5

Latin America

4.4%

NAFTA

120105

46

2.7 %

Japan

9889

50

1.9 %

2

2027

Asia w/o Japan

6.2 %


* demand equals processed volumes


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Packagingby far represents the largest

end-use market

Building & Construction,Automotive and E & E

follow

Othersincludes consumer, house-hold, appliances, furniture,

agriculture, medical, etc.

Over the last yearsthe share of end-use

applications remainedfairly stable


39.5 Mio t

Western Europe

Plastic Materials Demand by End Use Segments 2006

Others

22%

Building &

Construc-

tion 20%

Packaging

43%

E & E 7%

Automotive

8%


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The plastics industryconsists of three sectors:

Plastics Manufacturers Plastics Converters Plastics Machinery

Manufacturers

Large numberof enterprisesunderline the medium sized

business structure

Ongoing consolidation ofmarket players

European plasticsmachinery manufacturersremain in a leading position

globally

Number of Staff: 1,600,000 Number of Companies: 50,000

Revenue: 280 bn


Western Europe

Key Figures Plastics Industry 2006


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amorphous structure semi-crystalline structure

Standard

Plastics

EngineeringThermoplastics

TI = 100 - 150 C

High PerformancePolymers

TI > 150 C

100 C

150 C

Capability by Temperature Index by

Underwriter Laboratories, USA

> 2,000 EUR/ton

> 4,000 EUR/ton

> 10,000 EUR/ton

PEEK

FP

LCP

PPS

PPA PA 46

PET (Injection)

PBT

POM

PA 6 PA 66

PP

HDPE

LDPE LLDPE

PI

PAI

PEI

PES

PSU

PPE mod.

PC

PMMA

PA 11 PA 12

ABS, SAN

SAN EPS PS

PET (Bottle grade) PVC

Triangle of Thermoplastics

by Structure, Capability and Price

Standard Plasticsincludes Polyolefins,

PS, EPS, PVC

and PET (Bottle grade)

Engineering Plasticswith improved performanceat higher costs

High Performance Polymerspermitting exceptional

end-use-applications,

specialized niche products

at high costs

ThermoplasticsClassification


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ThermoplasticsMarket Share

Standard Plasticsare the basics materials

Polyolefinsare the largest product group

Polyethylene: 33 %Polypropylene: 22 %

Engineering Plasticsare a small but valuable

part of the market

High Performance Polymersare specialized for very

demanding applications

Triangle of Thermoplastics

Classified by Market Share

High Performance Polymers

Engineering Plastics

PE33 %

PP

22%

PVC18 %

PS & EPS8 %

PET7 %


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Global resource usage 2006


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Are Plastics Synonymous with

The cheap and nasty Synthetic and artificial

substitutes

All that is wrong withthe environment?


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10

20

30

40

50

60

70

80

90

100

10 20 30 40 50 60 70 80 90 100

Industry image

Glass

Aluminium

Steel & Tinplate

Cement & Concrete

Paper & Board Wood

PLASTICS

NET Averageindustries

NET Average materials

Poor image of plastics

a challenge for the industry


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Polymers in automotive


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Energy demand of a car

100kg of plastics in a car " fuel demand decreases by 0,5L per 100km

Manufactureof cars

6,0%

Manufacture

of materials6,0%

End-of-liferecovery

0,2%

Vehicleoperation

87,8%

Source: GUA/Denkstatt 2007

Source: Audi


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The sky is the limit


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Combination of several disciplines such as polymer chemistry,thermodynamics, characterization, modeling, safety, mechanics,

physics, and process technology

PRE problems are often of a multi-scale and multi-functionalnature to achieve a multi-objective goal

One particular feature of PRE is that the scope ranges from themicro scale on a molecular level up to the macro scale of complete

industrial systems


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PRE time and size scales


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PRE integrated approach


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Microstructural features

Chemical composition and monomer sequence distribution

Homopolymersproperties largely determined by the monomere.g. PS at room temperature rigid, poly(butyl acrylate) soft and

sticky

Copolymers


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Homo- and Copolymers

All monomer"units identical"Homopolymer" "(A-A-A-A-A-A-A)Two monomer

"types, single insertions" "Random Copolymer" " "(A-A-B-A-A-A-B)

Two monomer"types, arranged in blocks ""Block Copolymer" " "(A-A-A-A-B-B-B)


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Key steps in production of polymers

Reactor

Molecular andmorphological

characteristics of thepolymer

Polymeric

materialmicrostructure

End use

properties

Processvariables

Formulation

Processingcompounding

Chemical composition Monomer sequence distribution MWD Polymer architecture Chain configuration (tacticity) Morphology


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Classes of copolymers

Type Structure Monomers Polym. method NameRandom ABBABABAAB Methyl

methacrylate,butyl acrylate

Free radicalpolymerization

Poly(methylmethacrylate-stat-butylacrylate)

Alternating ABABABABA Styrene,maleic

anhydrideFree radicalpolymerization

Poly(styrene-alt-maleic

anhydride)Block AAABBBAAA Styrene,

butadiene Ionicpolymerization Polystyrene-block-polybutadiene-block-polystyrene

Gradient AAABABABBB Styrene, butylacrylate Controlledradicalpolymerization


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Classes of copolymers

Type Structure Monomers Polym. method NameGraft AAAAAAAAAA

BCBCC

B

Styrene/acrylonitrile,polybutadiene

Free radicalpolymerization

Polybutadiene-graft-poly(styrene-stat-acrylonitrile)


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Molecular weight distribution (MWD)

Number average

Weight average

Mn =n(D

n+P

n)!

(Dn+P

n)!wm

Mw =n

2(D

n+P

n)!

n(Dn+P

n)

!

wm


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Polydispersity

Ratio of the two averages is called polydispersity It is a measure of the breadth of the distribution

Polydispersity(PDI)=Mw

Mn

!1

DPn=

Mn

wm

DPw=

Mw

wm


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Polymer architectures


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Thermoplastic elastomer

Thermoplastic elastomers are a class of polymers that combine thecharacteristics of the thermoplastics and those of the elastomers

These materials are ABA tri-block copolymers composed by hardand soft segments, which form a processable melt at high

temperatures and transform into a solid rubber-like object upon

cooling

The transition between the strong elastic solid and the processablemelt is reversible


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Thermoplastic elastomer


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Chain configuration

When a monomer unit adds to a growing chain it usually does so ina preferred direction

Polystyrene, poly(methyl methacrylate) and poly(vinyl chloride) areonly a few examples of common polymers where addition is almost

exclusively head-to-tail (HT)


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Chain configuration

Obviously, steric factors play a role here, the great benzenerings on adjacent units would strongly repel during the

polymerization process if they were head-to-head

In other polymers, particularly those with smaller substituents,head-to-head and tail-to-tail placements can occur


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Chain configuration Polymerization of a vinyl monomer,

CH2=CHX, where X may be a halogen, alkyl

or other chemical group (anything except

hydrogen!) leads to polymers with

microstructures that are described in terms

oftacticity

The substituent placed on every othercarbon atom has two possible arrangements

relative to the chain and the next X group

along the chain These arrangements are called racemic diad (r) or meso diad (m)


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Chain configuration

isotactic syndiotactic

atactic

Regular structure:able to crystallize

PP, PB1, P4MP1,

Irregular structure:amorphous

PS, PMMA, PVC (largely atactic,

some syndiotacticsequences)


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Structural isomerism

Seen in the synthesis of polydienes from conjugated dienes:

where if

CH2=CX-CH=CH2X = H we have butadiene

X = CH3 we have isoprene X = Cl we have chloroprene

The polymers made from these monomers are elastomers or rubbers

Poly(isoprene): natural rubberPoly(chloroprene): neoprene


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Structural isomerism

nn

Trans 1,4 polyisopreneGuttapercha Cis 1,4 polyisopreneNatural rubber

higher Mw

2 types of 1,4 units: cis and trans

Refers to the arrangement of carbon atoms around the double bond


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Morphology

HIPS


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Classes of polymerization


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Chain growth polymerizations

In chain-growth polymerization, monomers can only join activechains

Monomers contain carboncarbon double bonds (e.g., ethylene,propylene, styrene, vinyl chloride, butadiene, esters of (meth)

acrylic acid)

The activity of the chain is generated by either a catalyst or aninitiator


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Chain growth polymerizations

Several classes of chain-growth polymerizations can be distinguishedaccording to the type of active center: Coordination polymerization (active center is an active site of a

catalyst)

Free-radical polymerization (active center is a radical) Anionic polymerization (active center is an anion) Cationic polymerization (active center is a cation)


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Chain growth / Step growth Chain growth Step growth

Monomers Should contain at least adouble bond

Should contain at least twofunctional groups

Growing principle Reaction of themonomer with the activecenter

Chain activity initiatedby a catalyst or an

initiator

Reactions of thefunctional groups ofeither the monomers orthe growing chains

No initiator required Catalyst used toaccelerate reactions

Reacting species Growing chain and monomer 2 different functionalgroups. Any two molecules(polymeric or monomers) inthe reaction mass mayreact

Number of growing chains Small (10-810-7 moll-1) All the macromoleculesGrowing chain lifetime Very short (0,5-10 s) Chains grow during the

whole process


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Chain growth / Step growth Chain growth Step growth

Monomer consumption Steadily throughout thereaction Faster than in chain-growth

Termination Chain termination eventinvolved

No termination involved,chains remain active

Molecular weight Very high from thebeginning of thepolymerization, no big

changes duringpolymerization

Smaller than in chaingrowth, continuous increaseduring the process.

Commercial chain lengthonly at very high monomerconversions.


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Step growth polymerizations


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Polymerization reactors

ReactorOperation

mode Polym.mechanism Polym.technique Examples SpecialcharacteristicsStirred tankreactor Batch Free-radical Suspension

EmulsionExpanded PSPVCFluorinated polym

Largely homopolym.Monomers with similarreactivities and moderateheat generation rate

Semibatch Free-radical Emulsion Carboxylatedstyrene-butadiene; acryliclatexes, vinyl

acetate latexes

Allows precise control ofpolymer quality and reactortemperatures

Continuous Coordination SolutionSlurryGas Phase

LLDPE HDPE PP

Dowlex; DSMMitsuiNovolen

Free-radical BulkEmulsion LDPE, EVASBR Autoclave (150-200 MPa)About 10 large (10-30 m3)

CSTR reactors in series

Tubular reactor Continuous Free-radicalStep growth

BulkBulk

LDPE PS, HIPSNylon 6,6Nylon 6

High p (200-350 MPa)Long reactor (1500 m)

Pre-poly in a CSTR2-phase systemPolycondensationVK tubeRing opening polym of-caprolactam


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Polymerization reactors

ReactorOperation

mode Polym.mechanism Polym.technique Examples SpecialcharacteristicsTubular reactorwith impeller/agitation andhead space

Continuous Step-radical Bulk PETPC

PolycondensationTransesterification

Loop reactor Continuous CoordinationFree-radical

SlurryGas PhaseEmulsion

HDPE PPBimodal PPVinyl acetate

Phillips (i-butane)Spheripol, Borstar(propylene)Spherizone

Fluidized bed Continuous Coordination Gas Phase PPHDPE, LLDPE Unipol, Spheripol, BorstarUnipol, Innovene, Spherilene

Mold Batch Free-radicalStep-growth

BulkReaction injectionmolding

PMMAPU

Pre-polymerized (5-20%)monomer is introduced inthe moldPolyaddition

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