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Polymerisation Processes

Polymerisation Processes

Why look processes like as they do? Polymer Processes

Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

Vorlesung Polymerisationstechnik, Universitt Paderborn, WS 07/08

Polymer processes

Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

Vorlesung Polymerisationstechnik, Universitt Paderborn, WS 07/08

Polymer processes

Polyethylene
Homo- und Copolymers of ethylene:

Polyethylene
LDPE LLDPE HDPE PP

structure

Long- and Short chainbranching PE is industrially produced bay radical- and coordinative polymerization Polyethylene (PE) is semi-crystalline, non-polar thermoplastic material Most important standard plastics with highest production volume crystallinity [%] Melting point [C] density [g/cm3]
Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen Vorlesung Polymerisationstechnik, Universitt Paderborn, WS 07/08 Polymer processes 3

Linear with short chainbranches

Linear with few short chainbranches

Linear

50 - 55 106 - 120 0,91 - 0,93

55 - 60 125 - 130 0,91 - 0,93

70 - 80 128 - 136 0,93 - 0,96

~ 70 164 - 166 0,91


Polymer processes 4

Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

Vorlesung Polymerisationstechnik, Universitt Paderborn, WS 07/08

Polyethylene applications

Polyethylene density
Density correlates with crystallinity and structure of PE: amorphous PE: crystalline PE: = 860 kg/m = 1000 kg/m

Films packaging material injection molding pipes electrical insulation material

Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

Vorlesung Polymerisationstechnik, Universitt Paderborn, WS 07/08

Polymer processes

Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

Vorlesung Polymerisationstechnik, Universitt Paderborn, WS 07/08

Polymer processes

Polyethylene melt flow index


Melt Flow Rate / Melt Flow Index = a measure for chain length / molecular weight Amount of molten polymer [dg/min], that flows at defined conditions (pressure and temperature) through a defined capillary. Standards: ASTM 1238 / ISO R1133 weight 2,16 kg / 21,6 kg

Polyethylen Processes

PE
radical
homogenous homogen bulk

coordinative
homogenous solution heterogenous
Suspension (3 Phase Slurry polymerization) Gas phase bimodal:

Reactions mechanism phases processes

temperature 190 C geometry capillary: D=2,095 mm L=8 mm High MFR = low molecular weight Low MFR = high molecular weight
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(LDPE high pressure process)

slurry-slurry slurry-GP GP-GP


Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen Vorlesung Polymerisationstechnik, Universitt Paderborn, WS 07/08 Polymer processes 8

High Pressure Polyethylene Processes

High Pressure Polyethylene Processes


M alternative T = 200 - 300C P = 2000 - 3000 bar Primary compressor Hyper Compr. Autoclave Tubular reactor

High pressure process in one phase region

High pressure cycle 150-300 bar

High pressure separator

low pressure process in two phase region

Low pressure cycle

Low pressure separator

Extruder Granules
Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen Vorlesung Polymerisationstechnik, Universitt Paderborn, WS 07/08 Polymer processes 9 Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

M
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Side Reactions inHigh Pressure Polyethylene


Chain scission unsaturated chains

Side Reactions inHigh Pressure Polyethylene


Intramolecular transfer to polymer short chain branching
CH2 R1 CH2 CH2 CH H H2C CH2 CH2 H2C CH2 H3C R1 CH2 CH2 C H CH2 CH2 CH2

R1 R1 CH2 CH CH2 R2 H2C

CH CH

CH2 R2

+ +

R2

H2C

R1 H2C
CH2 R1 CH2 CH2 CH CH2 CH H CH2 CH3

n n
H2C CH2

H2C

CH2

R1

CH2 CH2 CH CH2 CH2 CH2

CH2 CH2 CH2 CH2 CH2

Intermolecular transfer to polymer long chain branching


H2C CH2 CH2 R1 CH2 CH2 C H2 R1 CH2 CH2 CH2 CH3 H2C

C H2

Butyl side groups

CH2

CH3 CH2 CH3

+
CH2 R2 CH2 CH2 CH2 CH2 CH2 CH2 R3 CH2 R2 CH2 CH2

+
C CH2 H CH2 CH2

H 2C

CH2 R2

H2 C C H2

H2 C C H2

CH2 HC C H2

H2 C R3

R1

CH2 CH2 CH CH2

CH

H2C

CH2

R1

CH2 CH2 CH CH2 CH3

CH2 CH CH2 CH3

CH2 CH2 CH2

CH3

Ethyl side groups

R3

Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

Vorlesung Polymerisationstechnik, Universitt Paderborn, WS 07/08

Polymer processes

11

Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

Vorlesung Polymerisationstechnik, Universitt Paderborn, WS 07/08

Polymer processes

12

Activation energy and volumes in LDPE

Process parameters and properties - Trends

Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

Vorlesung Polymerisationstechnik, Universitt Paderborn, WS 07/08

Polymer processes

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Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

Vorlesung Polymerisationstechnik, Universitt Paderborn, WS 07/08

Polymer processes

14

Different operation modes in LDPE reactors


Single monomer feed of monomer Multiple initiator possible
I, M I, M I

Coordinative Polyethylene Processes

Multiple feed of monomer and initiator

I, M I, M 300

300

double initiator feed


200 200

Single initiator feed


100 100

Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

Vorlesung Polymerisationstechnik, Universitt Paderborn, WS 07/08

Polymer processes

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Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

Vorlesung Polymerisationstechnik, Universitt Paderborn, WS 07/08

Polymer processes

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Solution Coordinative Polyethylene Processes


Solution process: broad range of comonomer types and densities possible pure products limitation: high molecular weight (high temperature, transfer to solvent)

Solution Coordinative Polyethylene Processes


Flowsheet for solution polymerization (DSM)
Solvent recycle Solvent purification venting

Additives

temperature well above melting point of PE commercial processes: processes with very short residence time, e.g. 2 min: Nova Sclairtech / Advanced Sclairtech Sabic / Stamicarbon Compact solution process Dowlex Mitsui
Hexane solvent Temperature 130C Residence time ~ 10 min Solid content < 10 %
Vorlesung Polymerisationstechnik, Universitt Paderborn, WS 07/08 Polymer processes 17 Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

Flash -Tank

Ethylen Comonomer solvent

Absorber

Reactor

Flash-Tank

Mixer Extruder
Additive HDPE-Granules

processes with longer residence time e.g. 30 min:

adiabatic High space time yield Reactor volume 5 m3 for 5 t HDPE/h


Polymer processes 18

Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

Vorlesung Polymerisationstechnik, Universitt Paderborn, WS 07/08

Solution Coordinative Polyethylene Processes


Sclairtech temperature pressure solvent Residence time heat removal: 200 - 300 C bis zu 100 bar cyclohexane approx. 2 min convective Dowlex 160 C 27 bar C8 / C9 paraffines approx. 30 min convective and conductive

Slurry Coordinative Polyethylene Processes


Slurry process: developed for HDPE Limitation: low density, low molecular weight: partial solubility of the polymer in the suspension media, fouling

suitable for densities above 930 kg/m resp. 920 kg/m (with SSC) CSTRs or slurry-loop reactors used suspension media: paraffines, e.g. hexane, isobutane many commercial processes: processes with loop reactor Phillips Loop Solvay Hostalen Mitsui CX
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processes with stirred tank reactors

Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

Vorlesung Polymerisationstechnik, Universitt Paderborn, WS 07/08

Polymer processes

19

Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

Slurry Coordinative Phillips Loop


Flowsheet of the Phillips Loop process a) Catalyst hopper and feed valve; b) Double loop reactor; c) Flash tank; d) Purge drier; e) Powder-fed extruder; f) Impeller; g) Sedimentation leg Suspension media: isobutane T = 85 100 C p = 37 bar residence time 30 60 min solid content: up to 50 % high specific surface reactor completely filled
Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen Vorlesung Polymerisationstechnik, Universitt Paderborn, WS 07/08 Polymer processes 21

Fluidized Bed Polyethylene Processes


Fluidized-bed process a) Catalyst hopper and feed valve; b) Fluidized-bed reactor; c) Cyclone; d) Filter; e) Polymer take-off system; f) Product recovery cyclone; g) Monomer recovery compressor; h) Purge hopper; i) Recycle compressor; j) Recycle gas cooler

T=80 100 C P = 7 20 bars RTD comparable to CSTR Body widening in upper part of the reactor in order to reduce gas velocity Partly condensation cooling (condensed mode

Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

Vorlesung Polymerisationstechnik, Universitt Paderborn, WS 07/08

Polymer processes

22

Polypropylene applications
PP is versatile in application: packaging material (flexible films and rigid packings) fibers injection molding parts for automotive, electrical applications, consumer electronics Chemical equipment, piping

Polypropylene structure

Isotactic PP

misinsertion

High growth rates for PP

syndiotactic PP atactic PP

Crystallinity correlates with stereo selectivity and melting point Isotactic = crystalline Atactic
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= amorphous
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Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

Types of Polypropylene
homopolymers random-copolymers with ethylene (1-8 wt.-%) mit 1-butene terpolymers heterophasic copolymers at least two-stage processes, in which a second, elastomeric phase is generated

Polypropylene Processes a variety


Slurry process Novolen Innovene Unipol Spheripol Mitsui Borstar MZCR in hydrocarbon slurry, tank or loop reactors gas phase, vertical stirred powder bed gas phase, horizontal stirred powder bed fluidized bed slurry loop reactors ( + gas phase copolymer) slurry bulk + gas phase liquid / scf proyplen (+gas phase copolymer) gas phasem, multi zone circulating reactor

Cat, cocat. C3, H2,

1.Reactor PP homopolymer slurry gas

Active powder

2. Reactor PP copolymer gas

Extrusion

C3, C2,

Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

Vorlesung Polymerisationstechnik, Universitt Paderborn, WS 07/08

Polymer processes

25

Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

Vorlesung Polymerisationstechnik, Universitt Paderborn, WS 07/08

Polymer processes

26

Spheripol Process
Spheripol process
a) Loop reactors; b) Primary cyclone; c) Copolymer fluidized bed; d) Secondary and copolymer cyclone; e) Deactivation; f) Purging 1. Stage: Matrix homopolymer in bulk in loop-reactors 2. stage: Impact-Copolymers in gas phas polymerization

BASF/ Novolen Gas Phase Process


BASF gas-phase Novolen process a) Primary reactor; b) Copolymerizer; c) Compressors; d) Condensers; e) Liquid pump; f) Filters; g) Primary cyclone; h) Deactivation/purge

Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

Vorlesung Polymerisationstechnik, Universitt Paderborn, WS 07/08

Polymer processes

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Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

Vorlesung Polymerisationstechnik, Universitt Paderborn, WS 07/08

Polymer processes

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Amoco Gas Phase Process


Amoco Chisso gas-phase process a) Horizontal reactor; b) Fluidized-bed deactivation; c) Compressor; d) Condenser; e) Hold/separator tank

Unipol Fludized Bed Gas Phase Process


UCC/Shell Unipol fluidized-bed process a) Primary fluidized bed; b) Copolymer fluidized bed; c) Compressors; d) Coolers; e), f) Discharge cyclones; g) Purge

Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

Vorlesung Polymerisationstechnik, Universitt Paderborn, WS 07/08

Polymer processes

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Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

Vorlesung Polymerisationstechnik, Universitt Paderborn, WS 07/08

Polymer processes

30

Borstar Process

processes with different reaction zones in one reactor:

G as c ir c u la tin g c o m p re s s o r M ZC R B A R R IE R S E C T IO N C ondenser

P r o p y le n e b a r r ie r s tr e a m R IS E R fa s t f lu id iz a tio n (u p w a rd tr a n s p o rt) D O W N ER packed bed ( m o v in g d o w n w a rd )

E th y le n e s tr ip p in g c o lu m n

P ro d u c t d is c h a r g e P r o p y le n e fe e d

C a ta ly s t in le t

H eat e xch a ng e r

Basells spherizone

Draught tube reactor proposed by Weickert


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Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

Vorlesung Polymerisationstechnik, Universitt Paderborn, WS 07/08

Polymer processes

31

Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

Tailoring of mwd and comonomer distribution


:

Melt flow dependent in mwd


melt flow behaviour of different HDPE at 190C
10
0 HDPE 3

Reduced

impact strength.
Migration, taste. Smoke and odour during extrusion

Processability, stiffness

Matrix

ESCR and creep resistance Mechanical strength Melt strength during extrusion

normierte Viskositt /o

10

-1

HDPE 2

Bimodal Conventional

rel. Hufigkeit

10

-2 HDPE 1

Molecular weight (= polymer chain length)

new property combinations

different approaches possible: multistage process reactors with different reaction zones multisite - catalysts
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10

-3

Molmasse

10

-4

10
Polymer processes 33

-5

10

-3

10 -1 Scherrate / s -1

10

10 3
Polymer processes 34

Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

Vorlesung Polymerisationstechnik, Universitt Paderborn, WS 07/08

Controlling mmd by different methods


Aternative processes for bimodal PP

Controlling mmd by different methods

V V
H2

Ti

Ti V Ti

H2

Weight %

Mi
t

Ti

Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

Vorlesung Polymerisationstechnik, Universitt Paderborn, WS 07/08

Polymer processes

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Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

Vorlesung Polymerisationstechnik, Universitt Paderborn, WS 07/08

Polymer processes

36

Bimodal properties by multi-site catalyst


unimodal process with multi-site catalysts:

hydrogen response for Ziegler catalysts

bimodal polymers can be produced with multi-site catalysts in single stage processes:

Kim, J. D., Soares, J. B. P., Journal of Polymer Science: Part A: Polymer Chemistry, 38, 1427-1432, (2000)

lower investment costs compared to multireactor processes / processes with multizone reactors control of polymer structure more difficult / less flexible narrower product window compared to multistage processes
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Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

Bimodal properties in a reactor cascade


1. Reactor
catalyst Cocatalyst Silo Catalyst poison

Bimodal properties in an oscillating reactor


2. Reactor high
Katalysator Cokatalysator

Temperatur[C] H2-concentration Mw

low low 800.0001,5 Mio

high 50.000200.000

Propylene hydrogen

Propylene hydrogen

1. Reactor

2. Reactor

Catalyst poison controls fraction in 2. reactor

Propylen Wasserstoff 1. Reaktor

Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

Vorlesung Polymerisationstechnik, Universitt Paderborn, WS 07/08

Polymer processes

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Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

Vorlesung Polymerisationstechnik, Universitt Paderborn, WS 07/08

Polymer processes

40

Styrenic Polymers
PS
-MeS
- transparent - stiff - brittle

Styrenic Polymers thermal initiation


Acrylnitril
* *

PSAN
-environmental stress resistant

P[S/a-MS] P[a-MS/AN]
-heat resistant

Bu

Polybutadienerubber

S/Bu (block-) copolymers


- tough - translucent - low weather resistance

HIPS
- tough - opaque - low weather resistance

Polybutadienrubber

Polyacrylaterubber

* *

* * * * H

ABS
- tough - opaque - low weather resistance

ASA
- tough - opaque - weather resistance
. H

MMA

Pn* CH3 * *CH

MBS, MABS
- tough - transparent
Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

MMA

+ +
Polymer processes 41 Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen
Pn

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Polymer processes

42

Styrenic Polymers processes over the years

Styrenic Polymers process and mwd


dm dP

10-2

Styrene / EB 50-80% conv. 130-170C

IG Farben, 1936

Union Carbide, 1943

Dow, 1952

BASF 1965
2000 4000 6000 8000
Polymer processes 44

Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

Vorlesung Polymerisationstechnik, Universitt Paderborn, WS 07/08

Polymer processes

43

Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

Vorlesung Polymerisationstechnik, Universitt Paderborn, WS 07/08

Degassing polymer solutions / melts


Falling strand devolatiizer
Heat exchanger
Vacuum Vacuum

Degassing of polystyrene
Vle S ber PS monomer

tubular / pipe degassing


Separation melt/gas in tubes Heating during evaporation Non-isothermal flash

Falling strangs Long diffusion Adiabatic flash

Vacuum

Extruder
Vacuum

Thin film evaporator


Extremely thin films

Renewal of melt surface Short diffusion paths Nearly isothermal flash


Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

Short diffusion ways Heating during evaporation Nearly isothermal flash


Polymer processes 45

Residual concentration of styrene deviates from equilibrium: mass transfer limitations degradation of polystyrene to monomer, dimers, trimers
Meister, Platt, Ind. Eng. Chem. Res., 28(1989)1662 Scheirs, Modern Styrenic Polymers
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Brittle and tough materials


Pure thermoplastic polymer, Tg>Tuse brittle, hard Thermoplastic polymer + rubber, Tg<<Tuse tough, hard

HIPS, High impact polystyrene / solution/mass ABS


Dissolve PBu rubber in styrene and start polymerization of styrene in the presence of rubber Rubber particles are formed, which toughen the brittle polystyrene

Tensile strength stress, strain, stress, strain,

Tear resistance at elongation at tear

elongation, Area= energy


Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

elongation,

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Polymer processes

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Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

Vorlesung Polymerisationstechnik, Universitt Paderborn, WS 07/08

Polymer processes

48

HIPS, solution/mass ABS - principles


Rubber ( PBu) dissolved in Styrene (/ Ethyl benzene) Polymerization of styrene, homo-PS and grafted PBu Phase separation ( PBu/S and PS/S) Phase inversion Particle formation End of reaction A Course of reaction

HIPS grafting and phase inversion


PBu in S PS in S

B D C

Phase separation B B B S SS B B S S S
S S S S

Phase inversion

S SS S

B B B B
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S BB S B B B

B BS SS B S S BB S

Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

HIPS phase inversion in first 2 reactors


Viscosity

HIPS phase inversion in first 2 reactors

Reactor 1

Reactor 2
Phase inversion when volume ratio = 1:1 of disperse : continuous phase

Viscosity

in

out

in

out
Stabilization of particles by graft polymers formed in 1. reactor

Homogene Lsung

conversion

Polybutadiene in styrene Polystyrene in styrene


Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen Vorlesung Polymerisationstechnik, Universitt Paderborn, WS 07/08 Polymer processes 51 Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

S S

Graft copolymers needed for stabilization of morphology


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Conversion
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HIPS various continuous processes

HIPS process with static mixers


Recycle solvent

solvent monomer comonomer additives water

water

additives

Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

Vorlesung Polymerisationstechnik, Universitt Paderborn, WS 07/08

Polymer processes

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Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

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Polymer processes

54

Specific heat removal capacity for different reactors

SAN copolymers

1 SMR, 2- static mixers, 3- empty tube, 4 stirred tank, 5 extruder


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SAN copolymerization behaviour


1.0 Copolymerisationsdiagramm fr Styrol / Acrylnitril 0.8

SAN copolymers by.


Suspension polymerization

W-% AN in polymer

only azeotropic composition water- solubility of AN

Emulsion polymerzation
semi- batch, starved feed shows some haze
65% AN 30% AN 24% AN 10% AN

0.6
X _S tyro l

Continuous solution polymerization in CSTR


all compositions available

0.4

0.2

rS=0.34 rAN=0.05

0.0 0 0.2 0.4


x_Styrol

0.6

0.8

conversion

Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

Vorlesung Polymerisationstechnik, Universitt Paderborn, WS 07/08

Polymer processes

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Polymer processes

58

SAN copolymers in CSTR


SAN, EB
M

Rubber modification of SAN > ABS rubber from emulsion or solution process
Emulsion polymerization
PRC

Solution polymerisation Mat surface White No waste water Solution polymerization of SAN in the presence of rubber as for HIPS

continous SAN-Polymerisation

High glance of surface Yellowish colour waste water Separate polymerization of SAN (solution polymerization) and rubber (in emulsion)

To flare degassing

Multiple degassing unit: toxic AN high temperatures give yellow polymer


Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

SAN-melt To Extruder

SAN-Granulat
Polymer processes 59 Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

1m

1m

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Polymer processes

60

Emulsion Rubbers for impact modification of SAN


100-250nm

ABS, ASA via emulsion rubber and solution SAN


M PRCS M M

SAN matrix
M

Base rubber

Crosslinked rubber SAN graft


Product Rubber type Double bonds Tg Weather resistance Low temperature impact resistance
Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

PRC

SAN grafting

Storage tank
M M

precipitation

ABS Polybutadiene Many -80C high

ASA Acrylic ester+ bifunctional monomer -40C High low


Polymer processes 61 Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

De-watering SAN-melt
M M M M

extruder ABS

vapor

Vacuum
Polymer processes 62

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PMMA Polymethyl methacrylate

PMMA gel an glass effect effect

Some special features Strong gel effect Low ceiling temperature Tendency to depolymerization High shrinkage Termination by combination and disproportionation
conversion

Due to glass effect

Due to Ceiling temperature 100%

50

100

150

200

T/C

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Polymer processes

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Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

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Polymer processes

64

PMMA weak links


From combination
2 O O O O O CH3 C* O

PMMA continuous bulk process

From disproportionation Starting point for depolymerization

C* O O O O O CH3 O

+ * CH2 O O

Comonomers stop unzipping MMMMMMMMMMMMMMMMMXMMMMMM* MMMMMMMMMMMMMMMMMX* + M

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Polymer processes

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Polymer processes

66

PMMA process for plates and sheets

PVC suspension process


p = ln(1 2 ) + 2 + 2 ln 1 2 p0 1

=0.98

p=const- = separate monomer phase

s = kH

p p0

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Polymer processes

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Polymer processes

68

PVC suspension process

PVC bulk process

Prepolymerization up to 10%

Post polymerization up to 85-90%


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PVC bulk process, post reactors


High solid Particle size 0.08-0.2 mm

PVC bulk process, particle size and stirring

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Polymer processes

71

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Polymer processes

72

The Nylon revolution 1945

Polyamides basic structures


PA 6: Perlon O NH ( CH2 )5 C n NH ( CH2 )6 NH PA6.6: Nylon O O n

C ( CH2 )4 C

PA 6:

Caprolactam

PA 6.6:

Hexamethylendiamine + Adipic acid Hexamethylendiamien + Sebacic acid Butandiamine + Adipic acid

PA 11:

Undecanlactam

PA 6.10:

O N (CH2)6 N H
Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

PA 12:

Laurinlactam

PA 4.6:

C (CH2)6 C n
Polymer processes 73 Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

H
Vorlesung Polymerisationstechnik, Universitt Paderborn, WS 07/08 Vorlesung Polymerisationstechnik, Universitt Paderborn, WS 07/08 Polymer processes 74

Polyamides base materials


-Caprolactam:
Phenol OH
+6H (Ni)

PA6 basic reactions


OH H
-2H

+H2NOH - H2O

N H

1. Ring opening
(H2SO4)

Cyclohexanol

Cyclohexanon

Cyclohexanon-oxim

NH (CH2)5 CO + H2O

H NH (CH2)5 COOH

+6H (Ni)

+CINO - HCI

H2C

H2 C

CO

Benzene

Cyclohexan

NH H2C H2C CH2 -Caprolactam:


+2NaCN - 2NaCl

2. Polyaddition
NH (CH2)5 CO + H NH (CH2)5 CO n OH H NH (CH2)5 CO
n+1

Hexamethylene diamine:
H2C = CH CH = CH2

+Cl2

H2C = CH CH = CH2 Cl Cl

OH

H2C CH = CH CH2 CN CN H2C H2C CH2 C

+2H (Ni)

NC (CH2)4 CN Adiponitrile H2C H2C CH2 C=O

+8H (Ni, NH3)

H2N (CH2)6 NH2 Hexamethylendiamin COOH (CH2)4 COOH Adipic acid


Polymer processes 75 Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen Vorlesung Polymerisationstechnik, Universitt Paderborn, WS 07/08 Polymer processes 76

3. Polycondensation
H NH (CH2)5 CO n OH + H NH (CH2)5 CO mOH H NH (CH2)5 CO OH + H2O

Adipic acid:

H OH

n+m

H2C CH2 Cyclohexanol


Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

H2C CH2 Cyclohexanone

Vorlesung Polymerisationstechnik, Universitt Paderborn, WS 07/08

Polyamide 6 - VK column
M

PA6-process modelling of each process unit


Melt polymerization Extraction of oligomers Schmelzepolymerisation im VK - Rohr Extraktion
Extractor 95C Caprolactam Caprolactam (+Kettenregler) + 0,5% H 2O (+chain regulator + H2O)
PA 6 - Granules

-Caprolactame

Trocknung/Temperung Drying,

solid state polymerization


melting 80C VK-column 270C Melt filter
Bedingungen: : 9 - 17 h T : 250 - 280 C p : 0 - 0,3 bar Bedingungen: : 17 - 30 h T : 95 - 120 C -H2O

Water

N2 Extracttwater N2 -O2

silo

water 280C preparation Pre condensation 250C, 40 bar


dry er 80C

Vacuum (1 mbar)

: 20 - 40 h

Bedingungen:

T : 135 - 180 C

nitorgen Water

granulation Mean residence time VK column 15 - 30 h throughput: 2000 moto


Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

Granules
Polymer processes 77

Granulation
Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

air

Polyamide 6
Polymer processes 78

Vorlesung Polymerisationstechnik, Universitt Paderborn, WS 07/08

Vorlesung Polymerisationstechnik, Universitt Paderborn, WS 07/08

PA6-process modelling of melt process


Model input: Kinetic scheme and parameters Non-ideal phase behavior using NRTL model Model output: Molecular weight end groups Residual monomer Oligomer concentration
180 160 140 120 100
0.5 1

PA6-process modelling of extraction


Model assumptions: Nernst law at phase boundaries Nernst coefficient dependent on monomer concentration Fick diffusion in polymer phase and liquid boundary layer Model output: Concentration profile of residual monomer and oligomer in polymer and liquid phase
79 Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

10 8 6 4 2 2 Top

0.9

% extractable

simulation results taking into account exp. binary VLE date


Extract, %, CL, H2O, Oligomers NH2-end groups degree of polymerization dimer, %
0.8

0.7

0.6

80
0.4

10 bottom 12

60
0.3

1 0.8 0.6 0.4 0.2 2 Top 4 6 8 10 12 bottom


Polymer processes 80

40 20 0 235 240 245 250 255 260 265 270 275


temperature in top of VK-Rohr

0.2

% dimer in granules

0.1

280

Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

Vorlesung Polymerisationstechnik, Universitt Paderborn, WS 07/08

Polymer processes

Vorlesung Polymerisationstechnik, Universitt Paderborn, WS 07/08

PA6-process modelling of solid state condensation


0 .2 0

PA66- basic reactions

mass fraction of caprolactam [%]

0 .1 8 0 .1 6 0 .1 4 0 .1 2 0 .1 0 0 .0 8 0 .0 6 0 .0 4 0 .0 2 0 .0 0 0 10 20 30

T T T m

= 1 4 5 C = 1 6 5 C = 1 9 0 C odel

Model assumptions: Polymer end groups, water, monomer und oligomere only in amorphous phase reaction kinetics as in melt diffusion coefficients dependent on degree of crystallinity surface is free of water Isothermal spherical particle Model output Pn, monomer and oligomer concentration
Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

O O HO C (CH2)4 C OH Adipic acid


40 50

+
+ H2O

H2N (CH CH2)6 NH2 Hexamethylene diamine

r e a c tio n tim e [h ]

450

AH-salt solution
T = 1 2 5 C T = 1 4 5 C T = 1 6 5 C T = 1 8 0 C T = 1 9 0 C m odel

number-average chain length

400

350

Polycondensation H2O O O HO C (CH2)4 C NH (CH2)6 NH H


81 Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen Vorlesung Polymerisationstechnik, Universitt Paderborn, WS 07/08 Polymer processes 82

300

250

200

150

100 0 10 20 30 40 50

r e a c t io n t im e [ h ]

Vorlesung Polymerisationstechnik, Universitt Paderborn, WS 07/08

Polymer processes

Polyamide 66 - tank process

Polyamide 66 continous tubular process


40-60% AH-Salt Solution Pump High energy consumption Evt. loss of volatiles in vapor tube reactor Devolatilisation e.g. Extruder

H2O-Steam

Pump

Polymer Melt Postcondensation

Separator

Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

Vorlesung Polymerisationstechnik, Universitt Paderborn, WS 07/08

Polymer processes

83

Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

Vorlesung Polymerisationstechnik, Universitt Paderborn, WS 07/08

Polymer processes

84

Polyamide 66 countercurrent process reactive distillation


Molten diacid feed (bb) Steam Pressure atmospheric typically

Polyethylen(butylen)terephtalat, PET, PBT


O CH3 O C O C O CH3 HO (CH2)x OH
Diol

O HO C

O C OH

Terephtalic acid ester transesterification

Terephtalic acid esterfication

Reactive distillation

O HO (CH2)x O C
Temperature conventional

O C O (CH2)x OH

Pre-condensation Post-condensation
Gaseous diamine feed (aa) Polymer (aabb) Product Mn 9000 typically
Vorlesung Polymerisationstechnik, Universitt Paderborn, WS 07/08 Polymer processes 85

O HO C

O C O (CH2)x O H
n

x=2: PET x=4: PBT

Side reactions: acetaldehyde, THF from butane diol (PBT)


Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen Vorlesung Polymerisationstechnik, Universitt Paderborn, WS 07/08 Polymer processes 86

Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

Some processes PET, PBT from DMT


O CH3 O C O C O CH3

Rotating disc reactor for PET, PBT

To force conversion from 0.95 to 0.99 0.995 ( or Pn>100), water removal more important than for polyamides, because of low equilibrium constants

Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

Vorlesung Polymerisationstechnik, Universitt Paderborn, WS 07/08

Polymer processes

87

Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

Vorlesung Polymerisationstechnik, Universitt Paderborn, WS 07/08

Polymer processes

88

Polyoxymethylene anionic polymerization of CH2O


CH2O Purification, drying CH2O R Hexane Formaldehyde (Gas) Formaldehyde (water solution.)

Polyoxymethylene anionic polymerization of CH2O

Suspensions polymerization

R O CH2 O CH2 O
n

Acetic anhydride End group stabilization by chemical modification O R O CH2 O CH2 O O CH3
n
Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen Vorlesung Polymerisationstechnik, Universitt Paderborn, WS 07/08 Polymer processes 89 Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen Vorlesung Polymerisationstechnik, Universitt Paderborn, WS 07/08 Polymer processes 90

Polyoxymethylene end group stabilization

Polyoxymethylene cationic bulk process Schalenkreis


Additives
Heat Stabilizier Antioxidant Milling Polymerized Material

Vacuum

Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

Vorlesung Polymerisationstechnik, Universitt Paderborn, WS 07/08

Polymer processes

91

Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

Vorlesung Polymerisationstechnik, Universitt Paderborn, WS 07/08

Polymer processes

92

Polyoxymethylene cationic kneader process

Dr. Klaus-Dieter Hungenberg, BASF AG Ludwigshafen

Vorlesung Polymerisationstechnik, Universitt Paderborn, WS 07/08

Polymer processes

93