Polymerization  

1
 Type  of  Polymerization

v Step  Growth  Polymerization

v Chain  Growth  Polymerization

Ø Free  Radical  Polymerization

Ø Ionic

Ø Cationic  

Ø Anionic

Ø Insertion

Ø Ring  opening  polymerization

2
 SG  Polyn vs Chain  Growth  Polyn

v S  G  Polyn v C  G  Polyn
§ Growth  throughout  matrix § Growth  by  addn of  monomer  
only  at  one  end  of  chain
§ Rapid  loss  of  monomer  early   § Monomer  remains  even  long  
in  the  reaction Reaction  time
§ similar  steps  repeated     § Different  steps  operate  at  
throughout    Reaction  process different  stage  of  mechanism
§ MW  increases  slowly  &  p  is   § Molar  mass  of  backbone  inc.  
required  for  high  MW very  fast  at  initial  stages
§ Ends  remain  active § Chains  not  active  after  
termination
§ No  initiator required § Initiator  required

3
Cationic  Polymerization

4
Anionic  Polymerization

5
 Proposed  Reaction  Mechanism  for  PLA
v Lactide reacts  with  PDP
Ø Via  Transfer  of  lone  pair  
electron

vForms  growing  polymer  

chain  (1a)
Ø High  MW  PLLA  Chains

vReaction  with  PDP+BA  =>

Ø Isolated  Polymer  Chains  (1b)
Ø Macrocyclics (1c)
Ø Low  MW  PLLA  

6
 Insertion  Polymerization
v Coordination  polymerization

v Monomer  adds  to  growing  macromolecule  

through  an  organometallic active  center

v Ziegler  natta catalyst  

7
 Scheme  for  ROP  of  L-­lactide by  NHC

Proposed  Metal  Mediated  Reaction  Pathways

8
Ring  Opening  Polymerization

9
 Polymerization  Techniques
v Bulk  Polymerization

v Solution  Polymerization

v Suspension  Polymerization

v Emulsion  Polymerization

v Solid  state  polymerization

v Plasma  Polymerization

v Polymerization  in  Ionic  liquid

v Polymerization  if  supercritical  medium

10
 Bulk  Polymerization

v Polymerization    of  undiluted  monomer

v By  addition  of  soluble  initiator  to  pure  monomer

v Viscosity  Inc.  dramatically  during  conversion

v 2  types  of  Bulk  Polymerization

Ø Quiescent  bulk  polymerization

Ø Phenol-­formaldehyde  condensation

Ø Stirred  bulk  polymerization

Ø Nylon  66;;  LDPE,  Polystyrene,  PMMA,  PC,  PLA

11
v Advantage:
Ø Polyn is  simple

Ø Polyn is  obtained  pure;;  easy  polymer  recovery

Ø MWD  can  changed  easily  by  C  T  Agent

v Disadvantage
Ø Heat  Transfer  and  mixing  become  difficult

Ø Highly  exothermic
Ø MWD  become  broader  due  to  high  viscosity  &  lack  of  heat  
transfer
Ø Relative  Low  MW;;  slower  termination  reaction  rate
12
 Metal-­Free  ROP  of  Lactide
O
O
O H O
Organo-­Catalysis
O OH
O              Approach n
O
O
PLLA
L-­lactide

– Polymerization  Temperature :  100-­180°C

– ROP  Initiator :  Metal-­Free  
– Lactide  to  Initiator  Ratio :  25  to  500
– ROP  Time :  2  Hrs  (Max.)
 Proposed  Reaction  Mechanism  for  PLA
v Lactide reacts  with  PDP
Ø Via  Transfer  of  lone  pair  
electron

vForms  growing  polymer  

chain  (1a)
Ø High  MW  PLLA  Chains

vReaction  with  PDP+BA  =>

Ø Isolated  Polymer  Chains  (1b)
Ø Macrocyclics (1c)
Ø Low  MW  PLLA  

14
 Solution  Polymerization
v Monomer  and  initiator  must  be  soluble  in  solvent,  formed  
polymer  stays  dissolved.

v Solution  does  not  increase  viscosity,  as  observe  in  Bulk

v Advantage
Ø Product  some  time  directly  usable,  controlled  heat  transfer

Ø Heat  transfer  problem  solved  by  using  conducting  solvent

v Disadvantage
Ø Solvent  contamination,  chain  transfer  by  solvent,  recycling  
of  solvent

Ø Applications:  Acrylic  coating,  fibre spinning,  film  casting.

15
 Suspension  Polymerization
Ø Liquid  or  dissolve  monomer  suspended  in  liquid  phase

Ø Water  insoluble  monomer  and  initiator

Ø Suspending  agent-­PVA,  methyl  cellulose

Ø Initiator

Ø Particle  size:  10-­500  μm

v Disadvantage
Ø Polymer  purity  is  low  due  to  presence  of  suspending  
additives  &  difficult  to  remove

16
17
 Emulsion  Polymerization
Ø Water;;  Monomer  (hyd-­bhobic);;  surfactant  (hy-­bho+hy-­
bhilic);;  

Ø Water  soluble  initiator,  surfactant;;  monomer  sparingly  

soluble  in  it.

Ø Size  of  monomer  droplet  depends  on  Polyn T  &  rate  of  
agitation;;  above  critical  micelle  concentration,  residual  may  
align  to  form  micelles.
Rubbers:  SBR,  Polybutadiene,  Polychloroprene

Thermoplastics:  PVC,  Polystyrene,  ABS  terpolymer

Dispersion  agent:  PVA  and  copolymers,  styrene  butadiene,

latex  acrylic  paint
18
Emulsion  Polymerization  contd..

19
 Emulsion  Polymerization  contd..

v Advantage
Ø High  MW  polymer;;  Fast  polyn rate,  improved  heat  
removal  from  system,  viscosity  always  close  to  water  and  
does  not  depend  on  MW,  final  product  can  used  as  it  is

v Disadvantages
Ø Surfactant  and  polymerization  adjuvants are  difficult  to  
remove;;  For  dry  polymer  water  removal  is  an  energy  
intensive  process,  can  not  use  for  condensation,  ionic  or  
Ziegler  natta polymerization.
20
 Gas  Phase  Ethylene  Polymerization
v Unipol Process

21
 Polyethylene  Terephthalate  (PET)

• Belongs to the polyester

• Terylene, Terene , Dacron.
• Semi-crystalline opaque and amorphous fully
transparent.
• Superb gas barrier properties, particularly against
oxygen and carbon dioxide, which helps to explain
its use in bottles for carbonated drinks
 Physical Properties
• Good TS, lightweight & hence easy and efficient to transport

• Excellent electrical insulating properties

• APPLICATION: -60 to 130°C

• low gas permeability

• PET doesn’t not break or fracture.

• A suitable glass-replacement in some applications.

• Excellent resistance to alcohols, aliphatic hydrocarbons, oils, greases and diluted

acids

• Moderate resistance to diluted alkalis, aromatic & halogenated hydrocarbon.

• Good resistance to mineral oils, solvents and acids, but not to bases.
 Production
vPET is obtained from condensation polymerization
qEsterification reaction between terephthalic acid
and ethylene glycol, OR
qTrans-esterification reaction between ethylene
glycol and dimethyl terephthalate
vTrans- esterification route is favored because the free
acid is not soluble in many organic solvents.
vThe reaction occurs in two stages
qMethanol is released in the first stage at approximately
200°C with the formation of bis(2-hydroxyethyl)
terephthalate.
q In the second stage, condensation polymerization
occurs, and excess ethylene glycol is driven away at
approximately 280°C and at lower pressures (≈ 0.01
atm):
v An  alternative  route  to  PET  is  by  the  direct  reaction  of  
terephthalic acid  and  ethylene  oxide.  
v The  product  bis(2  hydroxyethyl)terephthalate  reacts  in  
a  second  step  with  TPA  to  form  a  dimer  and  ethylene  
glycol,  which  is  released  under  reduced  pressure  at  
approximately  300°C.
v This  process  differs  from  the  direct  esterification  and  
the  trans-­esterification  routes  in  that  only  ethylene  
glycol  is  released.  In  the  former  two  routes,  water  or  
methanol  are  coproduced  and  the  excess  glycol  
released.  
 Uses
v Plastic  bottles
v In  packaging  applications

q In  tape  applications.
q In  mineral  water  and  carbonated  soft  drinks  packaging.
q food  packaging  applications
q packaging  trays  and  blisters
q Other  packaging  applications  include  rigid  cosmetic  jars,
microwavable  containers,  transparent  films,  etc
vRecycled PET can be converted to
qfibers
qFabrics
q sheets for packaging
q manufacturing automotive parts.
vPET monofilament is mainly used for making
qmesh fabrics for screen-printing,
qfilter for oil and sand filtration,
qbracing wires for agricultural applications (greenhouses
etc.), woven/knitting belt, filter cloth
 Extrusion

vPET is generally extruded to produce films

and sheets (can be thermoformed after).
vExtrusion temperature: 270-290°C.
 Limitations of Polyethylene
Terephthalate

vAffected by boiling water

vAttacked by alkalis and strong bases
vAttacked at high temperatures (>60°C) by
ketones, aromatic and chlorinated
hydrocarbons and diluted acids and bases
vBad burning behavior.
 Blow Molding
vBlow molding is generally used to produce
transparent bottles.
vMold temperature should lie between 10
and 50°C.
 3D Printing
v PET is an optimum polymer to produce 3D Printed objects having high
flexibility and toughness. Certain modified PET compounds have been
developed (such as PETG) for 3D Printing.

v PETG is PET copolyester with glycol modification. PETG filament is

more heat-resistant and tough than PLA, but easier to print than ABS. It
offers higher strength, lower shrinkage, and a smoother finish.

v Recommended hot end temperature: 240 and 260°C

v Bed temperature: 100°C

v Retraction speed slow at 30mm/s or less

Polyethylene its catalyst and
Cocatalysts

36
 Introduction

v Polyethylene  (polyolifins)

v Polymerization  using  ZIEGLER-­ NATTA  CATALYST  

v Polymerization  using  METALLOCENE  CATALYST

v ZIEGLER  NATTA  Vs  METALLOCENE  CATALYSTS  

37
 Ziegler  Natta  vs Metallocene Catalysts

Characteristics Ziegler  Natta Metallocene

Catalyst  
v Catalyst  sites Multiple Single
v Cocatalyst Simple  Alkyl  Aluminium Alkyl  aluminoxane &  
Both  internal  &  external   bulkyanions
v Electron  donor
needed Not  needed

Broad Narrow
Polymer
v MWD
Nonuniform Uniform
v Chainlength
High Low
v Bulk  density
Independent  on                   Dependent  on    
v Melting  Point  of  
polymerization  temperature Polymerizatio temperature
polymerization High Low
v Soluble  Content

38
Reaction  for  opening  of  active  sites

CL  623  Course  Presentation 39

Polymerization  of  Olefins  using  Metallocene
Catalyst
Initiation

Propagation

40
 Termination
By  Hydride  elimination

By  Hydrogenation

By  Chain  transfer  to  the  monomer  or  hydrogen

41
 Metallocene Catalyst  contd..
vStereorigid metallocenes
1.        Et(Ind)2ZrCl2
2.        Et(Ind)2ZrMe2
3.        Et(Ind H4)2ZrCl2

v Cationic  metallocenes

1.        Cp2MR(L)+ [BPh4]-­ (M  =  Ti,  Zr)

2.        [Cp2ZrMe]+ [  C2B9H11)2M]-­ (M  =  Co)

v Supported  metallocenes
1.        Al2O3 – Et[Ind H4]2ZrCl2
2.        MgCl2.Cp2ZrCl2
3.        SiO2.Et[Ind]2ZrCl2

42