University of Science and Technology of Hanoi

Department of Advanced Materials Science and Nanotechnology

Course:

Dr. NGUYEN DUC ANH

AMSN – USTH
Hanoi, 08/2016
IV.5. Coordination polymerization
IV.5.1. Introduction
IV.5.2. Ziegler – Natta Polymerization
IV.5.3. Ring-opening metathesis polymerization
IV.5.4. Ring-opening polymerization of heterocyclic monomers
V. Polymerization processes
V.1. Bulk polymerization
V.2. Solution polymerization
V.3. Suspension polymerization
V.4. Emulsion polymerization
V.5. Others
Coordination polymerization: Polymerization carried out in the presence of
coordination catalysts, when each addition involves a complexation of a
monomer before its enchainment at the active site of catalyst.
+ Active site includes a metal atom, surrounded by ligands…
Dr. Ziegler and Dr. Natta
 + Karl Ziegler’s discovery ( in Germany-1950s)

at low temperatures and pressures

transition metal compound (Ti, V, Cr)
+ Linear ethylene
Organometallic compound (AlR3)

linear polyethylene (HDPE) – denser, tougher, higher melting

HDPE (high-density polyethylene) – bottle, pipe

LDPE (low-density polyethylene) – lap, film, coating
LLDPE (linear low-density polyethylene)

1953 K. Ziegler, E. Holzkamp, H. Breil & H. Martin

Angew. Chem. 67, 426, 541 (1955); 76, 545 (1964).
+ Heterogeneous Ziegler-Natta Catalysts
(1) transition metal compound
(an element from groups Ⅳ to Ⅷ )
- catalyst
- halides or oxyhalides of Ti, V, Cr, Mo, Zr
Combination of
(2) organometallic compound
(a metal from groups Ⅰ to Ⅲ )
- cocatalyst
- hydrides, alkyls, or aryls of metals
(such as Al, Li, Zn, Sn, Cd, Be, Mg)

TiCl4-AlR3 (R = alkyl) system – initially exchange reactions

AlR3 + TiCl4 AlR2Cl + TiRCl3

AlR2Cl + TiCl4 AlRCl2 + TiRCl3
AlR3 + TiRCl3 AlR2Cl + TiR2Cl2
TiRCl3 TiCl3 + R
TiR Cl TiRCl + R
 X H
R Cl R Cl ① Monomer is complexed at a
CH2 CHX C
Cl Ti Cl Ti
Cl Cl Cl Cl C ② titanium atom exposed on the
① H H
catalyst surface.

② Shifting to the vacant

R H X H
R
Cl C Cl C octahedral position.
Cl Ti CH2 X Cl Ti
Cl Cl Cl Cl C ③ Insertion reaction
③ H H
R
④ Migration of the chain occurs

CH X to reestablish the vacant site on

CH2
Cl
Cl Ti the surface.
④ Cl Cl
 X H
R Cl R Cl ① Monomer is complexed at a
CH2 CHX C
Cl Ti Cl Ti
Cl Cl Cl Cl C ② titanium atom exposed on the
① H H
catalyst surface.

② Shifting to the vacant

R H X H
R
Cl C Cl C octahedral position.
Cl Ti CH2 X Cl Ti
Cl Cl Cl Cl C ③ Insertion reaction
③ H H
R
④ Migration of the chain occurs

CH X to reestablish the vacant site on

CH2
Cl
Cl Ti the surface.
④ Cl Cl
Initiation step
X H
R Cl R Cl ① Monomer is complexed at a
CH2 CHX C
Cl Ti Cl Ti
Cl Cl Cl Cl C ② titanium atom exposed on the
① H H
catalyst surface.

② Shifting to the vacant

R H X H
R
Cl C Cl C octahedral position.
Cl Ti CH2 X Cl Ti
Cl Cl Cl Cl C ③ Insertion reaction
③ H H
R
④ Migration of the chain occurs

CH X to reestablish the vacant site on

CH2
Cl
Cl Ti the surface.
④ Cl Cl
 Heterogenous Ziegler-Natta Polymerization
Stereospecificity in Propagation

H3C H3C
Et Et
CH CH
H3C
V Et H3C
CH H2C H2C CH3
CH2 HC
Ti CH2 Ti V Ti -
F F F CH2

H3C
Et
CH H3C H3C
H3C
V CH2 R R
CH2

Ti CH2
F

Polymer migrates back to vacancy  isotactic polypropylene

11

S.C.S. Lai, April 8th 2003

 Heterogenous Ziegler-Natta Polymerization
Stereospecificity in Propagation

CH3 CH3 CH3

H3C Et H3C Et
H3C H2C CH HC HC
V CH | CH2 Et
CH H2C
CH2
Ti CH2 Ti CH2 Ti V
F F F

H3C H3C

R R

Polymer doesn’t back to vacancy  syndiotactic polypropylene

12

S.C.S. Lai, April 8th 2003

 Heterogenous Ziegler-Natta Polymerization
Stereospecificity in Propagation
TABLE 8.2. Variation of Polypropylene Isotacticity with Catalysta

Catalystb Stereoregularity (%)

AlEt3 + TiCl4 35
AlEt3 + -TiCl3 45
AlEt3 + -TiCl3 85
AlEt3 + ZrCl4 55
AlEt3 + VCl3 73
AlEt3 + TiCl4 + P, As,
or SB compounds 35
AlEt2X + TiCl3 90-99
AlEtX2 + -TiCl3 + amine 99

a Data from Jordan6 and Dawans and Teyssié.7

b Et = ethyl; X = halogen.
 Heterogenous Ziegler-Natta Polymerization
Monomer reactivity

Ziegler-Natta polymerization – nonpolar monomers

monomer activity – decreases with increasing steric hindrance about

the double bond.

reactivity
CH2 CH2 > CH 2 CHCH3 > CH 2 CHCH2CH3 >
CH2 CHCH2CH(CH3)2> CH 2 CHCH(CH3)2 >
CH2 CHCH(CH CH ) > CH
2 32 2 CHC(CH3)3

> >
 Heterogenous Ziegler-Natta Polymerization
Termination
Termination

a. transfer to monomer
b. internal hydride transfer
c. transfer to cocatalyst or to an added alkylmetal compound
d. transfer to added hydrogen

R
CH2 CHR
CH2CH2R + CH2 C
R
CH2 CHR
CH CH + CH3CH
R R
CH2CH H + CH2 C
R
AlR'3
R' + R'2Al CH2CH
R
H2
H + CH3CH
 R
R
M : Zr, Ti, Hf
X
Metallocene Catalysts Z M
X : Cl, alkyl
Z : C(CH3)2, Si(CH3)2, CH2CH2
X R : H, alkyl
R
R

+ The first metallocene catalysts

Cp2TiCl2 R2AlCl

+ MAO – used in conjunction with metallocene catalysts

O O O

Al
CH3
Al Al
CH3 CH3 CH3
CH3 CH3 CH3 (CH3)2Al O Al Al (CH3)2
Al Al Al
O O O
 Homogeneous Ziegler-Natta Polymerization
-Mechanism
Initiation – Formation of active site

L CH3 CH3
Zr + Al O Al(CH3)O
L CH3 CH3

Al(CH3)O
-
L L O Al(CH3)O
O CH3 +
L Zr Zr Zr
CH3 CH3 CH3 L CH3 + Al(CH3)3

Difference between metallocene and heterogeneous Ziegler-Natta catalysts

① the former have well-defined molecular structure

② polymerization occurs at one position in the molecule
③ the transition metal atom.
 Homogeneous Ziegler-Natta Polymerization
-Mechanism
Propagation

-
O
O
L O
-
L O Al
Al
+ O
Zr CH2 O +Zr CH2
L L
CH2 CH2 CH2 CH2
CH2 CH2

- O
L O Al
+
Zr CH2 O
L CH2 CH2 CH2

Possible polymerization mechanism for ethylene.

 Homogeneous Ziegler-Natta Polymerization
-Polymer characteristics
Character of polymers prepared with metallocene catalysts

① Narrower molecular weight distributions

than those prepared with heterogeneous catalysts.

② Better mechanical properties.

③ Polydispersities (Mw/Mn) range from 2 to 2.5 for the former,

and 5 to 6 for the latter.

④ The molecular weight of the metallocene-based polymers decreases

with increasing polymerization temperature, increasing catalyst concentration,
and addition of hydrogen to the monomer feed.
Metathesis polymerization: The redistribution of fragments of alkenes (olefins)
by the scission and regeneration of carbon-carbon double bonds

+ Ring-opening metathesis polymerization

CATALYST
CATALYST R
R
R R

+ Acyclic diene metathesis polymerization

CATALYST
CATALYST R + CH
R R
2 2 CHCH
+ CH 2 2
 Ring-Opening Metathesis Polymerization

+ LnM ROMP R
R LnM

Initiators
N N
N N
N N N N
PCy3 Cl
Cl Cl
Cl Cl N Ru
Ru Ru N Ru
Ru Cl
Cl Cl Cl N
Cl O Br N
PCy3 PCy3

Grubbs 1 Grubbs 2
Br
Hoveyda Grubbs 2
Grubbs 3 Grubbs 3'

N N N
O O F3C O
Mo Mo Mo
F3C
CF3
O O O
F3C CF
CF3 3
Schrock 1 Schrock 2 Schrock 3
 Initiation

LnM
R [2+2] [2+2] R
LnM LnM
coordination LnM cycloaddition retroaddition
R R
metallacyclobutane metal alkylidene

Propagation

m
R R R
LnM LnM LnM
m+2
growing
macromolecule chain
Termination

R X Y R
LnM LnM X + Y
m+2 m+2

deactivated
macromolecule chain
- Controlled ROMP is a powerful technique to prepare well-defined structural copolymers
(i) Grafting-onto

(ii) Grafting from

(iii) Grafting through

 Acyclic Diene Metathesis Polymerization
+ ADMET polymerization uses the same initiators with ROMP

+ ADMET is also useful for the synthesis of functionalized polymers.

the synthesis of an unsaturated polymer containing ester functionality.

O O
CATALYST
CH2 CH(CH2)8COCH2CH2OC(CH2)8CH CH2
O O
[ CH CH(CH2)8COCH2CH2OC(CH2)8 ] + CH2 CH2
 Cyclic esters and their polymerization
O O O
O
O O
O O
O
O n n
LA CL

O O O O
O R O
O O O
O O O O O
R n n n
BL VL TMC

Organometallic Catalysts
O H
O
O O Al O O O
Sn Zn
O O O
O O O
H
Sn(Oct)2 Al(Oi-Pr)3 Zn(Lact)2
 Initiation

R
R O R O
O O H H
2 MeOH O O Me lactide O O Me
Sn Sn Sn
O coordination Me O O
Me O O O
O O H O
O R H O
O R
R
R = Oct
insertion

R O H
O R O
O Me H
O OMe ring-opening
Sn O O O
Me O O Sn O O
O
H Me O O
O O
O R H
O R

Propagation O

R O
O H n O R
O O H
O O OMe O
O O
Sn O O O Me
Me O Sn O
O O Me O
H O O n+1
O R H
O R
- ROP of cyclic esters are important to obtain biocompatible and biodegradable polymers
and copolymersfor biotechnology applications.

O
O O H
O H O O
O O O n
Grubbs 3 R
O n
R
O O
O O O
O 3
3
O O 45
O O 45 k
M16

O O O
= O
R O O O
O 3
O

Y. Li, J. Zou, B. P. Das, M. Tsianou, C. Cheng, Macromolecules 2012, 45,

4623-4629
 V. Polymerization Techniques

V.1. Bulk polymerization

V.2. Solution polymerization
V.3. Suspension polymerization

V.4. Emulsion polymerization

V.5. Others

28
 V.1. Bulk Polymerization
Paddle
Reactor

In the reactor:
- Liquid monomer Monomer
- Initiator
- Inhibitors
- Chain transfer agents I
I

I
I
Initiator

Homogeneous : Polymers remains dissolved in monomers. Eg. PMMA

Heterogeneous : Polymers is insoluble in its monomers. Eg. PVC

 Pros & Cons of Bulk Polymerization

Advantage Disadvantage

- Obtain purest possible polymer - Difficult to control

- Conveniently cast to shape - Reaction has to be run slowly

- Obtain highest polymer yield per - Cannot get high rate and high
reactor volume MW at the same time

- Difficult to remove last traces

of unreacted monomer
30
Bulk Polymerization System

31
 V.2. Solution Polymerization
Solution Polymerization: Monomer dissolved into inert solvent
- Monomer Paddle
- Initiator
- CTA
- Inert solvent
Monomer
I

I
I Initiator
Solvent helps controlling heat
transfer from reaction. I

I
Use for : Solvent
- Thermosetting condensation polymer (stop before gel point)

- Ionic polymerization

- Ziegler-Natta solution process 32

V.2. Solution Polymerization
 Pros & Cons of Solution Polymerization

Advantage Disadvantage
solvent
- Reduces the tendency toward - Rate [M]  reduce rate,
autoacceleration chain length xn
- Solvent waste
- Increases heat capacity/heat- - Need solvent separation &
transfer recovery
- Have traces of solvent, monomer
- Reduces viscosity
- Lower yield
- Minimize runaway reaction -Solvent may not be really inert
(act as CTA)
34
 V.3. Suspension Polymerization

Model of suspension polymerization

Suspending agent

(Hydrophobic)
(Hydrophilic)
monomer
+ Water
Initiator

Dispersion of monomer into water as suspension size in the range of 10 - 1000 m.
Suspension system is stabilized by stabilizers.

Inorganic stabilizers: kaolin, magnesium silicate, aluminum hydroxide, calcium/magnesium

phosphate
Polymers stabilizers: Polyvinyl Alcohol, gelatin, cellulose
35
V.3. Suspension Polymerization
 Pros & Cons of Suspension Polymerization
Advantage
1. Easy heat removal and control 1.
2. Product isolation is easy since the 2.
product is insoluble in water.
3. The process is comparatively cheap
as it involves only water instead of 3.
solvents. 4.
4. Viscosity increase is negligible.
5. Polymeric products with high purity
are generated in bead shape 
directly use
Disadvantage
Low yield / reactor volume
Traces of suspending agent on particle
surfaces
Cannot run continuously
Cannot be used for
-condensation polymers
-ionic or Ziegler-Natta polymerization
37
Suspension Polymerization System

38
Ref: S.L. Rosen, John Wiley & Sons 1993
 V.4. Emulsion Polymerization
Emulsion Polymerization : Use emulsifier / surfactants

Initiator Water
Soap monomer (Hydrophilic)

•Synthetic rubber-styrene-butadiene (SBR), Polybutadiene, Polychloroprene.

•Plastics-PVC, polystyrene, Acrylonitrile-butadiene-styrene terpolymer (ABS).
•Dispersions-polyvinyl acetate, polyvinyl acetate copolymers, latexacrylic paint,
Styrene-butadiene, VAE
39
 Steps in Emulsion Polymeriztion

Water-soluble initiator Monomer swollen micelle

Polymer born in water Polymer moves to micelle

-growing polymer particle

-Monomers inside the micelle decrease

Unreacted monomers in other

micelles and in droplets diffuse
through water to the growing particles

Reaction terminates when 2nd radical gets in 40

nd rd
reaction starts again for the 2 chain when 3 particle gets in.
Steps in Emulsion Polymeriztion

41
Emulsion Polymerization System

42
Ref: S.L. Rosen, John Wiley & Sons 1993
 Comparison of polymerization techniques

Pros Cons
Bulk - easy - Difficult to control temp. and heat transfer
- No contamination - High viscosity
Solution -good heat transfer - Need to use solvent –adding cost
-easy to control reaction temp. -Difficult to eliminate solvent entirely
-low viscosity -Solvents sometimes act as chain transfer agent 
-polymer produced may be used directly leading to lower MW polymer
in the solution form

Suspension - Good heat transfer
- easy to control reaction temp.
- low viscosity
- polymer produced may be used
directly as polymeric suspension
Emulsion -- Good heat transfer
- easy to control reaction temp.
- low viscosity
- polymer produced may be used
directly as polymer latex
-Need extra process in washing out suspending
agent/contaminants and drying the polymer beads
-Polymer beads may stick together and maybe
contaminated with suspending agent
-Good only for addition polymerization using
hydrophobic free radical initiator.
-Need extra process in washing out emulsifier/
contaminants and drying
-Good only for addition polymerization using
hydrophilic initiator.

43
 6. Other techniques:
+ Compressed gas polymerization
- Use Zieler-Natta catalyst
- No solvent
- Moderate P (7-20 atm)
- Monomer separation is easy
- Low temperature ( < 100 oC)
- Low capital + operating cost
- Use fluidized bed reactor

+ Miniemulsion and microemulsion polymerization

44
 Preparation of nanosize polymers