TTT Tooo oppp piii iccc csss s ttt tooo o bbb beee e CCC Cooo ovvv veee errr

rrr reee eddd d

Elements of Addition Polymerization
Branching and Tacticity
The Effect of Crystallinity on Properties
Chapters 1 & 2 in CD (Polymer Science and Engineering)
The term polyolefin embraces all polymers that are derived from simple unsaturated
aliphatic hydrocarbons that contain one double bond per monomer. Examples include:
The most important polyolefins in terms of production volume are polyethylene (PE),
polypropylene (PP) and the ethylene/propylene copolymers (EP). Other significant
polyolefins include, polybut-1-ene, poly-4-methylpent-1-ene and polyisobutene (PIB).
Isobutene
CH
2
C
CH
3
CH
3
4-Methylpent-1-ene
But-1-ene
Propylene
Ethylene
CH
2
C
H
CH
2
CH
3
CH
3
CH
CH
2
C
H
CH
2
CH
3
CH
2
C
H
CH
3
CH
2
CH
2
WWW Whhh haaa attt t AAA Arrr reee e PPP Pooo olll lyyy yooo olll leee efff fiii innn nsss s??? ?
LL
L L
oo
o o
ww
w w
DD
D D
ee
e e
nn
n n
ss
s s
ii
i i
tt
t t
yy
y y
PP
P P
oo
o o
ll
l l
yy
y y
ee
e e
tt
t t
hh
h h
yy
y y
ll
l l
ee
e e
nn
n n
ee
e e
~ 1890s
CH
2
N
2
-(CH
2
)
n
- + N
2
~ 1930s
ICI - chemical reactions under
pressure; Ethylene + Benzaldehyde
LL
L L
oo
o o
ww
w w
DD
D D
ee
e e
nn
n n
ss
s s
ii
i i
tt
t t
yy
y y
PP
P P
oo
o o
ll
l l
yy
y y
ee
e e
tt
t t
hh
h h
yy
y y
ll
l l
ee
e e
nn
n n
ee
e e
A modern cable coating
The original ICI pilot plant
This allowed
this to triumph
LL
L L
oo
o o
ww
w w
DD
D D
ee
e e
nn
n n
ss
s s
ii
i i
tt
t t
yy
y y
PP
P P
oo
o o
ll
l l
yy
y y
ee
e e
tt
t t
hh
h h
yy
y y
ll
l l
ee
e e
nn
n n
ee
e e
CC
C C
hh
h h
aa
a a
ii
i i
nn
n n
PP
P P
oo
o o
ll
l l
yy
y y
mm
m m
ee
e e
rr
r r
ii
i i
zz
z z
aa
a a
tt
t t
ii
i i
oo
o o
nn
n n
ss
s s
CC
C C
hh
h h
aa
a a
rr
r r
aa
a a
cc
c c
tt
t t
ee
e e
rr
r r
ii
i i
ss
s s
tt
t t
ii
i i
cc
c c
ss
s s
oo
o o
ff
f f
CC
C C
hh
h h
aa
a a
ii
i i
nn
n n
PP
P P
oo
o o
ll
l l
yy
y y
mm
m m
ee
e e
rr
r r
ii
i i
zz
z z
aa
a a
tt
t t
ii
i i
oo
o o
nn
n n
ss
s s
~~~~~~~CH
2
- CH

-

CH
2
- C*

Rest of Chain
~~~~~~~CH
2
- C*
X

-
CH
2
= CH
Rest of Chain
X

-
X

-
X

-
Active site
H

-
H

-
1. Initiation
2. Propagation
3.Termination
4. Chain Transfer
Need to consider;
CC
C C
hh
h h
aa
a a
ii
i i
nn
n n
PP
P P
oo
o o
ll
l l
yy
y y
mm
m m
ee
e e
rr
r r
ii
i i
zz
z z
aa
a a
tt
t t
ii
i i
oo
o o
nn
n n
ss
s s
CH
2
= CHX
CH
2
= CX - CH = CH
2
CH

CH
--
--
--
N
C
O
H
O
CH
2
- CH
2
Various Olefins and
Vinyl Monomers
Various Dienes
Acetylene
Caprolactam
Ethylene Oxide
CC
C C
hh
h h
aa
a a
ii
i i
nn
n n
PP
P P
oo
o o
ll
l l
yy
y y
mm
m m
ee
e e
rr
r r
ii
i i
zz
z z
aa
a a
tt
t t
ii
i i
oo
o o
nn
n n
ss
s s

--
- -
aa
a a
ss
s s
ii
i i
mm
m m
pp
p p
ll
l l
ii
i i
ss
s s
tt
t t
ii
i i
cc
c c
vv
v v
ii
i i
ee
e e
ww
w w
CH
2
= C
X

-
H

-
.
CH
2
- C
.
X

-
H

-
.
CH
2
- C
.
X

-
H

-
.
CH
2
- C
.
X

-
H

-
.
CH
2
- C
.
X

-
H

-
.
CH
2
- C
.
X

-
H

-
CH
2
- C -
X

-
H

-
CH
2
- C -
X

-
H

-

CH
2
- C -
X

-
H

-
-

CH
2
- C -
X

-
H

-
CC
C C
hh
h h
aa
a a
ii
i i
nn
n n
PP
P P
oo
o o
ll
l l
yy
y y
mm
m m
ee
e e
rr
r r
ii
i i
zz
z z
aa
a a
tt
t t
ii
i i
oo
o o
nn
n n
ss
s s
~~~~~~~CH
2
- CH

-

CH
2
- C
.
Rest of Chain
CH
2
= CH
X

-
X

-
X

-
~~~~~~~CH
2
- C
.
X

-
Rest of Chain
H

-
H

-
CCC Chhh haaa aiii innn n PPP Pooo olll lyyy ymmm meee errr riii izzz zaaa attt tiii iooo onnn nsss s TTT Tyyy yppp peee esss s
((( (nnn naaa attt tuuu urrr reee e ooo offf f ttt thhh heee e aaa accc cttt tiii ivvv veee e sss siii ittt teee e))) )
~~~~~~~CH
2
- CH

-

CH
2
- C*

Rest of Chain
~~~~~~~CH
2
- C*
X

-
CH
2
= CH
Rest of Chain
X

-
X

-
X

-
~~~~~~~CH
2
- C
.
X

-
CH
2
= CH
Rest of Chain
X

-
Anion or Cation
H

-
H

-
H

-
Free Radical
Anionic
Cationic
Coordination (Catalyst)
CC
C C
hh
h h
aa
a a
rr
r r
aa
a a
cc
c c
tt
t t
ee
e e
rr
r r
ii
i i
ss
s s
tt
t t
ii
i i
cc
c c
ss
s s
oo
o o
ff
f f
CC
C C
hh
h h
aa
a a
ii
i i
nn
n n
PP
P P
oo
o o
ll
l l
yy
y y
mm
m m
ee
e e
rr
r r
ii
i i
zz
z z
aa
a a
tt
t t
ii
i i
oo
o o
nn
n n
ss
s s
~~~~~~~CH
2
- CH

-

CH
2
- C*

Rest of Chain
~~~~~~~CH
2
- C*
X

-
CH
2
= CH
Rest of Chain
X

-
X

-
X

-
Active site
H

-
H

-
1. Initiation
2. Propagation
3.Termination
4. Chain Transfer
Need to consider;
FF
F F
rr
r r
ee
e e
ee
e e
RR
R R
aa
a a
dd
d d
ii
i i
cc
c c
aa
a a
ll
l l
PP
P P
oo
o o
ll
l l
yy
y y
mm
m m
ee
e e
rr
r r
ii
i i
zz
z z
aa
a a
tt
t t
ii
i i
oo
o o
nn
n n

--
- -
II
I I
nn
n n
ii
i i
tt
t t
ii
i i
aa
a a
tt
t t
ii
i i
oo
o o
nn
n n
R - O - O - R 2 R - O
.
R - O
.
+ CH
2
= CHX
R - O - CH
2
- C
.

Peroxide Peroxide
Radical
INITIATION
H

-
X

-
FF
F F
rr
r r
ee
e e
ee
e e
RR
R R
aa
a a
dd
d d
ii
i i
cc
c c
aa
a a
ll
l l
PP
P P
oo
o o
ll
l l
yy
y y
mm
m m
ee
e e
rr
r r
ii
i i
zz
z z
aa
a a
tt
t t
ii
i i
oo
o o
nn
n n

--
- -
PP
P P
rr
r r
oo
o o
pp
p p
aa
a a
gg
g g
aa
a a
tt
t t
ii
i i
oo
o o
nn
n n
~~~~~~~CH
2
- CH

-

CH
2
- C
.
Rest of Chain
~~~~~~~CH
2
- C
.
X

-
CH
2
= CH
Rest of Chain
X

-
X

-
X

-
H

-
H

-
FF
F F
rr
r r
ee
e e
ee
e e
RR
R R
aa
a a
dd
d d
ii
i i
cc
c c
aa
a a
ll
l l
PP
P P
oo
o o
ll
l l
yy
y y
mm
m m
ee
e e
rr
r r
ii
i i
zz
z z
aa
a a
tt
t t
ii
i i
oo
o o
nn
n n

--
- -
TT
T T
ee
e e
rr
r r
mm
m m
ii
i i
nn
n n
aa
a a
tt
t t
ii
i i
oo
o o
nn
n n
X

-
X

-
~~~~~~~CH
2
- CH

- CH - CH
2
~~~~~~~

X

-
X

-
~~~~~~~CH
2
- C
.
Rest of Chain
.
C - CH
2
~~~~~~~
Rest of Chain
H

-
H

-
~~~~~~~CH

- C
.
X

-
Rest of Chain
.
C - CH
2
~~~~~~~
Rest of Chain
X

-
H

-
H

-
H

-
~~~~~~~CH

= CHX H
2
XC - CH
2
~~~~~~~
Rest of Chain Rest of Chain
SSS Shhh hooo orrr rttt t CCC Chhh haaa aiii innn n BBB Brrr raaa annn nccc chhh hiii innn nggg g iii innn n
PPP Pooo olll lyyy yeee ettt thhh hyyy ylll leee ennn neee e
Formation of short chain
branches in polyethylene
~~~CH
2
- CH - CH
2
- CH
2
.


C
4
H
9 -
~~~CH
2
- CH

CH
2
- CH
2
CH
2
.
CH
2
H
~~~CH
2
- CH

CH
2
- CH
2
CH
2
.
CH
2
H
~~~CH
2
- CH - CH
2
- CH
2
- CH
2
- CH
2
.


C
4
H
9 -
CH
2
= CH
2
CH
2
= CH
2
LLL Liii innn neee eaaa arrr r aaa annn nddd d BBB Brrr raaa annn nccc chhh heee eddd d PPP Pooo olll lyyy ymmm meee errr rsss s
Linear
Branched
CCC Crrr ryyy ysss sttt taaa alll llll liii innn niii ittt tyyy y iii innn n PPP Pooo olll lyyy ymmm meee errr rsss s
Let's establish a simple connection between structure and properties right
from the beginning. We'll explore polymer morphology in more detail later,
but simplistically we can get:
RANDOM COILS
Like cooked spaghetti
SEMICRYSTALLINE POLYMERS
A bit like "uncooked spaghetti
TTT Thhh heee e EEE Efff ffff feee eccc cttt t ooo offf f CCC Crrr ryyy ysss sttt taaa alll llll liii innn niii ittt tyyy y
ooo onnn n PPP Prrr rooo oppp peee errr rttt tiii ieee esss s
We will be asking how crystallinity affects
Strength
Stiffness
Toughness
Barrier Properties
Solubility
Transparency
Thermal Properties
Etc
LLL Liii innn neee eaaa arrr r aaa annn nddd d BBB Brrr raaa annn nccc chhh heee eddd d PPP Pooo olll lyyy ymmm meee errr rsss s
Linear
Branched
Which of these is more likely to crystallize?
TTT Thhh heee e aaa annn nsss swww weee errr r iii isss s lll liii innn neee eaaa arrr r !!! !
Various grades of polyethylene are produced commercially and are often
referred to as high density or low density. Which do you think is the
high density polyethylene
A. The linear, more crystalline stuff ?
B. The (somewhat) branched less crystalline stuff ?
Crystallizes
more like this
than this
TTT Thhh heee e aaa annn nsss swww weee errr r iii isss s
sss sttt tiii illl llll l lll liii innn neee eaaa arrr r !!! !
Chains that cannot crystallize
(e.g., highly branched ones), or
even linear chains that are
heated above their crystalline
melting points, actually look
something like cooked spaghetti
or random coils.
They do not pack as closely
together as in the crystalline
state.
TTT Thhh heee e EEE Efff ffff feee eccc cttt t ooo offf f CCC Crrr ryyy ysss sttt taaa alll llll liii innn niii ittt tyyy y
ooo onnn n PPP Prrr rooo oppp peee errr rttt tiii ieee esss s
The type of polyethylene that goes into
milk jugs is stronger, stiffer, but more
opaque (less optically clear) than the type
of polyethylene that is used to make film
wrap (greater optical clarity,more flexible,
but less strong) . Can you figure out which
type of polyethylene is used to make film
wrap ?
A. High density
B. Low density
Property
Strength
Stiffness
Toughness
Optical Clarity

Barrier Properties
Solubility

Generally increases with degree of crystallinity
Generally increases with degree of crystallinity
Generally decreases with degree of crystallinity
Generally decreases with increasing degree of
crystallinity.Semi-crystalline polymers usually appear opaque
because of the difference in refractive index of the amorphous
and crystalline domains, which leads to scattering. Will depend
upon crystallite size.
Change with Increasing Degree of Crystallinity
Small molecules usually cannot penetrate or diffuse through
the crystalline domains, hence barrier properties, which
make a polymer useful for things like food wrap, increase with
degree of crystallinity
Similarly, solvent molecules cannot penetrate the crystalline
domains, which must be melted before the polymer will dissolve.
Solvent resistance increases with degree of crystallinity
High Pressure
High Temperature
Low Molecular Weight
Products (Oligomers)
-olefin
Propylene
CH
2
CH
R
CH
2
CH
CH
3
High Pressure
High Temperature
CH
2
CH
2
Ethylene
Polyethylene (LDPE)
WWW Whhh haaa attt t iii isss s ttt thhh heee e PPP Prrr rooo obbb blll leee emmm m www wiii ittt thhh h PPP Prrr rooo oppp pyyy ylll leee ennn neee e??? ?
FFF Fiii irrr rsss sttt t --- - TTT Thhh heee e MMM Meee ettt taaa alll l OOO Oxxx xiii iddd deee e CCC Caaa attt taaa alll lyyy ysss sttt tsss s
aaa annn nddd d LLL Liii innn neee eaaa arrr r PPP Pooo olll lyyy yeee ettt thhh hyyy ylll leee ennn neee e
Hogan and Banks synthesized polypropylene and linear
polyethylene in a low pressure process using metal oxide
catalysts.
The French can make even
polyethylene look sexy!


AA
A A
CC
C C
oo
o o
mm
m m
pp
p p
aa
a a
nn
n n
yy
y y
MM
M M
aa
a a
kk
k k
ee
e e
rr
r r

The Hula Hoop!
ZZZ Ziii ieee eggg glll leee errr r aaa annn nddd d NNN Naaa attt tttt taaa a
ZZZ Ziii ieee eggg glll leee errr r aaa annn nddd d ttt thhh heee e OOO Orrr rggg gaaa annn nooo ommm meee ettt taaa alll llll liii iccc c CCC Caaa attt taaa alll lyyy ysss sttt tsss s
High Pressure Ziegler Metal Oxide
Polyethylene Polyethylene Polyethylene
Molecular Weight (Mn) 20000 15000 15000
Number of Me groups/1000 Carbons 30 6 < 0.15
Density (g/cc) 0.92 0.95 0.96
Crystalline Melting Point (C) 108 130 133
In his lecture at the Nobel Prize award
ceremony, Ziegler described his preliminary
worka thus, The development began at the end
of 1953 when Holzkamp, Breil, Martin and
myself, in a few almost dramatic days, observed
that the gas ethylene could be polymerized at
100, 20, or 5 atmospheres and finally even at
atmospheric pressure very rapidly in the
presence of certain, easily prepared, catalysts
to give a high molecular weight plastic.
NNN Naaa attt tttt taaa a aaa annn nddd d SSS Sttt teee errr reee eooo orrr reee eggg guuu ulll laaa arrr riii ittt tyyy y
In the middle of 1954, Natta and his coworkers, having been informed by
Ziegler of the nature of his original HDPE catalyst, used it to polymerize
propylene and obtained a partially crystalline, essentially i sotactic,
polypropylene (more on this shortly). Subsequently, Natta and his coworkers
made changes to the catalyst, replacing TiCl
4
with TiCl
3
, which increased the
isotacticity of polypropylene from 50-70 to 80-90%.
II
I I
nn
n n
tt
t t
oo
o o
CC
C C
oo
o o
uu
u u
rr
r r
tt
t t
!!
! !
Nattas research in this area
was funded by the Italian
company Montecatini and a
patent was filed jointly soon
thereafter. Unfortunately, this
caused considerable bad
blood between Ziegler and
Natta and resulted in one of
the longest lasting patent
cases of all time.
SS
S S
uu
u u
mm
m m
mm
m m
aa
a a
rr
r r
yy
y y
1950 - 1953
Ziegler-Natta Catalysts
Metal Oxide Catalysts
Linear PE and stereoregular polyolefins
CC
C C
oo
o o
oo
o o
rr
r r
dd
d d
ii
i i
nn
n n
aa
a a
tt
t t
ii
i i
oo
o o
nn
n n
PP
P P
oo
o o
ll
l l
yy
y y
mm
m m
ee
e e
rr
r r
ii
i i
zz
z z
aa
a a
tt
t t
ii
i i
oo
o o
nn
n n
~~~~~~~CH
2
- CH
X
Rest of Chain
CH
2
= CH
X

-


-
Catalyst
III Isss sooo ommm meee errr riii isss smmm m iii innn n PPP Pooo olll lyyy ymmm meee errr rsss s
Two molecules are said to
be isomers if they are
made up of the same
number and types of
atoms, but differ in the
arrangement of these
atoms.
Sequence isomerism
Stereoisomerism (in vinyl polymers)
Structural isomerism (in diene polymers)
Polymerization of a vinyl
monomer, CH
2
= 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 of
tacticity.
SSS Sttt teee errr reee eooo oiii isss sooo ommm meee errr riii isss smmm m iii innn n
VVV Viii innn nyyy ylll l PPP Pooo olll lyyy ymmm meee errr rsss s
Meso Diad
Racemic Diad
III Isss sooo ottt taaa accc cttt tiii iccc c CCC Chhh haaa aiii innn nsss s
Part of an isotactic
polypropylene chain
seen from the side
The same chain seen
more from the top
SS
S S
yy
y y
nn
n n
dd
d d
ii
i i
oo
o o
tt
t t
aa
a a
cc
c c
tt
t t
ii
i i
cc
c c
CC
C C
hh
h h
aa
a a
ii
i i
nn
n n
ss
s s
Here are two more polypropylene chains, both shown as if we were looking
down from on top. One of these consists of units that are all racemic to
one another and is called syndiotactic. The other has a random arrangement
of units and we call such chains atactic. Which one is the atactic chain , A
or B ?
A
B
TTT Taaa accc cttt tiii iccc ciii ittt tyyy y iii innn n SSS Sooo ommm meee e CCC Cooo ommm mmmm meee errr rccc ciii iaaa alll llll lyyy y
III Immm mppp pooo orrr rttt taaa annn nttt t PPP Pooo olll lyyy ymmm meee errr rsss s
Polystyrene - atactic
Polypropylene - largely isotactic
PVC - largely atactic
(Some syndiotactic sequences ?)
PMMA - atactic