POLYMERIZATION REACTIONS

Understand the differences between step-growth and

chain-growth polymerization reactions.
Predict the products of polycondensation and polyaddition
reactions.
Explain how reactant ratios and monomer purity may affect
the degree of polymerization.
Understand the initiation, propagation, and termination
processes in free-radical, ionic, coordination (Ziegler-
Natta), and ring-opening polymerizations.
Explain how the nature of the reaction catalyst influences
polymer structure (stereoregularity and tacticity).

STEP-GROWTH POLYMERIZATION
Formerly: Condensation polymerization (Carothers,
1931)

Monomers are difunctional each has two reactive

functional groups

Chain growth occurs through coupling (condensation,

addition) reactions

[Monomer] decreases rapidly before any high-MW

polymer is formed

Rate of polymerization is highest at outset, decreases

as chain ends are consumed long reaction times

Pzn Reactions 4-1

 Schematic:

( )n
nA + nB AB

Addition: ( )n
nA + nB AB
Condensation: ( )n + Y
nA + nB AB

The number average degree of polymerization

(Xn) is
N0 Number of molecules at start
DP = Xn = =
N Number of molecules at end

The ratio [A]:[B]

The ratio [A]:[B] strongly
strongly
influences
influences chain
chain length
length

N0/N Xn
A B A B A B A B A B A B 12/12 1
A B A B A B A B A B A B 12/11 1.1
A B A B A B A B A B A B 12/10 1.2
A B A B A B A B A B A B 12/9 1.3
A B A B A B A B A B A B 12/8 1.5
A B A B A B A B A B A B 12/7 1.7
A B A B A B A B A B A B 12/6 2
A B A B A B A B A A A B 12/5 2.4
A B A B A B A B A B A B 12/4 3
A B A B A B A B A B A B 12/3 4
A B A B A B A B A B A B 12/2 6
A B A B A B A B A B A B 12/1 12

Pzn Reactions 4-2

 Degree of Polymerization

10

Xn 6

2 4 6 8 10
Reaction Step Number

Representative Step-Growth Reactions

Condensation Reactions
Polyester (Polyethylene terephthalate/PET) O

HO (CH2)2 OH + HOOC COOH O (CH2)2 OC COO + H2O

Polyamide (Nylon-6,6) O
H2N ( CH2)6 NH2 + HOOC ( CH2)4 COOH HN ( CH2)6 NC ( CH2 )4 CO + H2O
H

Addition Reactions
Polyurethane
DABCO
HO (CH2)2 OH + OCN CH2 NCO O

O (CH2)2 OCN CH2 NHCO

H

See also Table 3.2, pp 25-26

Pzn Reactions 4-3

 Predicting Molar Mass in Step-Growth Pzns

The extent of reaction (p) is

Number of functional groups reacted
p =
Initial number of functional groups

Since the total number of molecules (N) decreases by 1

for each condensation step,
N0 N N0 1
p = or =
N0 N 1p

11
XXn ==
Carothers equation
n
1p
1p

Carothers Equation

150

Xn 100

50

0.2 0.4 0.6 0.8

p

Pzn Reactions 4-4

 Step-Growth Reactions: MW Distribution

N0 1
Xn = =
N 1p
The corresponding weight-average degree of poly-
merization is
1+p
Xw =
1p
The molecular weight distribution (polydispersity)
is therefore
Xw
= 1 + p
Xn
as p 1, MWD 2 for any linear step-growth
pzn

Molecular Weight Control

( )n
nA + nB AB
Lowering the temperature before the reaction is complete
can reduce product MW.
Result: a thermally unstable product.
Alternative: use a non-stoichiometric reactant ratio ([A] <
[B]). The less abundant reactant is consumed completely.
In terms of functional groups (NA < NB), the reactant ratio
is
NA
r = < 0
NB
Substituting gives the general Carothers equation:

11 +
+ rr
XXn =
n =
11 +
+ rr 2rp
2rp

Pzn Reactions 4-5

 Molecular Weight Control (cont.)
11 +
+ rr
XXn ==

n
11 +
+ rr 2rp
2rp

Xn
r p = 0.900 p = 0.950 p = 0.990 p = 0.999
1.000 10.0 20.0 100.0 1000.0
0.999 10.0 19.8 95.3 666.8
0.990 9.6 18.3 66.8 166.1
0.950 8.1 13.4 28.3 37.6
0.900 6.8 10.0 16.1 18.7

Molecular Weight Control (cont.)

Producing high-MW step-growth polymers requires

High conversions (p > 0.98)

Stoichiometric ratios of functional groups

High-purity monomers

No side reactions

Pzn Reactions 4-6

 CHAIN-GROWTH POLYMERIZATION
Formerly: Addition polymerization (Carothers, 1931)

Polymerization requires an initiator, a substance that

starts the reaction

Chain growth occurs by addition of monomer to a

relatively small number of initiation sites (free
radicals, anions, cations, transition metal complexes)

Reaction mixture contains monomer, high polymer,

and a low concentration of growing chains

[Monomer] decreases steadily as polymer is formed

Schematic:

Initiator nM Mn

Initiation: I + M IM*
Propagation: IM* + nM IMnM*
Termination: Reactions depend on M and M*

Moles of monomer consumed

DP = Xn =
Moles of chains produced

The ratio [initiator]:[monomer]

The ratio [initiator]:[monomer]
strongly
stronglyinfluences
influenceschain
chainlength
length

Pzn Reactions 4-7

 Molcons Xn
I A A A A A A A A A A A A 0
I A A A A A A A A A A A A 1 1
I A A A A A A A A A A A A 2 2
I A A A A A A A A A A A A 3 3
I A A A A A A A A A A A A 4 4
I A A A A A A A A A A A A 5 5
I A A A A A A A A A A A A 6 6
I A A A A A A A A A A A A 7 7
I A A A A A A A A A A A A 8 8
I A A A A A A A A A A A A 9 9
I A A A A A A A A A A A A 10 10
I A A A A A A A A A A A A 11 11
I A A A A A A A A A A A A 12 12

Degree of Polymerization

10

Xn 6

2 4 6 8 10
Reaction Step Number

Pzn Reactions 4-8

 Representative Chain-Growth Reactions
Free-Radical Vinyl Pzns
Poly(methyl methacrylate)
COOCH3 COOCH3
K2S2O8
H2C C CH2 C
n
CH3 CH3

Carbocationic/Anionic Pzns
Butyl Rubber (IIR)
CH3 CH3 CH3 CH3
AlCl3
H2C C + HC C CH2 C CH2 C CH CH2
CH3Cl
98n 2n
CH3 H2C CH2 CH3

Coordination Pzns See also Table 3.2, pp 25-26

Polypropylene
H H H H H
TiCl3/AlCl3
H2C C CH2 C CH2 C CH2 C CH2 C
Al(C2H5)2Cl
R2O n
CH3 CH3 CH3 CH3 CH3

Reactant Compatibilities
Mechanism*
Monomer Radical Cationic Anionic Coordn
Ethylene + + +
-Olefins ( C3) +
1,1-Dialkylalkenes +
1,3-Dienes + + + +
Styrene, -Me styrene + + + +
Vinyl chloride + +
Tetrafluoroethylene + +
Acrylate/methacrylate esters + + +
Acrylonitrile, methacrylonitrile + + +
Vinyl ethers + +
Vinyl esters +
*Plus (+) sign = high polymer; minus () sign = no reaction or oligomer.

See also Table 5.1, p 124

Adapted in part from G. Odian, Principles of Polymerization, 4th Ed, 2004, p
200; and F.W. Billmeyer, Jr, Textbook of Polymer Science, 3rd Ed, 1994, p 83.

Pzn Reactions 4-9

 Vinyl Free Radical Polymerization

Alkene, 1,3-diene monomers

Haloethylenes: H2C CH Cl

Styrene: CH CH2 O

Acrylic, methacrylic acid derivatives: H2C CH CN H2C C C OCH3

CH3
Free radical initiators O O

Benzoyl peroxide: C O
2
2 C O
CH3

Azobisisobutyronitrile (AIBN): NC C(CH3)2
2
N2 2 NC C + N2
CH3
2 2
K persulfate (peroxydisulfate): O3SO OSO3 2 O3SO

Thermal, redox, or photochemical initiation

Initiation
O O

C O
2
2 C O = I

H H H

I + H2C C I C C
H

Propagation
H H H H H H H

I C C + H2C C I C C C C

H H H

Pzn Reactions 4-10

 Termination
H H H H H H H H
Chain
C C C C + H R C C C C H + R
Transfer
H H H H

H H H H H H H
C C C C H + C C C C
H H H H

H H H H H H H H
C C C C + C C C C
H H H H

H H H H H H H H
C C C C C C C C
Chain
Addition H H H H

Molecular Weight Control

Most monomer is (or should be) consumed by polymer

chain growth, not initiation.
Termination involves reactions that stop polymerization.
Chain transfer to monomer, solvent, or initiator kills the
polymer chain but continues the kinetic chain (new chains
can be initiated):
Mi + X Mi + X
Chain length is proportional to [M] and 1/[I]:

[M]
[M]
XXn = K
n = K
[I]
[I]

To maximize DP, increase [M]:[I] in the reaction mixture or

increase K by the choice of monomer.

Pzn Reactions 4-11

 Molecular Weight Control (cont.)

If chain transfer processes to both monomer (M) and

solvent (S) are important:

11 11 [S]
[S]

= =
+ +CCSS
+CCMM+ Mayo (Mayo-Walling) eqn
XXn XXn0 [M]
[M]
n n0

where Xn0 is the DP you get with no chain transfer.

If transfer to monomer is not important, then

11 11 [S]
[S]

= =
+ +CCSS
Simplified Mayo eqn
XXn XXn0 [M]
[M]
n n0

The
The reciprocal
reciprocal of of DP
DP should
should be
be aa linear
linear function
function of
of the
the
ratio of [S]
ratio of to [M].
[S] to [M]. The
The slope
slope would
would be be aa function
function of
of the
the
rate
rateof
ofchain
chaintransfer
transfertotosolvent.
solvent.

Styrene Pzn: Chain Transfer to Solvent

CH3

CH

CH3
CH2CH3

150

CH3

105
100
Xn

50
H

1/Xn0

5 10 15 20
[S]/[M]

Adapted from R.A. Gregg & F.R. Mayo, 1947 Disc. Faraday Soc., 2, 328-337

Pzn Reactions 4-12

 Styrene Pzn: Chain Transfer to Solvent

Mi + XH MiH + X

H H

P CH2C + XH P CH2C H + X

Function slopes show relative ease of radical (X) formation:

CH3 H H

C > C > C >

CH3 CH3 H

Carbocationic Chain-Growth Pzn

Alkene, 1,3-diene monomers CH3

Isobutylene (2-methylpropene): H2C C CH3

Isoprene (2-methyl-1,3-butadiene): H2C C CH CH2

-Pinene: CH3
CH2

H3C
Lewis acid catalysts CH3

AlCl3
BF3
(CH3CH2)2AlCl

Brnsted acid or carbocation-donor co-catalysts

HCl or H2O: BF3 + H2O F3BOH2
RCl: AlCl3 + (CH3)3CCl (CH3)3C+AlCl4

Pzn Reactions 4-13

 Initiation

F3BOH2 F3BOH + H+

CH3 CH3

F3BOH + H+ + H2C C H3C C+ F3BOH

CH3 CH3

Propagation
F3BOH
F3BOH CH3 CH3 CH3 CH3

H3C C+ + H2C C H3C C CH2 C+

CH3 CH3 CH3 CH3

Termination

CH3 H CH3 CH3 H CH3

Chain
CH2 C C C+ CH2 C C C + F3BOH2
Transfer
CH3 H CH3 CH3 CH3
F3BOH

CH3 H CH3

CH2 C C C+ + H O R

CH3 H CH3
F3BOH Quenching

CH3 H CH3

CH2 C C C OR + F3BOH2

CH3 H CH3

Pzn Reactions 4-14

 Molecular Weight Control

11 CCt

= =
+
t
+CCMM Simplified Mayo equation
XXn [M]
[M]
n

Reactions are extremely rapid controlling heat

transfer is important.
Chain transfer to monomer is often significant.
DP is independent of initiator concentration.
For a typical exothermic polymerization, the reaction
rate increases as the temperature is reduced.
Net outcome:
DP increases at lower temperature

Anionic Chain-Growth Polymerization

Alkene, 1,3-diene monomers

1,3-butadiene: H2C CH CH CH2

Styrene: CH CH2
H3C O

Methyl methacrylate: H2C C C OCH3

Vinyl pyridine: CH CH2

N

Catalysts: Lewis bases, organometallics

NH2
CH3CH2CH2CH2Li (n-butyllithium)

Na+

Pzn Reactions 4-15

 Initiation

H H H
C4H9 Li + H2C C C4H9 C C Li+
H

Propagation

H H H H H H H

C4H9 C C Li+ + H2C C C4H9 C C C C Li+

H H H

Molecular Weight Control

Anionic polymerizations lack inherent termination

processes (ion-pair rearrangements, anion-metal
cation reactions).

Monomer molecules only react with the anionic end

groups on the propagating polymer chains.

Polymer chains continue to grow as long as

additional monomer is added. These chains are

Living Polymers

Pzn Reactions 4-16

 Molecular Weight Control (cont)

[M]0
DP = Xn = p
[I]0
where p is the fraction of monomer converted.
At complete conversion, DP is the monomer:initiator ratio at
the outset of reaction:

[M]
[M]00
DP
DP= =
=XXnn=
[I]
[I]00

The MWD (polydispersity) is therefore :

XXw 11 The
The MWD
MWD of
of aa living
living anionic
anionic polymer
polymer

=
w
+
=11+ will
XXn

XXn will be extremely narrow, tending
be extremely narrow, tending
n n toward
towardaavalue
valueofof11asasXXn increases.
increases.
n

Anionic Pzn as a Route to Block Copolymers

Living polymerization yields polymer chains with reactive

end groups:
RSSSSLi+

These living chains can react with a second monomer to

extend the chain and create a final product with unique
chemical and physical properties:
RSSSSLi+ + nB RSSSSBBBBLi+

Block copolymers comprise two or more homopolymer

subunits. These are referred to as n-block copolymers.

Commercial block copolymers include SIS (styrene-

isoprene-styrene) and SBS (styrene-butadiene-styrene)
triblocks.

Pzn Reactions 4-17

 Controlling Stereochemistry

Natural polymers have a high level of structural regularity:

H CH3 H CH3 H CH3 H CH3 H CH3
3C C2 C C C C C C C C
H2C CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2
4 1

cis-1,4-Polyisoprene (NR)

Synthetic polymers often contain many structures:

H CH3 H CH3 H CH3 Mi CH2 CH3

C C Mj Mj C C C C C C
H2C CH2 Mi Mi CH2 CH2 Mi CH2 CH2 Mj H CH2 Mj

1,2-addition 3,4-addition cis-1,4-addition trans-1,4-addition

STEREOCHEMISTRY
STEREOCHEMISTRY
Properties
Propertiesthat
thatrelate
relateto
toaa
molecules
molecules3-dimensional
3-dimensionalstructure.
structure.

Controlling Stereochemistry (cont.)

IR Structure, mol fraction
Conditions
cis-1,4 trans-1,4 1,2 3,4

Free-radical, 20C 0.01 0.90 0.05 0.04

Free-radical, 100C 0.23 0.66 0.05 0.06

Anionic, RLi, 30C 0.94 0.01 0.00 0.05

Polymer structures depend on

Monomer structure and conformation (cisoid vs. transoid)
H CH3 H CH2
C C C C
H2C CH2 H2C CH3

Nature of active unit structure (free radical vs. anion)

Stability of active unit structure (cis-trans isomerization in 1,4-
addition)

Pzn Reactions 4-18

 Controlling Stereochemistry (cont.)
H CH2 H CH2
C C C C
H CH2 H2C CH3 H CH2 CH2 CH3

C C C C
P CH2 CH3 P CH2 CH3 1,4-trans addition

H CH3
Free-radical C C
H CH2 CH2 CH2
C C
P CH2 CH3 1,4-cis addition
Anionic

H CH3 H CH3 H CH3

C C C C C C

P CH2 Li+ CH2 P CH2 CH2 Li+ P CH2 CH2
H2C Li CH2
+
H2C CH3 H2C CH2
C C C C C C
H CH2 H CH3 H CH3

1,4-cis addition

Ziegler-Natta Catalysis:
Coordination Chain-Growth Polymerization
Alkene, cycloalkene, 1,3-diene monomers
Propylene (Propene): H2C CH2 CH3

1,3-Butadiene: H2C CH CH CH2

5-Ethylidene-2-norbornene: CH CH3

Group 4B-8B transition metal catalysts

TiCl4
VCl4
Ti Cl
Ti, Zr metallocenes Cl

Group 1A-3A metal co-catalysts/activators

(CH3CH2)3 Al (with TiCl4)
[Al(CH3)O]n (with titanocene dichloride)

Pzn Reactions 4-19

 Ziegler-Natta Catalysts

Active catalyst produced by reaction of transition metal

component with Group 1A-3A co-catalyst:

TiCl4 + (C2H5)3Al Cl3TiC2H5 + (C2H5)2AlCl

The concentration of active catalyst [C*p] is (0.01-10)n% of

[transition metal component].

Termination reactions are relatively unimportant.

DP tends to be high
Reactions must be quenched by active H sources (H2):

Cl3TiMnC2H5 + [H] Cl3TiH + HMnC2H5

Kinetics of Coordination Polymerization (cont.)

Cl Cl Cl

Cl Cl Cl
Ti Cl Ti Cl Ti
Cl Cl Cl
Et H
Et CH2
H C CH3
C CH3 Cl
H C
H C C H
H H3C
H Et
Specific
stereochemistry
Adapted in part from E.J. Arlman, Jr, & P. Cossee, 1964 J. Catal., 3, 99-104.

Pzn Reactions 4-20

 Stereochemistry of Polymerization

The stereochemistry of polymer chain propagation

controls the relative stereochemistry (tacticity) of the
polymer.
In ionic polymerizations, high stereoregularity can be
achieved if there is strong coordination of the
counter-ion with the terminal unit on the growing
chain. (Promoted by low reaction T, polar substituent
groups)
Stereoregularity influences chain-chain interactions,
chain stiffness, crystallizability.

TACTICITY
TACTICITY
The
Therelative
relativestereochemistry
stereochemistryof
ofadjacent
adjacent
chiral centers within a macromolecule
chiral centers within a macromolecule

H H H R H R H H H R H H

C C C C C C C C C C C C

H R H H H H H R H H H R

ATACTIC
ATACTIC
random
randomconfigurations
configurations

Pzn Reactions 4-21

 H H H H H H H H H H H H

C C C C C C C C C C C C

H R H R H R H R H R H R

ISOTACTIC
ISOTACTIC
identical
identicalconfigurations
configurations

H H H R H H H R H H H R

C C C C C C C C C C C C

H R H H H R H H H R H H

SYNDIOTACTIC
SYNDIOTACTIC
alternating
alternatingconfigurations
configurations

Pzn Reactions 4-22

 Stereoselective Polymerizations
Monomer Conditions Structure

IsoC4 vinyl ether Et2OBF3 in propane, 80 to 60C isotactic

n-C4H9Li in toluene, 78 to 0C isotactic
Me methacrylate
n-C4H9Li in THF, 78C syndiotactic
TiCl4-Et3Al in heptane, 50C isotactic
Propylene
VCl4-Et3Al + PhOCH3 in toluene, 78C syndiotactic

Atactic Isotactic Syndiotactic

Property Polypropylene Polypropylene Polypropylene

Melting point, C 160-171 130-160

Crystallinity, % 0 55-65 50-75

Adapted from G. Odian, Principles of Polymerization, 4th Ed, 2004, p 640.

Comparing Step-Growth & ChainGrowth Pzn

Step-Growth Chain-Growth

Any two species can Rapid addition to small

Monomer addition combine (monomer or number of active
polymer) centers

Much slower than chain

Reaction rate growth
Rapid and constant

Increases continuously High MW present even

MW growth as monomers react at low conversion

Continuous, semi-
Process type Batch
batch

BR, IR, SBR, IIR,

Examples Nylon, PETE
EPM, EPDM

Adapted from ExxonMobil Chemical Polymer Technology Course 2009.

Pzn Reactions 4-23

 RING-OPENING POLYMERIZATION
Chain-growth reactions. Proceed by relieving
Strain in small-ring monomers
Steric crowding in large-ring monomers

Reactions are catalyzed by

Free radicals
Anions
Cations
Transition metal-carbene complexes

(C6H11)3P
Cl H

Example: Ru C
Cl
(C6H11)3P

RING-OPENING PZN (cont.)

Polymerizations follow two general pathways:
Ring opening of cyclic monomers: ethers (epoxides),
esters (lactones), amides (lactams), etc.
(CH2)x
n (CH2)x Y Y = O, COO, CONH
n
Y

Ring-opening metathesis polymerization (ROMP) of

olefins: cycloalkenes, bicycloalkenes
H H M
M RHC C M RHC C
+ (CH2)x (CH2)x HC HC CH HC CHR
H
HC HC C HC HC C C
(CH2)x n+1
H H n (CH2)x
C
H

METATHESIS
METATHESIS
The
Theexchange
exchangeor
ortransposition
transpositionof
of
bonds
bonds between tworeactants
between two reactants

Pzn Reactions 4-24

 Representative Ring-Opening Pzns
Ring-Opening Pzn of Epoxides
Polyethylene glycol (PEG) from ethylene oxide

H2C HOCH2CH2OH
n O HOCH2CH2 OCH2CH2O CH2CH2OH
KOH
H2C n1

Ring-Opening Pzn of Lactams

Nylon-6 from -caprolactam
H2 O
C C O
H2C 260C
n NH N2 C CH2CH2CH2CH2CH2 NH
H2C
C CH2 n

H2

ROMP of Bicycloalkenes
Polynorbornene Rubber (PNR)
H
RuCl3/HCl C
n
C4H9OH C C C
H H n H n

COPOLYMERIZATION
Simultaneous polymerization of two or more mono-
mers yields copolymers with unique properties unlike
those of homopolymers from each monomer.
Copolymers with irregular (random) monomer
sequences can have rubber-like properties because
of reduced crystallinity.
Appropriate reaction conditions can provide a range
of tailored structures:
Random (statistical) ABBABAABABBAABAB
Alternating ABABABABABABABAB
Block AAAABBBBAAAABBBB
Graft AAAAAAAAAAAAAAAA
BBBB BBBB

Pzn Reactions 4-25

 Composition Control

Monomers differ in their ability to copolymerize.

The relative rates of monomer reaction are a function

of the monomer concentrations ([M1],[M2]) and the
monomer reactivity ratios (rn):

k11 k22
r1 = r2 =
k12 k21

where kij is the rate constant for the reaction of

monomer i with monomer j.

Reactivity ratios determine copolymer composition

and structure.

Free Radical Pzn: Reactant Ratios

Monomer 1 r1 Monomer 2 r2 T, C
0 Acrylonitrile 7 20
Ethylene
0.79 Vinyl acetate 1.4 130
0.58 1,3-Butadiene 1.4 50
Styrene 0.29 Acrylonitrile 0.020 60
55 Vinyl acetate 0.01 60
0.78 1,3-Butadiene 1.4 5
Me acrylate 0.84 Acrylonitrile 1.5 50
6.4 Vinyl acetate 0.03 60

Adapted from G. Odian, Principles of Polymerization, 4th Ed, 2004, pp 491-492.

Pzn Reactions 4-26

 Composition Control (cont.)

Limiting (or idealized) reactivity ratios:

r1 = r2 = 0 Neither chains end adds its own monomer.

Results: 1. a perfectly alternating copolymer and 2. an
azeotropic copolymer composition (the ratio of monomers
in the feed = the ratio of monomer units in the copolymer).

r1 = r2 = Each chain adds only its own monomer. Result:

a mixture of homopolymers.

r1r2 = 1 or r1 = r2 = 1 All chain ends add either monomer

with equal probability in an ideal copolymerization. Result:
a random copolymer.

Composition Control (cont.)

In most cases ri is not exactly 0, 1, or ; polymers tend

toward a particular composition and type of structure.

Comonomer sequences can be inferred from r1r2 values:

r1r2 < 1 Tendency toward alternating structure
r1 r 2 > 1 Tendency toward block structure
r1r2 >> 1 Tendency toward homopolymer structure

When r1 >> 1 >> r2 there is copolymer composition drift.

At low conversions, the copolymer is enriched in the more
reactive monomer.
At high conversions, the copolymer is enriched in the less
reactive monomer that remains.

Composition drift can be reduced by delayed or (semi-

batch) continuous addition of the more reactive monomer.

Pzn Reactions 4-27

 Composition Control (cont.)
In terms of the mole fraction () of each monomer in the
co-monomer mixture,

[M1] [M2]
1 = 2 = 1 1 =
[M1] + [M2] [M1] + [M2]

the copolymer equation, expressed as the mole fraction

(F) of each monomer unit in the copolymer chain, is:
r112 + 12
F1 =
r112 + 212 + r222
F2 = 1 F1

These equations can be used to calculate the relationship

of reactant feed composition to instantaneous polymer
composition for various reactant ratios.

Copolymer Composition: Impact of r1r2

sition
compoift
dr
0.8
Styrene Vinyl Cl
17 0.02
r1r2 = 0.34

0.6

alternating
F1
Maleic
Stilbene Anydride
0.4
m
do
0.03 0.03
n r1r2 = 0.0009
ra
Styrene Butadiene
0.2
0.78 1.39
r1r2 = 1.1

0.2 0.4 0.6 0.8

1

Pzn Reactions 4-28

 Exercise

The graph shows the feed and product

compositions for the free-radical
reaction of styrene (monomer 1) 0.8
and acrylonitrile (monomer 2).
What feed composition do you need to
0.6
get a copolymer that is 50%
styrene? F1

a) About 55% styrene 0.4

b) About 55% acrylonitrile

c) About 25% styrene
0.2

What kind of copolymer will you get?

a) One that tends to have an
0.2 0.4 0.6 0.8
alternating structure. 1
b) One that is enriched in styrene.
c) One that tends to be a mixture of
copolymers.

Polymerization 4-29