CN4203 Polymer Engineering

Chapter 2. Step Polymerization

Lecturer: Dr. Liu Bin
Office: E5-02-17
Tel: 6516-8049
Email: cheliub@nus.edu.sg

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 Polymer Chemistry
• Cowie and Arrighi: chapters 2, 3, 5
(Young and Lovell: chapters 1, 2)
– Week 2: Step polymerization
– Week 3: Chain polymerization
– Week 4: Copolymerization

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 Polymer Synthesis
• Step Polymerization
• Chain Polymerization
• Ionic Polymerization
• Copoloymerization
• Other polymerization, e.g. coordination,
ring-opening, group-transfer, and living
polymerization

3
 Step Polymerization
• Also known as condensation polymerization or
step-growth polymerization
– Condensation polymerizations to yield polymers with
repeat units having fewer atoms than present in the
monomers from which they are formed
– Addition polymerizations to yield polymers with repeat
units having identical molecular formulae to those of the
monomers from which they are formed
• Some addition polymerization are now also part of
step polymerization

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 Step Polymerization
• Features:
– Polymer formed from step-wise intermolecular
reaction of one type only
– Monomer units react with each other or with
polymers of any size
– Functional end-groups of monomers are
assumed to have same reactivity as that of
end-groups of polymers
– Functionality?
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 Linear Step Polymerization
• To produce linear polymer, what is the
functionality of the monomer?
• Functionality of 1
CH3COOH + CH3CH2OH CH3COOCH2CH3 + H2O

• Functionality of 2
HOOC COOH + HOCH2CH2OH

HOOC COOCH2CH2OH + H2O

• Functionality of >2
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Linear Step Polymerization

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Examples

8
Examples

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 Polycondensation
• Polymerization reactions with by-products that
are eliminated
• RA2 + RB2 polymerizations:
nHOOC R1 COOH + nHO R2 OH

H OOC R1 COO R2 nOH + (2n-1) H2O

• ARB polymerizations:
nHO R COOH HO R COO n H + (n-1) H2O

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 Polycondensation
nHO R OH H O R n OH + (n-1) H2O

nHOOC R1 COOH + nH2N R2 NH2

H HN R1 NHOC R2 CO n OH + (2n-1) H2O

CH3 CH3
nCl Si Cl + (n+1) H2O HO Si O H + 2n HCl
CH3 CH3
n
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 Polyaddition
• Polymerization reactions without by-products
• RA2 + RB2 polymerizations:
nO C N R1 N C O + nHO R2 OH

O O
C NH R1 NH C O R2 O
n

• RA2 polymerizations:

(n+1) +
n

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 Carothers Theory
• To predict molecular weight, define number-
average degree of polymerization
No
xn =
N
N0:number of molecules present initially
N: number of molecules remaining after a time t of polymerization
• Extent of reaction p at time t

# of functional groups reacted N o − N

p= =
# of initial functional groups No
1
⇒ xn =
1− p 13
 Carothers Theory
• Number average molecular weight
M n = M o xn M0:mean molar mass

• If the reactant ratio, r = (NA/NB)

N A + N B N B (1 + r )
then N o = =
2 2
number of unreacted A groups = N A − pN A = rN B (1 − p )
N B (1 + r − 2rp )
⇒N=
2
1+ r
∴ xn =
1 + r − 2rp 14
Examples

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 Statistical Theory
• To predict size distribution, by Flory
• Using probabilities, at extent of reaction p
( x −1)
P ( x) = (1 − p) p
• P(x) of random molecule is mole fraction, so
total number of molecules, N and
N x = N (1 − p ) p ( x −1) = N o (1 − p ) p ( x −1)

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 Statistical Theory
• If wx = weight fraction of molecules with x-
monomers, then
• Most Probable Distribution (Schultz-Flory)

N x ( xM 0 )
wx =
No M 0
( x −1)
= x(1 − p ) p
2

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 Mole Fraction Distribution

P(x)

Mole fraction distribution for various extents of reaction in a linear step polymerization
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 Weight Fraction Distribution

Wx

Weight fraction distribution for various extents of reaction in a linear step polymerization
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 Statistical Theory
• From distributions, calculate number-average
molecular weight
M n = ∑ P( x) M x = ∑ xM 0 (1 − p ) p ( x −1)

M0
simplifies to M n =
(1 − p )
• And weight average molecular weight
M w = ∑ wx M x = M 0 (1 − p ) 2 ∑ x 2 p ( x −1)
(1 + p )
simplifies to M w = M 0
(1 − p )
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 Statistical Theory
• Therefore, weight average DP
(1 + p )
xw =
(1 − p )

• And PDI
Mw
= 1+ p
Mn

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 Kinetics
• Because of equal reactivities, define overall rate
of reaction as
d[A] d[B]
− =− = k[A][B]
dt dt
dc
or − = kc 2
dt
• Integrate from t = 0 and c = c0 gives
1 1
− = kt
c c0
1
or − 1 = c0 kt
1− p 22
 Kinetics
• If polymerization is catalyzed by monomers,
d[A]
− = k ''[A][B][A]
dt
dc
⇒ − = k '' c 3
dt
integrated to
1 1
2
− 2 = 2k '' t
c c0
1
or − 1 = 2c 2
0 k '' t
(1 − p) 2

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 Polymerization systems
• Due to problems with forming high molar mass polymers
(what are the problems?), special polymerization
systems are developed
• For polyesters, direct esterification is followed by ester
interchange

HOOC COOH + (2+x) HOCH2CH2OH

HOCH2CH2OOC COOCH2CH2OH + 2 H2O + x HOCH2CH2OH

n HOCH2CH2OOC COOCH2CH2OH

HOCH2CH2O OC COOCH2CH2O H + (n-1) HOCH2CH2OH

n
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 Polymerization systems
• For polyamides, melt polymerization is used from nylon
salt
nH2N(CH2)6NH2 + nHOOC(CH2)4COOH

+ + - -
NH3N (CH2)6N H3O OC(CH2)4COO

H NH(CH2)6NHOC(CH2)4CO nOH + (2n-1) H2O

• Interfacial polymerization is also used for polymerization

of nylon at low temperatures

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 Non-linear Step Polymerization
• For monomers with functionality >2, branched and
network polymers are formed
• Gel-point is when the first network molecule is formed,
causing gelation

– Gelation: an abrupt change of the reacting mixture from a

viscous liquid to a solid gel which shows no tendency to flow

• Formaldehyde resins (phenol-, urea-, melamine-

formaldehyde)
• Epoxy resins
• Polyurethanes

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 Gelation
• To predict gel-points, Carothers theory is used
• Number-average functionality
f av = ∑ N i f i / ∑ N i
• Total number of functional groups initially is Nofav
• The extent of reaction is then
2( N o − N ) 2 ⎛ 1⎞
p= = ⎜1 − ⎟
N o f av f av ⎝ xn ⎠
2
or xn =
2 − pf av
• The critical extent for gelation is then
pc = 2 / f av
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 Gelation

2
Values of Xn for different p and fav calculated using xn =
2 − pf av

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 Gelation

Variation of p, Xn, and η with time for the polymerization of ethylene

glycol with succinic acid and 1,2,3-propane tricarboxylic acid.
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 Gelation
• Using statistical theory (by Flory) of f-functional
monomers
• Branching coefficient, α, is the probability of f–functional
unit connected to chain of difunctional units connected to
another f–functional unit
(f-1) AR AB R B[A R AB R B]iA R A(f-1)
• Initial ratio of A groups from RAf to total A groups is γ,
then probability of general linkages is
p A [ pB (1 − γ ) p A ]i pBγ

• And α is probability of sequences with all values of i is

∞ i

α = pA pBγ ∑ [ pA pB (1 − γ ) ] = pA pBγ [1 − pA pB (1 − γ )]−1

i =0 30
 Gelation
• The critical branching coefficient for gelation is then
1
αc =
( f − 1)
• And the product of critical extents of reaction at gelation
is
1
( p A pB ) c =
1 + γ ( f − 2)
• With reactant ratio, r such that pB= rpA,

( pA )c = [r + rγ ( f − 2)]−1/ 2
( pB )c = r1/ 2 [1 + γ ( f − 2)]−1/ 2
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