Chapter 3-Step-Condensation Polymerization-2

Step/Condensation Polymerization
Chapter Overview
Examples of step polymerization
Basic requirements and assumptions
Kinetics of step polymerization
Molecular weight
Complications in the kinetic analysis of the data
Equilibrium condensation polymerization
closed system
open system
molecular weight control
1
Examples of step polymerizations: Polyamides, fiber-forming polymers
(diamine) (diacid)
O O (equilibrium)
n H2N-R1-NH2 + n HO C R2 C OH
(polyamide: Nylon 66 with R1=-(CH2)6- and R2 =-(CH2)4-)
H H O O
H N R1 N C R2 C OH + (2n-1) H2O
n
(diamine) (diacyl chloride) Adipic acid-vs-

O O Adipoyl chloride
n H2N-R1-NH2 + n Cl C R2 C Cl
H H O O
H N R1 N C R2 C Cl + (2n-1) HCl
n 2
Making the News!
On October 27, 2005, Apple officially
introduced the i-phone to a crowd of 4,000
enthusiasts at the future site of the New York
Worlds Fair. But while the excitement was
building, the i-phones themselves would not
become commercially available for another 18
months. At that point the only customers who
could experience the i-phones firsthand either
worked for Apple or were married to Apple
scientists in the i-phone division. A limited
supply of the first i-phones went on sale in
Wilmington, Delaware, in October 2006, but
the i-phones did not reach the national market
until May 15, 2007. When they did, the stores
were taken by storm and they were sold out at
most locations by noon.
Making the News!
On October 27, 2005, Apple officially On October 27, 1938, DuPont officially
introduced the i-phone to a crowd of 4,000 introduced the nylon stockings to a crowd of
enthusiasts at the future site of the New York 4,000 enthusiasts at the future site of the New
Worlds Fair. But while the excitement was York Worlds Fair. But while the excitement
building, the i-phones themselves would not was building, the stockings themselves would
become commercially available for another 18 not become commercially available for another
months. At that point the only customers who 18 months. At that point the only customers
could experience the i-phones firsthand either who could experience the stockings firsthand
worked for Apple or were married to Apple either worked for DuPont or were married to
scientists in the i-phone division. A limited DuPont scientists in the nylon division. A
supply of the first i-phones went on sale in limited supply of the first stockings went on
Wilmington, Delaware, in October 2006, but sale in Wilmington, Delaware, in October 1939,
the i-phones did not reach the national market but the stockings did not reach the national
until May 15, 2007. When they did, the stores market until May 15, 1940. When they did, the
were taken by storm and they were sold out at stores were taken by storm and they were sold
most locations by noon. out at most locations by noon.
Nylon
March 1st, 1935: Wallace Carothers at Dupont invents Nylon, or
poly(hexamethyleneadipamide) or polyamide 66 made from
hexamethylenediamine and adipic acid.
1938: The New York Times carries an article on New Silk made on a
chemical basis. Because of its impact on the silk trade, it stated that
Japan had reason to worry. Nylon was described as mans very first
synthetic fiber, stronger than steel, fine as a spiders web, more elastic
than any of the common natural fibers, splendidly shiny.
May 15th, 1939: Nylons were placed on sale throughout the United
States at US$ 1.15 1.35 a pair. The shops were taken by storm and
almost five million pairs were bought on that day alone!
5
O H O
n H2N R C OH H N R C OH + (n-1) H2O
n
O
If R = CHR, H2N R C OH is an a-amino acid used to make
proteins.
Polyamides generate good fibers which exhibit high strength,
flexibility, and toughness. Polyamides are used to make ropes,
clothes, or the bristles of paint brushes.
n Polymerization of caprolactam yields

Nylon 6. This trick enabled BASF from
N O Germany to circumvent Duponts patents.
H O
H NH (CH2)5 C NH R 6
n
Examples of step polymerizations: Polyesters
(diol) (diacid)
O O
n HO-R1-OH + n HO C R2 C OH
(polyester)
O O
H O R1 O C R2 C OH + (2n-1) H2O
n
(Tb = 100 oC)
If R1 = -CH2-CH2- and R2 = then
the polyester is poly(ethylene terephthalate) = PET used to make

Coca-Cola bottles. 7
(diol) (diester)
O O
n HO-R1-OH + n H3C O C R2 C O CH3
(polyester)
O O
H O R1 O C R2 C O CH3 + (2n-1) CH3OH
n
(Tb = 65 oC)
Methanol can be more easily removed than water under

reduced pressure equilibrium is displaced to the right.
8
(diol) (diester)
O O
n HO-R1-OH + n H3C O C R2 C O CH3
(polyester)
O O
H3C O R1 O C R2 C O CH3 + (2n-1) CH3OH
n
O O
n HO R C OH H O R C OH + (n-1) H2O
n
9
Examples of step polymerizations: Polyurethanes
(diol) (di-isocyanate)
n HO-R1-OH + n O C N R2 N C O
(polyurethane)
O H H O
O R1 O C N R2 N C
n
No elimination reaction.
Polyurethanes are used to make foams for insulation and for
coatings and adhesives. This is achieved by adding water
which after reaction with some isocyanate functions forms
CO2 to generate the voids in the foam.
10
Examples of step polymerizations: Polysiloxanes
R1 R1
HCl
n HO Si OH H O Si O H + (n-1) H2O
R2 R n 2
R1 = R2 = CH3 poly(dimethyl siloxane) = PDMS

Polysiloxanes are excellent elastomers. They remain flexible
down to -120 oC.
11
Examples of step polymerizations: Polycarbonates
(phosgene) (bisphenol A)
O CH3
n Cl C Cl + n HO C OH
CH3
(polycarbonate)
CH3 O
H O C O C Cl + (2n-1) HCl
CH3 n
Polycarbonates have good mechanical properties. They are transparent

and are used for packaging. They have a high melting temperature.
12
Beside plastic baby bottles,
polycarbonates are also used to
make bullet proof glass.
The glass layer reduces the energy of the

incoming bullet and spreads it over a
larger surface. When the slowed bullet hits
the more flexible polymer, it is stopped. 13
Examples of step polymerizations: Crosslinked polymers
deformation
The polymeric material is deformed.

14
Examples of step polymerizations: Crosslinked polymers
crosslinker
The formation of a crosslinked network with a high

density of crosslinkers prevents deformation
hard material 15
Examples of step polymerizations: Phenol-formaldehyde resins
(phenol) (formaldehyde)
OH
basic or acidic
O conditions
n +p H C H
OH
CH2
+ x H2O
CH2 n
16
O
C
H H H H H H
O O O
H O H O
H
C H +H+ C H
H H
-H+
H
O
CH2OH
17
H H H H OH H
O O O O O
H
CH2 H CH2
18
H H H H OH H
O O O O O
H
CH2 H CH2
H H
O O
CH2
+ H2O
19
(phenol; f = 3) (formaldehyde; f =2)

OH
O
n +p H C H
OH
CH2
+ x H2O
CH2 n
crosslink 20
Examples of step polymerizations: Urea-formaldehyde resins
(urea) (formaldehyde)
O O
H O H
N C N CH2 + x H2O
n H2N NH2 + p H H n
H
H
O
H O
N C N CH2
n
H O CH2
N C N CH2
n
Crosslink? 21
Examples of step polymerizations: Melamine-formaldehyde resins
(melamine) (formaldehyde)
H H
O
H2N N NH2 N N N CH2
n +p H N N + x H2O
N N H
NH2 NH2 n
H H H
H
N N N CH2
O
N N
NH n
H H2C
N N N CH2
N N
Crosslink? 22
NH2 n
Examples of step polymerizations: Epoxy resins
(epichlorohydrin) (bisphenol A) strongly basic
O CH3 conditions
n H2C CH CH2 Cl + p HO C OH
CH3
(pre-polymer)
H3C
H O C O CH2 CH CH2 Cl + x HCl
H3C OH n
O O
O
O
O O
Crosslink? 23
Chapter Overview
Molecular weight
closed system
open system
24
Basic Requirements and Assumptions (BRA):
BRA #1: Each monomer must have a functionality f 2.
Case #1: Both monomers are bifunctional (f = 2) or

polyfunctional (f > 2) and each monomer posseses only one
type of functional group.
f=2 n A-A + n B-B -(A-AB-B)n-
Case #2: A single monomer contains both types of

functional groups.
f=2 n A-B -(A-B)n-
25
BRA #2: A high conversion is needed to get useful products.
MW2
Mechanical Sterngth
MW1
MWo Polymer Molecular Weight
26
BRA #2: A high conversion is needed to get useful products.
Monomer + Monomer Dimer

Monomer + Dimer Trimer Only small
molecules are being
Dimer + Dimer Tetramer
formed in the early
Trimer + Monomer Tetramer times of the reaction.
Large molecules are
Monomer + Tetramer Pentamer
formed at the end of
Dimer + Trimer Pentamer the reaction.
Etc ..
27
Basic Requirements and Assumptions:
p = conversion = extent of reaction

p = mole fraction of functional groups which have reacted
functions which have: reacted / not reacted / Xi

A-AB-BA-AB-BA-AB-BA-A 12 2 7
B-BA-AB-BA-A 6 2 4
B-BA-AB-BA-AB-BA-AB-BA-AB-BA-AB-B 20 2 11
sums = 38 6 22
Xn = 22/3 = 7.3 p = 38/(38+6) = 0.86 (1 p)-1 = 7.3

28
p = mole fraction of functional groups which have reacted

1 p = fraction of functional groups which have not reacted
1 p = (# of unreacted functional groups) / (total # functional groups)
(1 p)-1 = (total # of FGs) / (# of unreacted FGs # of ends)
(1 p)-1 = (total # of FGs/2) / (# of ends/2)
(1 p)-1 = (total # of structural units) / (# of polymer molecules)
(1 p)-1 = number of structural units per chain
(1 p)-1 = degree of polymerization = Xn
29
p = conversion = extent of reaction

p = mole fraction of functional groups which have reacted.
functions which have: reacted / not reacted / Xi

A-AB-BA-AB-BA-AB-BA-A 12 2 7
B-BA-AB-BA-A 6 2 4
B-BA-AB-BA-AB-BA-AB-BA-AB-BA-AB-B 20 2 11
sums = 38 6 22
Xn = 22/3 = 7.3 p = 38/(38+6) = 0.86 (1 p)-1 = 7.3

30
100
90 Monomer + Monomer Dimer
80 Monomer + Dimer Trimer
Xn = (1 - p )-1
70
Dimer + Dimer Tetramer
60
50 Trimer + Monomer Tetramer
40 Monomer + Tetramer Pentamer
30 Dimer + Trimer Pentamer
20
Etc ..
10
0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
p 31
100
90 Polymers yielding materials having good
80 mechanical properties need to have a high
degree of polymerization > 50
Xn = (1 - p )-1
70
60
50 p must be close to 1.0
40

30
The reaction must run to completion!
20
10
0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
p 32
Consequence: Monofunctional impurities cap the chains
prematurely and prevents the formation of long chains. If the
reaction goes to completion (p 1), all chain ends are terminated by
either the monomer A-A or the monofunctional impurity is A-,
N 0 1+ r nBo - B
Xn =
1
= = r o
n A- A 2n Ao -
1- p N 1- r
N0: initial number of monomer molecules; N: number of unreacted
functional groups; r: the ratio of the number of molecules of the
reactants
33
COOH
3 AA + 3 BB = AA-BB-AA-BB-AA-BB
4 AA + 3 BB = AA-BB-AA-BB-AA-BB-AA
A + 3AA + 3BB = AA-BB-AA-BB-AA-BB-A
A + 100 AA + 100 BB = ?
2A + 100 AA + 100 BB = ??
nBo - B
r o = 3/(3+2) = 0.6 Xn = (1+0.6)/(1-0.6) = 4
n A - A 2n A -
o
r = 100/(100 + 2x1) = 0.98 Xn = (1 + 0.98)/(1-0.98) = 99
r = 100/(100 + 2x2) = 0.96 Xn = (1 + 0.96)/(1-0.96) = 49

34
BRA #3: The reactivity of the molecules is assumed to be independent

of the molecular weight of the species involved in the reaction.
Rational: When the molecular weight increases, the diffusion rate of the
species decreases, but the collision rate remains roughly unaffected.
kD kR
. kD diffusion-controlled rate
A+B (A B) A-B
k-D constant for encounter
k-D diffusion-controlled rate
constant for dissociation
kR reaction rate constant
35
Basic Requirements and Assumptions: (#3)
kD kR
A+B (A.B) A-B
k-D
As the step polymerization proceeds, the polymers increase in size and

the viscosity increases.
h = ho[1 + B1fP + B2fP2 + . ]
ho solvent viscosity; B1, B2, are constants
VP = volume occupied by
VP
fP the polymer coils
V V = total volume of the 36
solution
kD kR
A+B (A.B) A-B
k-D
d [ A B ]
k D [ A] [ B] - (k - D k R )[ A B] 0
dt
kD
[ A B ] [ A] [ B] (Steady-state assumption)
k- D k R
d [ A - B] kR kD
k R [ A B ] [ A] [ B]
dt k R k- D
37
kD kR
A+B (A.B) A-B kD diffusion-controlled rate
d [ A - B] d [ A] kR kD
- [ A] [ B] constant for dissociation
dt dt k R k- D
Case #1: kR >> k-D The reaction occurs before dissociation of the
complex can take place.
The rate of formation of A-B is

d [ A - B]
k D [ A] [ B] diffusion controlled; it depends on the
dt viscosity of the solution. This is very
rarely the case in step polymerization.
38
kD kR
A+B (A.B) A-B kD diffusion-controlled rate
d [ A - B] d [ A] kR kD
- [ A] [ B] constant for dissociation
dt dt k R k- D
Case #2: kR << k-D The complex can dissociate before the reaction
takes place. This is more often the case in step polymerization.
d [ A - B] k D
k R [ A] [ B]
dt k- D
39
kD kR Case #2: kR << k-D

.
A+B (A B) A-B
k-D d [ A - B] k D
k R [ A] [ B]
dt k- D
As the step polymerization proceeds, the polymers increase in size and

the viscosity increases. The increase in viscosity affects kD and k-D in
a similar manner, so that
the ratio kD/k-D remains constant.
Consequently, the overall reaction rate is unaffected by the viscosity
increase.
40
BRA #4: The reactivities of both functional groups of a bifunctional
monomer are the same. The reactivity of a functional group is the same
irrespective of whether or not the other functional group has reacted.
The reactivity of a functional group is independent of the size of the
molecule to which it is attached.
k1
HO2C-(CH2)x-CO2H + 2 R-OH R-O2C-(CH2)x-CO2H + R-OH
k2
R-O2C-(CH2)x-CO2-R
k1 k2 if x > 3
41
Summary
#1: The monomer must have a functionality 2.
#2: High conversion must be obtained.
#3: The reactivity of the chain ends does not depend on the
chain length.
#4: The reactivity of a functional group A-A is the same
irrespective of whether or not the other functional group
has reacted.
42
Chapter Overview
Molecular weight
closed system
open system
43
Kinetics of Step Polymerization: Polyesterification
O k1 O H
k1 [C (OH ) 2 A- ]
R1 C + H-A R1 C A K
O H k2 O H k2 [COOH ] [ AH ]
The first step of the reaction involves the protonation of the

carboxylic acid with an acid.
O H k3 O H
R1 C A + HO-R2 R1 C O H A
O H k4 O
H R2
In the second step, the k5

protonated acid reacts with O
an alcohol to yield the R1 C + H2O + AH
ester. O R2
44
O k1 O H
k1 [C (OH ) 2 A- ]
R1 C + H-A R1 C A K
O H O H
k3 In a typical
k4 polyesterification:
O H O
H R2 k4 0
The polymerization is driven to k5
k1, k2, k5 >> k3
the right by removing the small O
molecules (H2O) produced. R1 C + H2O + AH
O R2
k4 0
Rate limiting step45
O k1 O H
k1 [C (OH ) 2 A- ]
R1 C + H-A R1 C A K
O H O H
k3 Rate limiting step
k4
O H O
H R2

d [C (OH ) 2 A- ]
Rp - k3[C (OH ) 2 A- ][ R2 - OH ]
dt
46

d [C (OH ) 2 A ] - k1 [C (OH ) 2 A- ]
Rp - k3[C (OH ) 2 A- ][ R2 - OH ] K
dt k2 [COOH ] [ AH ]
O OO H
k
AH + R1 C + HO-R
+ H-A2 RR1 1 CC + H2O + AH
A
O H OO RH2
d [ R1 - CO2 H ]
Rp - k3 [C (OH ) 2 A- ][ R2 - OH ]
dt
d [ R1 - CO2 H ]
Rp - k3 K [ R1 - CO2 H ][ AH ][ R2 - OH ]
dt
47
d [ R1CO2 H ]
Rp - k3 K [ R1 - CO2 H ][ AH ][ R2 - OH ]
dt
A-H = R1-CO2H: The reaction is self-catalyzed.
d [ R1CO2 H ]
Rp - k[ R1 - CO2 H ]2 [ R2 - OH ] where k = k3K
dt
In order to obtain high molecular weights, the concentration of the
two functional groups must be equal: [R1-CO2H] = [R2-OH] = [M]
d[M ]
Rp - k[ M ]3
dt
[M ] t
d[M ] 1 1
- k dt
d[M ]
3
- k dt 3 2
- 2
2k t
[M ] [ M ]o
[M ] t 0
[ M ] [ M ]o
48
A-H = R1-CO2H: The reaction is self-catalyzed.
1 1
2
- 2
2k t
[ M ] [ M ]o
The conversion p is the fraction of the hydroxyl or carboxyl
groups that have reacted at time t.
[ M ]o - [ M ]
p [M ] [M ]o (1 - p)
[ M ]o
1
1 2 k [ M ]o t
2
(1 - p) 2
NOTE: [M]o is the concentration of functional groups. If the monomers

are bifunctional, it is equal to twice the concentration of monomers! 49
HOOC-(CH2)4-COOH + HO-CH2CH2-O-CH2CH2-OH polymer
(adipic acid) (diethylene glycol)
1
1 2 k [ M ]o t
2
(1 - p) 2
p > 0.93
THE
MODEL
WORKS!
p < 0.8050
Kinetics of Step Polymerization: Reasons for non-linearity
O O
n HO CH2CH2 O CH2CH2 OH + n C (CH2)4 C polar
HO OH
less polar
O O
C (CH2)4 C
HO CH2CH2 O CH2CH2 O O H + (2n-1) H2O
n
The low conversion region:
1) As the polyesterification takes place, the mixture changes its
composition from rich in carboxylic and hydroxyl functions to rich
in ester linkages. The polarity of the solution decreases. At low
conversion, the
polarity of the solution is high and the reaction
intermediate C (OH ) 2 is stabilized. The reaction proceeds more
slowly. 51
O O
n HO CH2CH2 O CH2CH2 OH + n C (CH2)4 C
HO OH
O O
C (CH2)4 C
n
The low conversion region:
2) The concentration in acid and hydroxyl functions is very high.
Activities should be used instead of concentrations.
52
O O
HO OH
O O
C (CH2)4 C
n
The high conversion region:
1) To drive the polymerization to the right (products side), the
polymerization is carried out at moderate-to-high temperatures and
under partial vacuum. Under these conditions, small amounts of the
reactants are lost by degradation or volatilization. Such losses
become important at the later stages of the reaction (p > 0.93).
53
O O
HO OH
O O
C (CH2)4 C
n
The high conversion region:
2) As the conversion increases, the viscosity of the solution
increases as well and removal of the small molecule by-products is
hindered. As a result, the rate of reaction decreases.
54
The reaction is catalyzed by a strong acid:
O OH O
S H3C S OH
O OH
O
sulfuric acid p-toluenesulfonic acid
d [ R1CO2 H ]
Rp - k3 K [ R1 - CO2 H ][ AH ][ R2 - OH ]
dt
Since [A-H] remains constant during the polymerization, Rp can be
rewritten as:
d [ R1CO2 H ]
Rp - k '[ R1 - CO2 H ][ R2 - OH ] where k = k3K[AH]
dt
d[M ]
[R1-CO2H] = [R2-OH] = [M] Rp - k ' [ M ]2
dt 55
The reaction is catalyzed by a strong acid:
d[M ]
Rp - k ' [ M ]2
dt
[M ] t
d[M ] d[M ] 1 1
[M ]2
- k ' dt
[ M ]o
[M ]2
- k ' dt
t 0
-
[ M ] [ M ]o
k't
[M] = [M]o(1 - p)
1
1 k '[ M ]o t
1- p
NOTE: [M]o is the concentration of functional groups. If the monomers

are bifunctional, it is equal to twice the concentration of monomers! 56
p-toluene-
HOOC-(CH2)4-COOH + HOCH2CH2OCH2CH2OH polymer
(adipic acid) (diethylene glycol) sulfonic acid
1
1 k '[ M ]o t
1- p
THE
MODEL
WORKS!
57
p-toluene-
(adipic acid) (diethylene glycol) sulfonic acid
The non-linearity observed at low conversion for the

polyesterification of adipic acid and ethylene glycol
seems to be a characteristic of the esterifications.
58
Self-catalyzed Catalyzed with a strong acid
1500 minutes
180 minutes
or 25 hrs
or 3 hrs 59
Polymerization occurs on a much faster time scale when it is catalyzed
by a strong acid.
Self-catalyzed Catalyzed with a strong acid
Xn t X n t
1500 minutes 180 minutes 60

Chapter Overview
Molecular weight
closed system
open system
61
Molecular Weight:
p = mole fraction of functional groups which have reacted.

1 p = fraction of functional groups which have not reacted
1 p = (# of unreacted functional groups) / (total # functional groups)
(1 p)-1 = (total # of FGs) / (# of unreacted FGs # of ends)
(1 p)-1 = (total # of FGs/2) / (# of ends/2)
(1 p)-1 = (total # of monomers) / (# of polymer molecules)
(1 p)-1 = degree of polymerization = Xn
62
Molecular Weight:
Xn can be used to calculate the number average molecular weight of
the polymer:
Mn = XnMo + Meg
Mo: Average molecular weight of the structural unit
Meg: Molecular weight of the end-groups
To yield a polymeric material having good mechanical strength, Xn
should be larger than 100. For large polymers, the contribution of
the end-groups to Mn can be neglected.
Mn = XnMo
63
Molecular Weight:
Mn = Xn
60 Mo
Acid-catalyzed
50
1
Xn 1 k '[ M ]o t
1- p
40
Xn
30
Self-catalyzed
20 1
Xn 1 2k[ M ]o2 t m t
1- p
10
0
0 100 200 300 400 500
64
time, min.
Molecular Weight Determination of Xn and Xw using probabilities:
A-AB-BA-AB-BA-AB-BA-AB-BA-AB-B
x structural units; # of A-A monomers = x/2, number of A functions = x
One considers Nx the probability at time t of finding a polymer molecule
having x 1 functions A that have reacted and 1 unreacted function A.
Since the conversion p represents the probability that an A function has
reacted, one finds:
Nx = px-1(1 p)
The number Nx of polymer molecules at time t that contain x structural
units
Nx = Npx-1(1 p)
Where N equals the total number of polymer molecules at time t.
65
Since Xn = No/N, then N = No(1 p) where No represents the initial
number of structural units, so that Nx equals:
Nx = Nopx-1(1 p)2
The expression of Nx can be used to determine Xn and Xw.
Xn
Nx x
x p x -1
Nx p x -1
Xw
x
N x 2

x 2
p x -1
Nx x x p x -1
66
A-AB-BA-AB-BA-AB-BA-AB-BA-AB-B
x structural units; # of A-A monomers = x/2, number of A functions = x
2 p 1
x 2 p x-1
1 1

p x -1
(1 - p)
xp x -1

(1 - p) 2

(1 - p)3 (1 - p) 2
Xn
Nx x
x p x -1

1
Nx p x -1
1- p
PDI
Xw
1 p 2
p 1
Xn
Xw
x
N x

2
x 2
p x -1

1 p
Nx x x p 1- p
x -1
67
Chapter Overview
Molecular weight
closed system
open system
68
Complications in the Kinetic Analysis of the Data:

1) Rp(catalyzed) Rp(self-catalyzed)
In general: Rp(self-catalyzed) << Rp(catalyzed)
But, if Rp(catalyzed) Rp(self-catalyzed) then:

Rp = Rp(catalyzed) + Rp(self-catalyzed)
Rp = k[M]2 + k[M]3
The trends will be different from those obtained in the simpler cases
when the polymerization is only catalyzed or only self-catalyzed.
69

2) Non-equivalence of the reacting groups
H3C N C O X para
N 2,4-tolylene diisocyanate ortho meta

C
O OH OH OH
glycerol
CH2 CH CH2
Reaction of 2,4-tolylene diisocyanate with glycerol yields a

crosslinked polymer.
70

urethane linkage
71

H

H3C N C O H3C N C O
O
N N
C H ? C
R
O
O R O
?
Electron pushing; the effect is more strongly
felt by the closest isocyanate (ortho)
72

H

H3C N C O H3C N C O
O
N N R
C C H
O
O O
R
The reactivity of the second isocyanate is ~ 12 times smaller
than that of the first one because the urethane linkage pulls
the electrons much less than the isocyanate function.
The kinetics are more complex!

73
3) Side-reactions
1
1 2 k [ M ]o t
2
(1 - p) 2
p > 0.93
THE
MODEL
WORKS!
74
p < 0.80
3) Side-reactions - degradation
Problems due to
decarboxylation of
1
1 2 k [ M ]o t
2
adipic acid and
(1 - p) 2
dehydration of
diethylene glycol
p > 0.93
THE
MODEL
WORKS!
75
p < 0.80
3) Side-reactions - degradation
HOOC-(CH2)4-COOH CH3-(CH2)3-COOH + CO2

decarboxylation
O
HO-CH2CH2-O-CH2-CH2-OH 2 CH2 CH2 + H2O
dehydration
76
3) Side-reactions - cyclization
(ester)
HO-R1-OH + HOOC-R2-COOH HO-R1-OOC-R2-COOH
cyclization
O R2 O
C C H-(O-R1-OOC-R2-CO)n-OH
O O Polymer!
R1
Probability of cyclization depends on:
1) Kinetic considerations: The longer the chain and the harder it is for
one end to find the other.
2) Thermodynamic considerations: Most stable rings contain 6-12 atoms
77
3) Side-reactions - cyclization
(ester)
HO-R1-OH + HOOC-R2-COOH HO-R1-OOC-R2-COOH
cyclization
O R2 O
C C H-(O-R1-OOC-R2-CO)n-OH
O O Polymer!
R1
All in all, the conditions for cyclization are optimal for 5-, 6-, or 7-
member rings.
78

4) The reactive groups become inaccessible
A polymer is often less soluble in a solvent than the

monomers it is made of. If the polymer precipitates before it
has reached a satisfying molecular weight, the functional ends
are caught in the bulk and become inaccessible. The polymer
stops growing.
79
Chapter Overview
Molecular weight
closed system
open system
80
Equilibrium Condensation Polymerization:
In condensation polymerization, the monomers and polymers are

in equilibrium. One distinguishes between condensation
polymerizations taking place in a closed or an open system.
O k1 O
R1 C + H O R2 R1 C + H2O
O H k2 O R2
81
Equilibrium Condensation Polymerization in a closed system:
Closed system: A system where none of the products are

removed. Nothing is done to push or drive the equilibrium
towards the products (polymer). Under those conditions, the
concentrations of products (polymer and small molecule) build up
until the rate of the reverse reaction (depolymerization
k2[CO2][H2O]) equals the rate of polymerization
(k1[COOH][OH]).
O k1 O
R1 C + H O R2 R1 C + H2O
O H k2 O R2
82

O k1 O
R1 C + H O R2 R1 C + H2O
O H k2 O R2
[CO2 ] [ H 2O] k1
At equilibrium: K
[COOH ] [OH ] k 2
[COOH] = [OH] = [M] = [M]o (1 p)

[CO2] = [H2O] = [M]o [M] = p [M]o
2 2
(CO2 ester bond) p [M ]
K o
(1 - p) 2 [ M ]o2 83

O k1 O
R1 C + H O R2 R1 C + H2O
O H k2 O R2
p 2 [ M ]o2 p
K K
(1 - p) 2 [ M ]o2 1- p
K
p
K 1
1
Xn K 1
1- p 84
O k1 O
R1 C + H O R2 R1 C + H2O
O H k2 O R2
K
p
K 1
K = k1/k2 p (at eq.) Xn (at eq.)

1 0.50 2.0
10 0.76 4.2
100 0.91 11.0
1,000 0.97 32.6
10,000 0.99 101.0
85
Minimum required Xn for good mechanical properties
Polyesterification: K ~ 1 - 10
O k1 O
R1 C + H O R2 R1 C + H2O
O H k2 O R2
Transesterification: K ~ 0.1 - 1
O k1 O
R1 C + H O R2 R1 C + CH3 OH
O CH3 k2 O R2
Polyamidation: K ~ 100-1,000
O k1 O
R1 C + H2N R2 R1 C + H2O
O H k2 N R2 86
H
Polyesterification: K ~ 1 10
All K values are
Transesterification: K ~ 0.1 1 smaller than 10,000!
Polyamidation: K ~ 100 1,000
The high molecular weights that must be obtained for good
mechanical properties of the polymers can not be reached by
equilibrium polymerization!
K = k1/k2 p (at eq.) Xn (at eq.)
1 0.50 2.0
10 0.76 4.2
100 0.91 11.0
1,000 0.97 32.6
10,000 0.99 101.0
87
Minimum required Xn for good mechanical properties
Chapter Overview
Molecular weight
closed system
open system
88
Equilibrium Condensation Polymerization in an open, driven system:
O k1 O
R1 C + H O R2 R1 C + H2O
O H k2 O R2
Open system: A system where at least one of the products of the forward
reaction is removed from the reaction mixture to drive the
polymerization toward high molecular weights.
Removal of small molecules is

achieved by a combination of high Small molecules are easier to
temperature, reduced pressure, and remove from the reaction
purging with an inert gas. mixture (higher vapor pressure)
At high conversion where the polymers are large, the viscosity is large
and removal of small molecules is more difficult. 89
O k1 O
R1 C + H O R2 R1 C + H2O
O H k2 O R2
Good mechanical properties
High molecular weights
High conversion
Open system Viscous solutions

+ Problem! +
Difficult removal of
Removal of small molecules
small molecules
90
O k1 O
R1 C + H O R2 R1 C + H2O
O H k2 O R2
At high conversion where the viscosity of the solution is high, the

rate limiting step of the polymerization becomes the rate at which the
small molecule (water, methanol) can be removed from the reaction
mixture.
For a given K (= k1/k2), the water concentration required to reach a
degree of polymerization Xn can be estimated.
[CO2 ] [ H 2O] k1
K
[COOH ] [OH ] k 2
91
O k1 O
R1 C + H O R2 R1 C + H2O
O H k2 O R2
[CO2 ] [ H 2O] k1
K
[COOH ] [OH ] k 2 p [ H 2O ]
K
[COOH] = [OH] = [M] = [M]o(1 p) (1 - p) 2 [ M ]o
[CO2] = [M]o [M] = [M]op
1 K [ M ]o
Xn [ H 2O ]
1- p X n ( X n - 1)
92
O k1 O
R1 C + H O R2 R1 C + H2O
O H k2 O R2
K [ M ]o
[ H 2O ] Assumption: [M]o = 5 M
X n ( X n - 1)
Xn [H2O] Xn [H2O]
mmol.L-1 mmol.L-1
20 13.2 20 1320
K=1 50 2.0 K = 100 50 204
100 0.51 100 51
200 0.13 200 13
500 0.02 500 2 93
O k1 O
R1 C + H O R2 R1 C + H2O
O H k2 O R2
The higher K, the less necessary it is to remove water. Thus the
synthesis of polyamides (K ~ 100 1,000) is easier from the
equilibrium viewpoint than the synthesis of polyesters (K ~ 0.1 1.0)
Xn [H2O] Xn [H2O]
mmol.L-1 mmol.L-1
20 13.2 20 1320
K=1 50 2.0 K = 100 50 204
100 0.51 100 51
200 0.13 200 13
500 0.02 500 2 94
Chapter Overview
Molecular weight
closed system
open system
95
Equilibrium Condensation Polymerization molecular weight control:
O k1 O
R1 C + H O R2 R1 C + H2O
O H k2 O R2
With an exact stoichiometry ([COOH] = [OH])
1
Xn
p 1
1- p
1) The properties of a polymeric material depend on the molecular
weight of the polymer. Having an infinitely long polymer implies that
the molecular weight of the polymer is not known exactly, which in
turn implies that the properties of the resulting polymeric material can
not be predicted.
2) The presence of reactive groups at the ends of the polymer chains
implies that the material could be driven to react further while being
processed. But as the molecular weight changes, so do the properties of
96
the polymeric material.
Equilibrium Condensation Polymerization molecular weight control :
O k1 O
R1 C + H O R2 R1 C + H2O
O H k2 O R2
Control of the molecular weight of a polymer is achieved in two ways:

1) Addition of a slight excess of one of the monomers
O O
diacid + excess diol HO R1 O C R2 C O R1 OH
n
The limiting reactant is completely used up and all the chains are
terminated with the same functional group, the group that is in excess.
97
O k1 O
R1 C + H O R2 R1 C + H2O
O H k2 O R2
Control of the molecular weight of a polymer is achieved in two ways:

2) Addition of a small amount of monofunctional monomer
Acetic acid (CH3COOH) or lauric acid (CH3(CH2)10COOH) are
often used as monoacids to achieve molecular weight stabilization
of polyamides.
n A-A + n B-B + x B B-B(A-AB-B)n-A-AB
(diamine) (diacid) (monoacid)
terminates polymerization
98
Case #1: A-A + excess of B-B
nA = # of functional groups of type A
nB = # of functional groups of type B
NA = # of A-A molecules = nA/2
NB = # of B-B molecules = nB/2
r = nA o /nB o < 1
No = the initial total number of molecules
nAo nBo nAo 1

No 1
2 2 r
99
Number of unreacted A groups = nA = nAo(1 p)
Number of unreacted B groups = nB = nBo (nAo nA)
n o
n n o
nA o
nB nB 1 - o o nB 1 - o 1 - o nB (1 - p r )
o A A o A
nB nB nB n A
r p
1
(n Ao nBo )
total # of monomers 2
Xn
1 1
total # of ends ( n A nB ) 100
2 2
Number of unreacted A groups = nA = nAo(1 p)
Number of unreacted B groups = nB = nBo(1 pr)
n Ao 1
N o 1
2 r
1
(n Ao nBo )
total # of monomers 2
Xn
1 1
total # of ends ( n A nB )
2 2
n Ao 1
1
2 r 1 r
Xn
1
2

n Ao 1 - p nBo (1 - p r ) 1 r - 2 pr 101
1 r
Xn
1 r - 2 pr
If the monomers are present in stoichiometric amounts: r = 1
1
Xn
1- p
If the polymerization approaches completion, p 1
1 r
Xn
1- r
102
1 r
When p 1 Xn where r = nAo/nBo < 1
1- r
r Xn
0.5 3?
0.9 19?
0.99 199?
0.999 1999
?
103
Case #2: A-A + B-B + small amounts of B (monofunctional monomer)
equimolar
amounts
1 r
The same equation holds: Xn
1 r - 2 pr
BUT! r is defined differently:
o
n
r o A
nB 2nBo '
104
Case #2: A-A + B-B + small amounts of B (monofunctional monomer)
equimolar
amounts
1 r
Xn
1 r - 2 p r
If the polymerization approaches completion, p 1

1 r
Xn
1- r
105
Case #3: A-B + small amounts of B (monofunctional monomer)
equimolar
amounts
same as Case #2
1 r n Ao
Xn and r o
1 r - 2 pr nB 2nBo '
106
Chapter Overview
Molecular weight
closed system
open system
107
Under a given set of experimental conditions (temperature

concentrations, pressure ), the polymerization of an equimolar amount
of AA and HD yields a polymer with an Xn = 60. The experiment is run a
second time under the same set of experimental conditions until the same
conversion is reached but with a slightly different feed ratio of AA and
HD. What was the feed ratio of adipic acid and hexamethylene diamine
if a polymer with an Xn value of 30 was obtained?
108
Under a given set of experimental conditions (temperature

concentrations, pressure ), the polymerization of an equimolar amount
of AA and HD yields a polymer with an Xn = 60. The experiment is run a
second time under the same set of experimental conditions until the same
conversion is reached but with a slightly different feed ratio of AA and
HD. What was the feed ratio of adipic acid and hexamethylene diamine
if a polymer with an Xn value of 30 was obtained?
1 1
Xn 60 p 1 - 0.9833
1- p Xn
1 r X n -1
Xn 30 r 0.967
1 r - 2rp 1 X n (2 p - 1)
109
For the following reaction, which chemical structure best describes the
polymers?
n +n
+ (2n-1) CH3OH
110

Chapter 3-Step-Condensation Polymerization-2

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Chapter 3-Step-Condensation Polymerization-2

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Step/Condensation Polymerization

(diamine) (diacyl chloride) Adipic acid-vs-

n Polymerization of caprolactam yields

If R1 = -CH2-CH2- and R2 = then

the polyester is poly(ethylene terephthalate) = PET used to make

Methanol can be more easily removed than water under

R1 = R2 = CH3 poly(dimethyl siloxane) = PDMS

Polycarbonates have good mechanical properties. They are transparent

The glass layer reduces the energy of the

The polymeric material is deformed.

The formation of a crosslinked network with a high

(phenol; f = 3) (formaldehyde; f =2)

Case #1: Both monomers are bifunctional (f = 2) or

f=2 n A-A + n B-B -(A-AB-B)n-

Case #2: A single monomer contains both types of

f=2 n A-B -(A-B)n-

MWo Polymer Molecular Weight

Monomer + Monomer Dimer

p = conversion = extent of reaction

functions which have: reacted / not reacted / Xi

Xn = 22/3 = 7.3 p = 38/(38+6) = 0.86 (1 p)-1 = 7.3

p = mole fraction of functional groups which have reacted

(1 p)-1 = degree of polymerization = Xn

p = conversion = extent of reaction

functions which have: reacted / not reacted / Xi

Xn = 22/3 = 7.3 p = 38/(38+6) = 0.86 (1 p)-1 = 7.3

r = 100/(100 + 2x1) = 0.98 Xn = (1 + 0.98)/(1-0.98) = 99

r = 100/(100 + 2x2) = 0.96 Xn = (1 + 0.96)/(1-0.96) = 49

BRA #3: The reactivity of the molecules is assumed to be independent

As the step polymerization proceeds, the polymers increase in size and

h = ho[1 + B1fP + B2fP2 + . ]

ho solvent viscosity; B1, B2, are constants

The rate of formation of A-B is

kD kR Case #2: kR << k-D

As the step polymerization proceeds, the polymers increase in size and

The first step of the reaction involves the protonation of the

In the second step, the k5

NOTE: [M]o is the concentration of functional groups. If the monomers

NOTE: [M]o is the concentration of functional groups. If the monomers

The non-linearity observed at low conversion for the

Self-catalyzed Catalyzed with a strong acid

1500 minutes 180 minutes 60

p = mole fraction of functional groups which have reacted.

(1 p)-1 = degree of polymerization = Xn

Complications in the Kinetic Analysis of the Data:

In general: Rp(self-catalyzed) << Rp(catalyzed)

But, if Rp(catalyzed) Rp(self-catalyzed) then:

Complications in the Kinetic Analysis of the Data:

N 2,4-tolylene diisocyanate ortho meta

Reaction of 2,4-tolylene diisocyanate with glycerol yields a

Complications in the Kinetic Analysis of the Data:

Complications in the Kinetic Analysis of the Data:

Complications in the Kinetic Analysis of the Data:

The kinetics are more complex!

HOOC-(CH2)4-COOH CH3-(CH2)3-COOH + CO2

Complications in the Kinetic Analysis of the Data:

A polymer is often less soluble in a solvent than the

Equilibrium Condensation Polymerization:

In condensation polymerization, the monomers and polymers are

Equilibrium Condensation Polymerization in a closed system:

Closed system: A system where none of the products are

Equilibrium Condensation Polymerization in a closed system:

[COOH] = [OH] = [M] = [M]o (1 p)