Polymer Engineering

CM-4305 IQ0570

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 Chapter IV

Polymer Formation

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Polymer Formation

 Polymerization is the process of joining together small

molecules by covalent bonds.

 Ultimate starting materials for synthetic polymers are few:

 petroleum,

 natural gas,

 coal tar, and

 cellulose are the main sources.

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Process of building up polymers from simple repeating
units (monomers) can be classified by:

 The functionality, the number of bonds each monomer can

form in the reaction used.
 The kinetic scheme governing the polymerization reaction,
radical polymerization vs stepwise reactions.
 The chemical reaction to produce new bonds: esterification,
amidation, etc.
 The number of monomers used to give homopolymer,
copolymer, terpolymer, etc.
 The physical arrangement, bulk, solution, suspension, or
emulsion system.

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4.2 Functionallity
 1. Functionality of 1 (A-): A-A-

 2. Functionality of 2 (B-): A-B-A-B-

 3. Functionality of 3 (C-): A-B-A-B-A-B-

|
C

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4.3 Kinetic Schemes
 Stepwise polymerization: each polymer formed can
react further with monomer or other polymers. Each
dimer, trimer, etc. is just as reactive as the monomer.

 Chain polymerization: each polymer is formed in a

comparatively short time, and then is “dead” and remains
unchanged by the reaction of the remaining monomer.

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4.4 Chain Polymerization

 Initiation: the reaction of an “active” center such as

a free-radical, carbanion, or carbocation ion.

 Propagation: the addition of more monomer to a

growing chain.

 Termination: disappearance of an “active” center.

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 Each reaction is characterized by a rate constant.

 It is a cornerstone of polymerization theory that the

reactivity of a growing polymer chain depends almost
completely on the last unit added and not on previously
added units or on the length of the chain.

 Therefore kp is the same for a chain of any length.

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 The kinetic model presupposes that radicals form fast,
thus the other steps are slowly enough that a steady
state is reached, where the radical population does not
change rapidly with time during propagation:

d R 
(moles / liter )
dt
d M 
dt
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Radical Polymerization
 The material balance can be written without the
subindices preserving only the last element
characteristics to account for reactivity.

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 The propagation reaction occurs much more slowly than
the radical generation reaction. By the time the
propagation is important the radical generation has
ceased and it is no longer important.

 This is the rate of reaction in radical chain polymerization mechanism.

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 The kinetic chain-length Vn is the number of monomer
units converted per initiating radical, so that:

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 The number-average degree of polymerization Xn is:

 Stepwise Polymerization:
 unreacted monomer is included in the numerator
 unreacted monomer are counted in the denominator

 Chain Polymerization:
 unreacted monomer is not included in the numerator
 unreacted monomer is not counted in the denominator

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4.5 Ionic and Insertion Polymerizations

 A major difference between radical polymerization and

the various ionic methods is that in ionic methods the
incoming monomer unit must fit between the growing
chain and an associated ion or complex.

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 Cationic only  Free radical only

 Isobutylene and derivates  Halogenated vinyls

 CH2=C(CH3)2  CH2=CHX

 Anionic only  Cationic or free radical

 Vinyldiene cyamide  N-vinylpyrrolidone

N-vinylpyrrolidone
 CH2=C(CN)2

N
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 Free radical or anionic  Butadiene
 Acrylic and methacrylic  CH2=CH-CH=CH2
esters  Styrene
 Vinyldiene esters
 CH2=C(COOR)2  Coordination or supported
metal oxide catalyst
 Cationic, free radical, or  -olefins including ethylene
anionic  Dienes
 Ethylene  alkyl vinyl ethers
 CH2=CH2

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Cationic Systems
 Cationic polymerization tend to be very rapid even at low
temperatures.
 The polymerization of isobutylene with AlCl3 or BF3 is
carried out commercially at -100º C.
 An estimate of the lifetime of a growing chain of
isobutylene in this case is about 10-6 s.
 There is a counter ion “gegen” ion that can lead to stereo
regularity because the incoming has to fit between the
chain and gegen ion.
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 Carbocation (cationic polymerization):
 Generation of the carbocation.

 Propagation:
 Addition with stereospecific conformation.

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 Termination:
 External agent added.

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Anionic Systems
 If it uses lithium alkyls will not have termination step.

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Anionic Systems
 If it uses lithium alkyls, the reaction will not have termination step.

 Can achieve block copolymerization.

 Simple styrene polymerization

 Initiation:
 Formation of negative ion.

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 Propagation:
 Extension of chain with a specific conformation.

 Termination:
 Addition of external scavenger –mild acid/base/water

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 You are likely to get a narrow molecular weight distribution (Poisson).
Commercial copolymers, based on styrene and butadiene, have
been prepared by this method. Both the random (both monomers
present) and block first one monomer then the next) are available.

 The number average degree of polymerization is given by Xn= [M] /

[I] , where units [M] is the initial monomer concentration and [I] is the
initiator, (moles/unit volume).

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 Mathematically we would expect:

 d [M ]
 kp [ M ][ R s ]
dt
or
ln[[ M ] 0 / M ]  k p t [ R s ]

 Concentration of growing polymer seeds is constant straight

line with time.

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 The rate is proportional to
the initiator concentration
to the first power in
hydrocarbon solvents. This
is because the lithium is
associated in non polar
solvents as a dimmer .

The final step is

decomposition of the
 First-order rate plots for “seeded” butyl lithium
polymerizations for monomers in benzene, hexane, or lithium alkyl by the addition
tetrahydrofuran. of water or alcohol.

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Insertion polymerization systems

 Production of stereospecific polymers with synthetic

catalysts.

 Structures that cannot be achieved by free radical or

ionic routes.

 Relates to a hindered propagation site, it can not grow

randomly, the catalyst gives stereospecificity.

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 Ziegler-type catalysts originally involved the formation of a complex
precipitate from aluminium triethyl and titanium tetrachloride:

 If you bubble ethylene through a suspension of this material at room

temperature, the ethylene polymerizes very rapidly to give a high-
molecular-weight, linear polyethylene. This linearity leads to a higher
crystallinity than that for the branched polymer.

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 Remember this differs from the high pressure, free-radical
polyethylene that formed a more branched polymer.

 Insertion polymerization is a more general description of

polymerizations that include a “hindered propagation site”.

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 Stereochemistry:

TiCl3 – AlR3

With Al/ Ti > 1 gives

96% cis-
polyisopropene.

With Al /Ti < 1 gives

95% trans-
polyisopropene.

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 Metal oxides:
 Linear polyolefins, nickel, cobalt, chromic, or vanadium oxides
supported on silica alumina effective for ethylene and α-olefin
copolymers at low T.

 Linear polyethylene: SiO2/Al2O3 support saturated with aqueous

CrO3 solution. Heat in air at 500-800ºC, chromates and
dichromates formed by reaction with support surface hydroxyl
group. Reduction of the chromium by monomer or hydrogen
leads to a site where ethylene can attach to form a chromium
alkyl bond.

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Group Transfer Polymerization

 Ionic polymerization can make olefins, diolefins, and styrene

with narrow molecular weight distributions.

 Anionic methods are not very successful with acrylic

monomers.

 Group transfer polymerization produces linear, living polymer

systems using organosilicon initiators.

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 The mechanism is basically an anion – catalyzed polymerization with
the initiator consisting of a butane silyl acetal.

 Needs:

 Methyl trimethyl silyl butane acetal ----- starting material

 Methyl methacylate ----- monomer

 Nucleophilic activator bifluoride ion

 Molecular distributions can be very narrow.

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 In a clean system there is no termination step, termination is
controlled by putting a reactive site at one or both ends of the
final polymer.

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4.6 Stepwise Polymerization

 This can make a low molecular weight polymer by stepwise

polymerization and then increase its molecular weight by more
of the same reaction. This is a major point of difference
between chain and stepwise polymerization.

 The principle of equal reactivity regardless of molecular weight

is fundamental to stepwise polymerization.

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 Monomer: A (Hydroxyl)—B(carboxyl)
 Dimer A—E (ester)—B
 Trimer A—E—E—B
 x-mer A -(-E-)- x-1-B

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 Starting with NA molecules and forming NE ester groups, we define
the extent of polymerization p as:

NE Number of ester groups

p  
NA Number of initial molecules of monomer

NR  NA  NE

 p= Probability of reaction

 NR= Number of free molecules/monomer

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 The number average degree of polymerization Xn becomes:

NA 1
Xn  
NR 1 p
NA
NA NA N 1
Xn    A

NR NA  NE NA  NE 1 p
NA NA
 Stepwise reactions can offer special problems in controlling reaction
rate and molecular weight.

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 Urethane foams
hard to control
due to the speed
of the reaction.

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 Urethane foams
hard to control due
to the speed of the
reaction.

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 Stepwise Polymerization Theoretical Distributions

 In a typical stepwise polymerization

we are adding in order A or B to the
chain or a simple A if it is double
funcitionalized.

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  probability that any particular
= reactive site has been
esterified

probability that a monomer unit is

still unreacted (probability that a
monomer unit selected at random
is a part of a polymer with degree
of polymerization x is written
(Pr)x).
Probability of having reacted

Probability of being free

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UU means two monomers that have not reacted. number of molecules with length x
UEU means two units have reacted.

The number of units that have reacted is the number of E’s plus one.

x is the number of monomers in a chain (degree of polymerization).

x Nx xNx
Monomer -UU- 1 25 25
Dimer -UEU- 2 15 30
Trimer -UEEU- 3 2 6
Tetramer -UEEEU- 4 4 16
Pentamer -UEEEEU- 5 2 10
Hexamer -UEEEEEU- 6 1 6
Heptamer -UEEEEEEU- 7 1 7
50 100
Total number Total
of molecules number of
monomers
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 Probability of having reacted

 Probability that a monomer has not

been added to a polymer length of
1 (i. e. not reacted).

 Probability that a monomer has

been added (or reactor to become a
dimer).
Probability of a reaction taking place

The possibility that a unit has become a dimer

Probability that a monomer is used in the reaction

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
 1


 1
 1


 1

 1 Probability that a monomer has

been added to a polymer chain of
length x.

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Average number molecular weight
 <P>=expected value=

 = f probability distribution, x
independent variable.

 <P>=

 <Mo x>=
 =
 =

 <Mn>=
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

1 1-p
-(1-p) 1+p+p 2

p
-(p-p )
2

p 2
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

 =

 = =

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Ring-Scission Polymerization

 A ring is opened to form a linear polymer.

 An equilibrium may exist between open chain and ring

structures when the monomer is as reactive as a growing
polymer.

 Usually only small rings are involved in such equilibrium

 The silicones are an exception in that they can form rings of

increasing size. Silicone rings can be isolated with up to 80
ring atoms.

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 Olefin Metathesis

 Catalyst: WCl6 with tetraalkyl tin modified with ethyl ether.

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Copolymerization

 This is the term used for the utilization of at least two monomers in the
formation of a polymer chain.

 Modelling assumptions:

 Over any short time interval, the concentration of the radicals does
not change appreciably with time, that is d(radicals)/dt = 0.

 A growing polymer chain`s reactivity is determined solely by the

last monomer unit added. This reactivity is independent of the
molecular weight.

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  The only monomer-consuming reactions taking place, together
with their constant are:

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 That is, a growing chain, whose last added unit was a
monomer A, has reactivity determined by A only. This chain
can add another A, in which case the reactivity is unchanged;
it may also react with B, in which case the new reactivity is
determined by B●.

 Propagation is the only reaction of importance, since it is

repeated many times for each initiation or termination step.

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Material Balances
 Copolymerization

 1. Rate of creation of radicals (t= time)

d  A 
 k 21 B  A   k 12  A B   0
dt
A   k 21 A 
B  k 12 B 
 2. Rate of consumption (disappearance) of monomers A and B:

d A 
  k 11  A  A   k 21 B  A 
dt
d B 
  k 12  A B   k 22 B B 
dt

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 We define the relative reactivities as:

k11
r1   the ratio of reactivity of monomer 1 (A) toward itself to
k12 the reactivity of monomer 1 toward monomer 2 (B).

k 22
r2 
k12

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 Define:
d A 
dt Mole fraction of monomer A
F1
d  A  d B  being added to the chain when
 the concentrations are [A] and
dt dt [B].

F1 d A 

F2 d B 

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 Now we let:
f1
A 
A   B 

f 1

A 
f 2 B 
 The relative dynamic addition of A with respect to B is written in
terms of measurable quantities as: F d A 
1

F2 d B 
 f1 
r1    1
F1  1  f1 

F2  1  f1 
r1    1
 f1 
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 F1 d A 

F2 d B 
 f1 
r1    1
F1  1  f1 

F2  1  f1 
r2    1
 f1 
 Instantaneous copolymer composition F1 related to
monomer concentration (gmol/liter), f1and kinetic
parameters r1 and r2.

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 Random Copolymer

SBBSSSBSBSSBSBBS
 An extreme case is the Block Copolymer. An example is the
sequential addition of butadiene, then styrene, then butadiene to
lithium alkyl will give structure with long runs of blocks of each
monomer.

S  (S )m  S  B  ( B)n  S  (S ) x  S

 S=Styrene, B=Butadiene

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  A third variety is the graft

copolymer. In this case,

branches are grown on a

main stem of a previously

formed polymer molecule:

polyethylene can be

irradiated in air with gamma

rays or accelerated electrons,

Graft Copolymer which have peroxides or free

radicals “trapped” on the

polymer backbone.

Exposed to a reactive monomer such as acrylonitrile (CH2=CHCN),

polymerization is initiated at the free radical sites, and branches of poly
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(acrylonitrile) grow on the polyethylene stem.
4.9 Biosynthesis of Polymers

 cis-1,4-polyisoproprene found in the latex of the rubber tree

Hevea brasiliensis.

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 Like other plants the tree has:

 A system of tubes or vessels that convey water and salts from the
roots to the leaves.

 A system that carries soluble sugars down from the leaves in the sap.

 Unlike most other plants, the rubber tree has a third system of vessels in
which the sugars are converted into latex. Latex is a stabilized emulsion
of rubber particles along with the other compounds necessary to the
process such as enzymes, sterols, and lipids.

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 The exact mechanism for the synthesis of latex is not known. The
manner in which the pyrophosphate adds to the growing chain and
the specific enzyme that is involved are not known with certainty.

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 Starch: one component amylose that dissolves in water

 Cellulose: insoluble in water

 RNA: Ribonucleic acid

 DNA: Deoxyribonucleic acid

 Polymer modifications: this refers to modifications to

polymers to increase their value and range of use.

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  Cellulose that is insoluble in water can be modified to be more
wettable.

α-Cellulose
Cellulose diacetate
Infusible and
Fusible; soluble in acetone, benzene
insoluble

*Fusible:
capable of being Methyl cellulose
molded or cast Fusible; soluble in water
in useful forms.
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 Chlorination of natural rubber decreases the flammability of
the polymer.

 Nitration of cellulose leads to cellulose nitrate or gun cotton.

The native cotton can be plasticized and molded.
Flammability is enhanced at the same time.

 Sometimes there is no monomer for a complex polymer, in this

case, we have poly (vinyl cinnamate) that polymerizes when
exposed to UV light.

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You need three steps for this polymer:

 1) Make poly(vinylacetate):  3) Esterify with cinnamic acid:

 2) Hydrolyze polymer to
polyvinyl alcohol:

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  Homework
 4.5
 4.6

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