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Reporters: Christian John R.

Ramento Initiation- involves the acquisition of the active site

John Martin B. Rosales by the monomer. This may occur spontaneously by
the absorption of heat, light (ultraviolet), or high-
energy irradiation. But most frequently, initiation of
CLASSIFICATION OF POLYMERS free radical polymerization is brought about by the
Chain-reaction (Addition) Polymers addition of small quantities of compounds called
Step-reaction (Condensation) Polymers initiators. Typical initiators include peroxides, azo
compounds, Lewis acids, and organometallic
Chain-reaction (Addition) Polymerization reagents. However, while initiators trigger initiation
- an important industrial method of polymer of the chain and exert an accelerating inuence on
preparation, involves the addition of unsaturated polymerization rate, they are not exactly catalysts
molecules to a rapidly growing chain. The most since they are changed chemically in the course of
common unsaturated compounds that undergo polymerization. An initiator is usually a weak organic
chain-reaction polymerization are olefins, as compound that can be decomposed thermally or by
exemplified by the following reaction of a irradiation to produce free radicals, which are
generalized vinyl monomer. molecules containing atoms with unpaired electrons.
A variety of compounds decompose when heated to
form free radicals. Dialkyl peroxides (ROOR),
diacylperoxides (RCOOOCOR), hydroperoxides
(ROOH), and azo compounds (RN NR) are typical
organic compounds that can be decomposed
thermally to produce free radicals. Benzoyl peroxide,
- The growing polymer in chain-reaction azo bisisobutyronitrile, and di-t-butylperoxide are
polymerization is a free radical, and polymerization commonly used free-radical initiators, as illustrated
proceeds via chain mechanism. Chain-reaction in Equations 2.22.4
polymerization is induced by the addition of free-
radical-forming reagents or by ionic initiators. Like
all chain reactions, it involves three fundamental
steps: initiation,
- propagation, and termination. In addition, a
fourth step called chain transfer may be involved.
- based on free radical, cationic, anionic, and
coordination reactions where a single initiating
species causes the growth of a polymer chain.
- is exothermic with the polymerization is mainly
controlled by steric and resonance factors of the
monomer. Generally, the less resonance
stabilization the more exothermic the reaction and
the greater the steric factors, the less exothermic
the polymerization.

Propagation- which is the rapid and progressive

addition of monomer to the growing chain without a
change in the number of active centers.
- During propagation, the initiated monomer
described above adds other monomers usually
thousands of monomer molecules in rapid
- involves the addition of a free radical to the double
bond of a monomer, with regeneration of another
radical. The active center is thus continuously
relocated at the end of the growing polymer chain
(Equation 2.11).

Propagation continues until the growing chain

radical is deactivated by chain termination or
transfer as discussed below.

The substituted carbon atom is regarded as the

head and the unsubstituted carbon atom the tail of
the vinyl monomer. There are, therefore, three
possible ways for the propagation step to occur:
headto-tail (Equation 2.11), head-to-head (Equation
2.12), and tail-to-tail (Equation 2.13). A random
distribution of these species along the molecular
chain might be expected. It is found, however, that
head-totail linkages in which the substituents occur
on alternate carbon atoms predominate; only
occasional interruptions of this arrangement by
head-to-head and tail-to-tail linkages occur. In
addition, exclusive head-to-head or tail-to-tail
arrangements of monomers in the chain are now

Termination- which involves the destruction of the

growth activity of the chain leaving the polymer
- In termination, the growth activity of a polymer
chain radical is destroyed by reaction with another
free radical in the system to produce polymer
molecule(s). Termination can occur by the reaction These structures contain double bonds in the 1,2
of the polymer radical with initiator radicals and 3,4 positions, each of which may participate
(Equation 2.14). This type of termination process is independently in polymerization giving rise to 1,2 and
unproductive and can be controlled by maintaining 3,4 units. A further possibility is that both bonds are
a low rate for initiation. involved in polymerization through conjugate reactions,
resulting in 1,4 units. These structures are shown in
Equation 2.18.

first species produced in these reactions are
- The termination reactions that are more important carbocations, and these were unknown as such
in polymer production are combination (or coupling) prior to World War II.
and disproportionation. It is now known that pure Lewis acids, such as
boron triuoride or aluminum chloride, are not
effective as initiators.
A trace of a proton containing Lewis base, such
as water, is also required. As shown in Eq. (7.1),
the Lewis base coordinates with the electrophilic
Lewis acid, and the proton is the actual initiator.
Since cations cannot exist alone, they are always
accompanied by a counterion, also called a
In termination by combination, two growing
polymer chains react with the mutual destruction of
growth activity (Equation 2.15), while in
disproportionation a labile atom (usually hydrogen) is
transferred from one polymer radical to another
(Equation 2.16).
Coupling reactions produce a single polymer,
while disproportionation results in two polymers from the
two reacting polymer chain radicals. The predominant
termination reaction depends on the nature of the Monomers with electron-donating groups like
reacting monomer and the temperature. Since isobutylene form stable positive charges and are readily
disproportionation requires energy for breaking of converted to polymers by cationic catalysts. Any strong
chemical bonds, it should become more pronounced at Lewis acid like boron triuoride (BF3) or FriedelCrafts
high reaction temperatures; combination of growing catalysts such as AlCl3 can readily initiate cationic
polymer radicals predominates at low temperatures. polymerization in the presence of a cocatalyst like water,
Chain Transfer- In chain-transfer reactions, a which serves as a Lewis base or source of protons.
growing polymer chain is deactivated or terminated
by transferring its growth activity to a previously
inactive species, as illustrated in Equation 2.17.

Ideally, free-radical polymerization involves three Isobutylene and boron

basic steps: initiation, propagation, and termination, as triuoride
discussed above. However, a fourth step, called chain
transfer, is usually involved. During initiation, a proton adds to the monomer
to form a carbonium ion, which forms an association with
DIENE POLYMERIZATION the counterion. This is illustrated for isobutylene and
Conjugated dienes such as butadiene (1), boron triuoride in the figure.
chloroprene (2), and isoprene (3) constitute a Propagation involves the consecutive additions of
second group of unsaturated compounds that monomer molecules to the carbonium ion at the growing
can undergo polymerization through their double chain end.
bonds. Termination in cationic polymerization usually
involves rearrangement to produce a polymer with an
unsaturated terminal unit and the original complex or
chain transfer to a monomer and possibly to the polymer
or solvent molecule.

are usually conducted in solutions and frequently

at temperatures as low as 80 to 100C.
Polymerization rates at these low temperature
conditions are usually fast. The cation and the
counterion in cationic polymerization remain in
close proximity. If the intimate association
between the ion pair is too strong, however,
monomer insertion during propagation will be
prevented. Therefore the choice of solvent in Monoolefins such as propylene and dienes such
cationic polymerization has to be made carefully; as butadiene and isoprene can be polymerized
a linear increase in polymer chain length and an using ZieglerNatta coordination catalysts.
exponential increase in the reaction rate usually The initiating species is a metalalkyl complex
occur as the dielectric strength of the solvent and propagation involves the consecutive
increases. insertion of monomer molecules into a polarized
titaniumcarbon bond. Coordination
polymerizations may be terminated by
Monomers that are suitable for anionic
introducing poisons such as water, hydrogen,
polymerization generally contain electron- aromatic alcohols, or metals like zinc into the
withdrawing substituent groups. reacting system.
Typical monomers include styrene, acrylonitrile,
butadiene, methacrylates, acrylates, ethylene
oxide, and lactones.
The initiator in anionic polymerization may be
any compound providing a strong nucleophile,
including Grignard reagents and other
organometallic compounds.

Styrene and
Initiation involves the addition of the initiator to
the double bond of the monomer.
The reaction produces a carbanion at the head
end to which is associated the positively charged
lithium counterion.
Propagation occurs by the successive insertion of
monomer molecules by anionic attack of the
carbanion. No chain transfer or branching occurs
in anionic polymerization, particularly if reactions
are carried out at low temperatures.
Termination of the growth activity of the
polymer chain takes place either by the
deliberate or accidental introduction into the
1930- M. E. P. Friedrich (unwanted byproduct
system of oxygen, carbon dioxide, methanol,
water, or other molecules that are capable of of the reaction of ethylene and a lithium alkyl
reacting with the active chain ends. compound)
1932- British scientists at the Imperial
We note that in anionic polymerization as well as
free-radical polymerization, the initiator or part of Chemical Industries (ICI)
it becomes part of the resulting polymer accidentally made polyethylene while
molecule, attached to the nongrowing chain end. investigating what products could be
In some systems, termination can be avoided if produced from the high-pressure reaction
the starting reagents are pure and the of ethylene with various compounds
polymerization reactor is purged of all oxygen March 1933- they found the formation of a white
and traces of water. This produces polymer solid when they combined ethylene and
molecules that can remain active even after all benzaldehyde under high pressure
the monomer molecules are consumed. When (about1400atm). They correctly identified the
fresh monomer is added, polymerization solid as polyethylene.
resumes. Such polymeric molecules are referred July 1939- enough polyethylene was made to
to as living polymers because of the absence coat one nautical mile of cable.
of termination.
Low Density Polyethylene (LDPE)
COORDINATION POLYMERIZATION Commercial LDPE typically has between 40 and
Monomers with side groups asymmetrically 150 short alkyl branches for every 1000 ethylene
disposed with respect to the double bond are units
capable of producing polymers in which the side Produced employing high pressure (15,000 to
groups have a specific stereochemical or spatial 50,000 psi and temperatures to 350degree
arrangement (isotactic or syndiotactic). Celsius).It has a density of about 0.912 to 0.935
Unbranched and stereospecific polymers are also Because of the branching, LDPE is amorphous
produced by the use of ZieglerNatta catalysts. (about 50%) and sheets can allow the ow-
These are complex catalyst systems derived from through of liquids and gases. Because of the
a transition metal compound from groups IVB to branching and low amount of crystallinity, LDPE
VIIIB of the periodic table and an organometallic has alow melting point of about 100 degree C,
compound usually from a group IA or IIIA metal. making it unsuitable for use with materials
A typical catalyst complex is that formed by requiring sterilization through the use of boiling
trialkyl aluminum and titanium trichloride as water. LDPE has a ratio of about 10 short
shown below: branches to every long branch.
Types of applications for the various polyethylenes
1. UHMWPE :battery separators, light weight
fibers, permanent solid lubricant materials in rail
High Density Polyethylene (HDPE) car manufacture, automobile parts, truck liners;
produced using organometallic catalysts, such as liners to hoppers, bins, and chutes; farm
the Ziegler-Natta or Phillips catalysts, have less machinery such as sprockets, idlers, wear plates,
than 15 (normally within the range of 16) short and wear shoes; sewage treatment bearings,
alkyl branches (and essentially no long branches) sprockets, wear shoes; lumbering chute, sluice,
per 1000 ethylene units. and chain-drag liners; neutron shields
Because of the regular structure of the ethylene 2. Typical HDPE: blow-molded products
bottles, cans, trays, drums, tanks, and pails;
units themselves and the low extent of
injection-moldedproductshousewares, toys,
branching, its chains can pack more efficiently,
food containers, cases, pails, and crates; films,
resulting in a material with greater crystallinity
pipes, bags, conduit, wire and cable coating,
(generally up to 90%), higher density (0.96), with
foam, insulation for coaxial and communication
increased chemical resistance, hardness,
stiffness, barrier properties, melting point (about
3. 3. Low molecular weight HDPE: spray
130C), and tensile strength. Low molecular
coatings, emulsions, printing inks, wax polishes
weight (chain lengths in the hundreds)
and crayons
is a wax, while typical HDPE is a tough plastic.
4. 4. LDPE: packaging products, bags, industrial
sheeting, piping and tubing, films, garbage cans,
industrial containers, household items
5. 5. LLDPE: telephone jacketing, wireandcable
insulation, piping and tubing, drum liners,
bottles, films
Polypropylene (PP)
is one of the three most heavily produced
Linear low-density polyethylene (LLDPE)
While PP was produced for some time, it only
can be produced with less than 300 psi and at
became commercially available in the late 1950s
about 100 C.
It is actually a copolymer of ethylene with about
ofsomewhatisotactic PP, iPP.
810% of an alpha- olefin such as 1-butene, 1- The abundance of PP is called for because of its
pentene, 1-hexene, or 1-octene produced by
variety and versatility being employed today in
solution or gas phase polymerization. Through
such diverse applications as a film in disposable
control of the nature and amount of -olefin, it is
diapers and hospital gowns to geo textile liners,
possible to produce materials with densities and
plastic applications as disposable food containers
properties between those of LDPE and HDPE.
and automotive components, and fiber
LLDPE does not contain the long branches found
applications such as carpets, furniture fabrics,
in LDPE.
and twine.
The first PP was not highly crystalline because
the tacticity was only approximate but with the
use of the Natta-Zeigler catalysts iPP was
produced that contained greater amounts of
stereoregular material with a corresponding
increase in crystallinity and associated properties
such as an increased stiffness,better clarity,and a
Ultrahigh Molecular Weight Polyethylene higher distortion temperature.
(UHMWPE) Today, with better catalysts, including the soluble
A high-density polyethylene with chain lengths of metallocene catalysts, the tacticity has been
over 100,000 ethylene units. increased so that 99% isotactic material can be
they intertangle causing physical crosslinks, readily produced. The more traditional Zeigler-
increasing the tensile strength and related Natta catalysts systems today have activities as
properties of these materials. (By comparison, high as producing 100 kg iPP per gram of
HDPE rarely is longer than 2000 ethylene units.) catalysts eliminating the need for catalyst
is about 45% crystalline and offers outstanding removal. Most iPP is made using bulk propylene,
resistance to corrosion and environmental stress either as a gas or liquid.
cracking, outstanding abrasion resistance and
impact toughness, and good resistance to cyclic
fatigue and radiation failure with a low surface
friction.. It has a density of about 0.93. It is
produced utilizing catalyst systems similar to
those employed for the production of HDPE (i.e.,
Ziegler-Natta and Phillips catalysts)
Because PIB is fully saturated, it is cured as a
thermoset elastomer through inclusion of about 1
to 2% isoprene that supplies the needed double
bonds used in the curing process. Other
POLYMERS FROM 1,4-DIENES materials including brominated para methyl
1,4-Butadiene can form three repeat units styrene are replacing isoprene for this use. PIB is
Commercial polybutadiene is mainly composed also used in sealing applications and medical
of the 1,4-cis isomer and is known as butadiene closures and sealants.
rubber, BR
is made from the use of stereoregulating
Olefin metathesis is a catalytically induced
reaction wherein olefins, such as cyclobutene
The composition of the resulting polybutadiene
and cyclopentene, undergo bond reorganization
is quite dependent on the nature of the catalyst resulting in the formation of so-called
such that almost total trans-1,4 units, or cis-1,4 polyalkenamers.
units, or 1,2 units can be formed as well as Because the resulting polymers contain double
almost any combination of these units.
bonds that can be subsequently used to
The most important single application of
introduce crosslinking, these materials have been
polybutadiene polymers is its use in automotive used to produce elastomeric materials as well as
tires where over 107 tons are used yearly in the plastics. Transition metal catalysts are required
US manufacture of automobile tires. for these reactions.
BR is usually blended with natural rubber, NR, or Catalysts include typical Natta-Ziegler types and
styrene-butadiene rubber, SBR, to improve tire other similar catalystcocatalyst combinations.
tread performance, particularly wear resistance. The reactions can be run at room temperature
Polyisoprene rubbers and the stereoregularity controlled through
are used in the construction of passenger, truck, choice of reaction conditions and catalysts.
and bus tires and inner liners as well as sealants
and caulking compounds, sporting goods,
gaskets, hoses, rubber sheeting, gloves, belts,
and footwear.


was the first commercially successful synthetic

elastomer introduced in 1932 under the
tradenames of DuPrene and Neoprene by For instance, the use of a molybdenum-based
Dupont. It was discovered by Carothers and catalyst with cyclopentene gives the cis product
coworkers whereas the use of a tungsten-based catalyst gives
is largely manufactured by emulsion the trans product.
polymerization using both batch and continuous As expected, the metathesis polymerization of
systems. Free radical products contain mainly more strained cycloalkenes such as cyclobutene
1,4-trans units. Along with the four main occurs more rapidly than less strained structures
structural units analogous to those of such as cyclopentene.
polyisoprene, sequence distributions are It is believed that polymerization occurs via a
available for both polyisoprene and chain polymerization where ring opening occurs
polychloroprene. Polymerization can occur with via complete scission of the carboncarbon
the growing end being the 4 end or the1 end. double bond through the reaction with metal
Generally the 1,4-polymerization sequence is carbene precursors giving an active carbene
favored with the growing end being carbon 4. species.
PIB, was initially synthesized in the 1920s.
is one of the few examples of the use of cationic
catalysis to produce commercial scale polymers.
Low molecular weight (about 5,000 Daltons) PIB
can be produced at room temperature but large where L is the ligand attached to the metal.
chains (over 1,000,000 Daltons) are made at low
temperatures where transfer reactions are
suppressed. does not require an initiator, catalyst, or some
other form of activation
These copolymerizations require a specific
combination of one monomer that is nucleophilic
and a second that is electrophilic. The interaction
of these two comonomers gives a zwitterion that
is responsible for both initiation and propagation.

Because of the symmetry of the monomer, it

might be expected that the materials would be
quite crystalline like linear polyethylene. While If growth involves only addition and condensation
PIB does crystallize under stress is does not reactions, then an alternating copolymer is formed.
under non-stressed conditions. This is because Sometimes a lateral reaction occurs where the zwitterion
the geminal dimethyl groups on alternating interacts with one of the monomers giving a product that
carbons in the backbone cause the bond angles is a statistical copolymer.
to be distorted from about the usual tetrahedral The zwitterionic copolymerization is illustrated by
bond angle of 109.5 to 123 forcing the chain to the reaction of 2-oxazoline with -propiolactone
be straightened out. below

polymer is a polyester, in consonance with the general
name of reactions between hydroxyl groups (OH) and
carboxylic acid groups (COOH)

Isomerization polymerizations are polyaddition
reactions whereby the propagating species
rearranges to energetically preferred structures
prior to subsequent chain growth.

An example of polyaddition-type step-growth

polymerization is the preparation of polyurethane by the
ionic addition of diol (1,4 butanediol) to a diisocyanate
(1,6 hexane diisocyanate)

Another example of polyaddition-type step-growth

polymerization is the preparation of polyurea from the
reaction of diisocyanate and diamine

In 1962 Kennedy reported the first isomerization

polymerization using 3-methyl-1butene to give a
1,1-dimethyl polypropylene as shown below.

In contrast to addition polymers, the structural

unit in step-growth polymers is not identical
Isomerization polymerizations can be associated with
chemically to the structure of the starting
coordination catalyst systems, ionic catalyst systems,
monomer(s). Consequently, step-growth
and free radical systems. The cationic isomerization
polymers derive their names from the reactive
polymerization of 4-methyl-1-pentene is of interest
In the presence of certain Zeigler catalysts, an
because the product can be viewed as an alternating
equilibrium exists between cis- and trans-1,3-
copolymer of ethylene and isobutylene. This structure
pentadiene.Here thecis-1,4-polypentadiene
cannot be obtained by conventional approaches.
isformed fromtrans-1,3-pentadiene or from a
mixture of cis and trans isomers
also called slurry polymerization, is a variety of
Such isomerizations are sometimes desired and
solution polymerization where the monomer is
sometimes are the cause of or explanation for
soluble but the polymer precipitates as a fine
unwanted structures. In the cationic
oc. The formation of olefin polymers via
polymerization forming poly(1-butene), nine
coordination polymerization occurs by a slurry
different structural units have been found.
process. Here, the catalyst is prepared and
Classical 1,2-hydride and 1,2-methide shifts,
polymerization is carried out under pressure and
hydride transfer, and proton elimination account
at low temperatures, generally less than 100C.
for these structures.
The polymer forms a viscous slurry. Care is taken
type (characteristic interunit linkage) involved in the
so that the polymer does not cake up on the
polymerization process. In the reaction between the
sides and stirrer.
glycol and dicarboxylic acid, for instance, the resulting