22.

7 Step-Growth Polymerization
Step-growth polymerization requires the reaction of two different difunctional
monomers to form an alternating copolymer. Each monomer type cannot react with itself; each
reacts only with the other. Thus, as the polymer molecule grows, the two different monomers
take turns reacting to bond onto the polymer chain. Polyesters, polyamides, and polyurethanes
are examples of copolymers that form following the step-growth polymerization pathway.
Most of the step-growth polymers discussed in this section have much lower molecular
weights than do vinyl polymers due to the increase of intermolecular interactions between the
functional groups. The functional groups interact more intermolecularly because of their
polarity. The advantage of this lower molecular weight is that it gives the polymer a lower
melting point than similar polymers with higher molecular weight. The lower melting point
makes it easier to mold useful items from the molten polymer.
Poly(ethylene terephthalate) is a typical polyester that is prepared via the
transesterification of dimethyl terephthalate and ethylene glycol.
REAKSI

In a transesterification reaction, one ester reacts with an alcohol forming a different ester.

Transesterifikasi
A transesterification reaction usually has an equilibrium constant near one, thus, at equilibrium
the reaction mixture has similar quantities of all the possible esters. Using the methyl ester
helps with the reaction because the methyl ester forms methanol, a low boiling point alcohol.
The methanol can be boiled off from the reaction mixture, thus driving the reaction to
completion.

Synthesis of Poly(ethylene terephthalate)

REAKSI

Distill ethylene glycol from sodium metal in a nitrogen atmosphere. Place 15.5 g of dimethyl
terephthalate and 11.8 g of the freshly distilled ethylene glycol in a heavy walled tube with a
constricted upper portion and a vacuum attachment. Add 25 mg of calcium acetate dihydrate
and 6 mg of antimony trioxide. Enclose the tube in a metal protective sleeve. Warm the reaction
mixture in an oil bath to dissolve the mixture. When dissolved, place a capillary tube with a
slow stream of nitrogen in the solution. Heat to 197oC and maintain the nitrogen flow. Heat 2-
3 hours at 197oC, or until all the methanol has been removed. Heat the tube to 225oC for 20
minutes and then at 285oC for an additional 10 minutes. Cap the top of the tube, connect the
side arm to a vacuum pump, and reduce the pressure to 0.3 mm of Hg. Heat at 285oC for 3.5
hours. Remove the tube from the heat and cool the tube behind a safety shield. On cooling, the
polymer contracts from the walls of the tube and may cause it to shatter. The yield of polymer
is 15.3 g, m.p. about 270oC.

Poly(hexamethylene adipate), more commonly called Nylon 66, is a typical example of

a polyamide. In one synthetic method used to prepare Nylon 66, as well as many other Nylons,
chemists dissolve a diacid chloride in an organic solvent and the diamine in aqueous sodium
hydroxide. Because the two solutions are not soluble in each other, the polymer forms at the
interface between the two layers in a process called interfacial polymerization. With thorough
mixing, the interface area of the two layers increases. After the polymer forms, the chemist
filters the polymer from the reaction mixture.
GAMBAR

Interfacial polymerization occurs when the monomers are dissolved in immiscible solvents. When they
thoroughly mix the two solutions together, the polymer forms.

If, instead of using an alkyl group with the diamine, the chemist uses an aromatic ring,
the polymerization process inserts an aromatic ring into the polymer. The polymer that forms
is much more rigid than the polymer that forms with an alkyl group because the aromatic ring
increases the crystallinity of the polymer. As a consequence, polymers with aromatic rings are
exceptionally strong. Kevlar™, for example, has a tensile strength much higher than steel but
is significantly lighter than steel.
REAKSI
Kevlar™ makes an excellent reinforcing fiber in tires. Bulletproof vests contain up to
18 layers of cloth woven from Kevlar™ yarn.
Polyurethanes are produced by a step-growth polymerization of a diisocyanate with a diol. For
example, toluene-2,4-diisocyanate reacts with ethylene glycol to form the polyurethane.
REAKSI
The mechanism for this reaction is a nucleophilic addition to the C=N bond of the isocyanate.
REAKSI
 Polyurethanes are widely used in making foams. Their major commercial use is in
cushions for furniture and as a foam-in-place insulating material. Industrial chemists have
several ways for making foams. Here is one of those ways. The chemist mixes a small amount
of water with the polyurethane reaction mixture. The water reacts with some of the isocyanate
groups to form an amine and carbon dioxide.
REAKSI
As the polymer forms, it traps the bubbles of carbon dioxide that are also forming.
These carbon dioxide bubbles give the polyurethane a foamy texture as the polymer hardens.
Generally, during the early part of the polymerization process, the manufacturers vigorously
stir the polymer mixture to encourage the formation of smaller bubbles. Then, as the foam
becomes more viscous, they inject the mixture into a mold to form the polymer into the desired
object.

Plastic Recycling
People today are very dependent on the use of plastics because plastics are used in a
wide variety of applications ranging from throwaway packaging to high-tech materials.
However, the use of plastics has created a disposal problem. In the United States, 21% of the
volume and 8% of the weight of garbage come from plastics. Most of this garbage is disposable
packaging materials. The very durability of plastics makes the problem of plastic garbage a
serious problem.
Recycling plastics is the obvious answer to the problem of plastic garbage. Their
durability and low reactivity make plastics ideal candidates for recycling. Then why aren’t
more plastics being recycled? The answer has more to do with consumer habits and economics
than technical obstacles. As recycling centers and curbside pickup become more common,
more plastics will be recycled. The Society of the Plastics Industry developed a code that is
now used on many plastic materials. This code provides information about the plastic used in
the product. The code guides both consumers and recyclers in separating various plastics. Table
22.3 shows the recycling code numbers.

Recycling Code Polymer Common Typical uses for

Consumer Products Recycled Plastic
1 Poly(ethylene Soft drink bottles Soft drink bottles
PET terephthalate) and household and household
chemical bottles chemical bottles
2 High-density Milk and water Bottles and molded
HDPE polyethylene jugs, bottles, and containers
grocery bags
3 Poly(vinyl Shower curtains, Plastic floor mats
V chloride), Vinyl, or shampoo bottles,
PVC vinyl siding, floor
tiles, credit cards
4 Low-density Sandwich bags, Trash and grocery
LDPE polyethylene shrink wrap, trash bags
and grocery bags,
squeeze bottles
5 Polypropylene Plastic lids, bottle Usually part of a
PP caps, toys, diaper mixed resin
linings, clothing material
fibers
6 Polystyrene Styrofoam Molded items:
PS materials, egg rulers, cafeteria
cartons, appliances, trays, Frisbees,
packaging. videocassettes
7 All other plastics Many Plastic “lumber”,
and mixed resins playground
equipment, road
reflectors
Table 22.3. Society of the Plastic Industry recycling codes.
Most recycling involves separation of the plastic from impurities, washing the plastic,
and packaging it for sale. Only poly(ethylene terephthalate) (PET) and high-density
polyethylene (HDPE) are currently being recycled in large quantities. Most other plastics are
recycled only in small quantities, if at all.
A typical recycling process begins with separation of the polymer from contaminants.
For example, a PET soft drink bottle usually has a paper label, a HDPE base, adhesive for
holding the base and label in place, and a HDPE or aluminum cap. These must be separated for
effective recycling. Mixtures of materials are not very useful for further manufacturing.
After sorting the various components of a soft drink bottle, the PET bottles are shredded
into small chips. An air cyclone is used to remove the paper and other lightweight materials,
and the chips are subjected to a detergent wash to remove any remaining labels and adhesives.
The PET chips are then separated from any HDPE chips by a floatation method. PET and
HDPE have different densities. Thus, choosing the correct solvent permits separation of the
two materials. The chips are dried and any remaining aluminum pieces are removed
electrostatically. The plastic chips are now nearly free from contaminants. Over 30% of all
PET soft drink bottles are recycled by this method.
The Eastman Kodak Company has developed an alternative to these physical methods
of purification called chemical recycling. Kodak uses large amounts of PET in making
photographic film. It recycles the scraps by a process known as methanolysis. Section 22.7
describes how PET is made by a transesterification reaction. Kodak recycles PET by a
transesterification reaction that is the reverse of the one used to synthesize PET.
REAKSI
The products, ethylene glycol and dimethyl terephthalate, are purified. They are then ready to
be used in further synthesis.