POLYMERS AND PLASTICS II: CONDENSATION POLYMERS THERMOPLASTIC POLYMERS Condensation reactions are probably named for the

water that is produced by some; they are substitution reactions in which small molecules (water, ammonia, HCl, etc.) are formed along with the organic product. Most condensation polymers are produced from carboxylic acids and their synthetic equivalents (esters, acid chlorides); the substitution thus occurs by addition (to the carbonyl) plus elimination. Most can be molded by heating to form a thick liquid (they are thermoplastic) or made into threads by extrusion of a solution through tiny holes (called spinnerets). They are usually rigid glasses at low temperature and flexible elastomers above Tg , the glass transition temperature; they may actually melt at a still higher temperature (Tm). Their properties and uses are determined partially by whether Tg is above or below the temperature during use. polyamides:
O HO O OH H2 N NH2

use: clothing and carpet fibers, spatulas, gears source: petroleum -> benzene -> cyclohexene ->
O N H H N O O N H

----> salt ----> heat

adipic acid
O Cl O

1,6-hexanediamine

nylon 66 +
O O N H

water
O N H

+ terephthaloyl chloride

Cl

H 2N

NH2

----> p-phenylenediamine

N H

Kevlar, an aramid +

HCl

polyesters:

uses: clothing fibers, bottles, source: petroleum -> ethylene and p-xylene ->
O O O O O O O O O

O O

HO + methyl terephthalate ethylene glycol

OH

----> polyethylene terephthalate (PET) +

methanol

urethanes:

uses: pillow foam, raincoats, insulation source: petroleum -> toluene and propene ->
O

C
N O C N

O HO HO

O O O O NH N H N H O O

OH

NH N H

2,4-toluenediisocyanate triol or polyol polycarbonates:

urethane elastomer

uses: eyeglasses and other high index-of-refraction glass substitutes source: petroleum -> propene + benzene ->> phenol ->
O
O

O O O O

HO

OH

[Ph]
O O

[Ph]

bis -phenol A

diphenylcarbonate or phosgene!

----> polycarbonate + polycarbonate +

phenol HCl

THERMOSETTING POLYMERS Other condensation polymers are made from nucleophilic substitution (epoxy) and aldehyde condensation (bakelite). These polymers have three sites of reactivity in one of the monomers, producing highly crosslinked materials that retain the shape into which they polymerize on heating; theyare relatively insoluble and decompose on melting. Such materials which cannot be remolded after polymerization are said to be thermosetting and are often called resins. epoxy: uses: canoes, auto parts, adhesives source: petroleum -> propene + benzene ->> phenol toxicity: Users are often exposed to the monomers, partially prepolymerized; the epoxy component is highly reactive and the catalyst is highly caustic; both irritate tissue. Wear gloves and ensure adequate ventilation.
O O O NH N H O O O NH O N H N H O O

HO

OH

Cl

bis -phenol A

+ epichlorohydrin

----> epoxy resin +

HCl

phenolic resins: uses: pot handles, electrical and thermal insulation source: petroleum ->benzene -> phenol, followed by an aldol condensation in acid or base (note that phenol is the enol of cyclohexa-2,4-dienone)
OH OH O OH H

+ phenol PLASTICIZERS

---> bakelite + water

formaldehyde

Polymers are often are too brittle or rigid for a particular application. They are softened by the addition of small molecules called plasticizers that dissolve in the polymer. The plasticizer in polymer is like the sauce on spaghetti, keeping it from setting up. The most common are dibutyl and dioctyl (really di(2-ethylhexyl)) phthalate, relatively non-toxic compounds. Previously polychlorinatedbiphenyls (PCB's) were used, but like DDT they have long-term toxic and reproductive effects on fish, birds, etc. and have been banned. It is the plasticizers that gum up the windshield of your car when it has been sitting in the sun, and their distillation from the polymeric object leaves it brittle and subject to cracking.
O O O O Cl Cl Cl Cl Cl

dioctyl phthalate FURTHER READING

PCB3

L. Mandelkern, An Introduction to Macromolecules, Springer Verlag, NY 1972, 1983. R. B. Seymour, C. E. Carraher, Jr. Polymer Chemistry: An Introduction, M. Dekker, NY, 1981. K. F. O'Driscoll, The Nature and Chemistry of High Polymers, Reinhold, NY, 1964. H. R. Allcock, F. W. Lampe, Contemporary Polymer Chemistry, 2nd Ed., Prentice-Hall, Englewood Cliffs, NJ, 1990. ORGANIC ENRICHMENT LMS 1993, 1998