Polyamides 2.

Chemistry
The synthesis of the commercially important nylons
Nylons are members of the family of polyamides, may be depicted by the general Eqns. (1), (2), and (3),
which are polymers whose structural units are inter- Equation (1) refers to the formation of AABB type
linked by the amide linkage NHCO. Generically, nylons. Equations (2) and (3) pertain to the synthesis
the term nylon refers to synthetic polyamides derived of AB type nylons entailing the polycondensation of
predominantly from aliphatic monomers. Synthetic amino acids (Eqn. (2)), and the ring opening poly-
polyamides in which at least 85% of the amide merisation of lactams (Eqn. (3)).
functions are directly adjacent to aromatic structures
are designated aramids, and are discussed separately.
Having recurring amide groups as integral parts of the
polymer backbone, nylons have been classified as
condensation polymers, regardless of the principal
reactions of the polymerisation process. Though many
approaches have been reported for the synthesis of
polyamides, the commercially important nylons are
obtained by two basic processes: one is the poly-
condensation of difunctional monomers, utilizing
either amido acids or stoichiometric pairs of di-
carboxylic acids and diamines; the other is the ring-
opening polymerisation of lactams. The polymers
formed by the condensation of diacids and diamines
are generally referred to as AABB types, whereas
those derived from either amino acids or lactams are Other approaches for the synthesis of nylons in-
called AB types. clude:
(i) the low-temperature polycondensation of di-
amines and diacid chlorides, a process important in
the production of aromatic polyamides;
1. Nomenclature (ii) the ring-opening polymerisation of N-carboxy-
α-amino-acid anhydrides, a process used for the
Straight-chain aliphatic nylons are commonly identi- synthesis of poly(α-amino acids) and polypeptides
fied either as nylon X, Y or nylon Z, where X, Y and Z (nylon 2)—Eqn. (4);
are numbers that signify the number of carbon atoms
in the respective structural (monomer) units. The pair
X, Y refers to the AABB type nylons, where X is equal
to the number of the carbon atoms in the diamine
backbone unit, and Y represents the number of carbon (iii) the hydrogen-transfer polymerization entailing
atoms in the corresponding diacid unit. The number Z addition of amines to activated double bonds (nylon
refers to the AB type nylons, and is equal to the 3)—Eqn. (5);
number of carbon atoms in the amino-acid backbone
unit. Thus, nylon 6, 10 is the polyamide produced
from the 6-carbon hexamethylene diamine and the 10- (iv) the polymerization of isocyanates (nylon 1)—
carbon sebacic acid, whereas nylon 11 is made from Eqn. (6);
the 11-carbon amino-undecanoic acid, and nylon 6
from the 6-carbon caprolactam. The coding of nylons (v) the reaction of dinitriles with formaldehyde
derived from ring structures usually entails either a (nylon 1,Y)—Eqn. (7).
single letter or a combination of letters representing
the ring-containing unit. For example, nylon 6, T
refers to a polyamide produced from hexamethylene
diamine and terephthalic acid, whereas nylon mXD, 6
is derived from m-xylylenediamine and adipic acid.
Copolymer compositions are represented by listing the The commercially important melt polyamidation by
components in order of decreasing percentages, and polycondensation (Eqns. (1) and (2)), involving the
adding the weight percentages in parenthesis. Thus, reaction between amino groups and carboxyl groups,
nylon 6,6–6,10 (60: 40) refers to a product obtained by results in an equilibrium, the principal constituents
copolymerising hexamethylene diamine, adipic acid being monomers, linear-polymer molecules and water.
and sebacic acid in such quantities that a composition Assuming equivalence of all the amide groups formed
containing 60% 6,6 units and 40% 6,10 units is and independence of the reactivities of the end groups
obtained. from the molecular-chain length, this condensation