Nylon
Nylon represents a family of
synthetic polymers, a
thermoplastic material, first produced on 28 February,
1935 by Gerard J. Berchet of
Wallace Carothers' research group at
DuPont. The first product was a nylon-
bristled
toothbrush (
1938), followed more famously by women's 'nylons'
stockings (
1940). It is made of
repeating units linked by
peptide bonds (another name for
amide bonds) and is frequently referred to as
polyamide (PA). Nylon was the first
commercially successful polymer and the first
synthetic fiber to be made entirely from
coal, water and air. These are formed into
monomers of intermediate
molecular weight, which are then reacted to form long
polymer chains. It was intended to be a synthetic replacement for
silk and substituted for it in
parachutes after the
United States entered
World War II in 1941, making stockings hard to find until the war's end. Nylon fibers are now used in
fabrics and
ropes, and solid nylon is used for
mechanical parts and as an
engineering material. Engineering grade Nylon is processed by extrusion, casting & injection molding. Type 6/6 Nylon 101 is the most common commercial grade of Nylon, and Nylon 6 is the most common commercial grade of cast Nylon.
Most nylons are
condensation copolymers formed by reacting equal parts of a
diamine and a
dicarboxylic acid, so that
peptide bonds form at both ends of each monomer in a process analogous to
polypeptide biopolymers. The numerical suffix specifies the numbers of
carbons donated by the monomers; the diamine first and the diacid second. The most common variant is nylon 6,6, also called nylon 66, which refers to the fact that the diamine (
hexamethylene diamine) and the diacid (
adipic acid) each donate 6 carbons to the polymer chain. As with other regular
copolymers like
polyesters and
polyurethanes, the
repeating unit consists of one of each monomer, so that they alternate in the chain. Since each monomer in this copolymer has the same
reactive group on both ends, the direction of the
amide bond reverses between each monomer, unlike natural polyamide
proteins which have overall directionality:
C terminal â†'
N terminal. In the laboratory, nylon 6,6 can also be made using
adipoyl chloride instead of adipic acid.
It is difficult to get the proportions exactly correct, and deviations can lead to chain termination at molecular weights less than a desirable 10,000
daltons (
amu). To overcome this problem, a
crystalline, solid "nylon
salt" can be formed at
room temperature, using an exact 1:1
ratio of the
acid and the
base to neutralize each other. Heated to 285 °C, the salt reacts to form nylon polymer. Above 20,000 daltons, it is impossible to spin the chains into
yarn, so to combat this, some
acetic acid is added to react with a free amine end group during polymer elongation to limit the molecular weight. In practice, and especially for 6,6, the monomers are often combined in a water solution. The water used to make the solution is evaporated under controlled conditions, and the increasing concentration of "salt" is polymerized to the final molecular weight.
DuPont patented
[History of Nylon US Patent 2,130,523 'Linear polyamides suitable for spinning into strong pliable fibers', U.S. Patent 2,130,947 'Diamine dicarboxylic acid salt' issued and U.S. Patent 2,130,948 'Synthetic fibers', all issued 20 September 1938] nylon 6,6, so in order to compete, other companies (particularly the German
BASF) developed the
homopolymer nylon 6, or
polycaprolactam â€" not a condensation polymer, but formed by a
ring-opening polymerization (alternatively made by polymerizing
aminocaproic acid). The peptide bond within the caprolactam is broken with the exposed
active groups on each side being incorporated into two new bonds as the monomer becomes part of the polymer backbone. In this case, all amide bonds lie in the same direction, but the properties of nylon 6 are sometimes indistinguishable from those of nylon 6,6—except for melt temperature (N6 is lower) and some fiber properties in products like carpets and textiles. There is also a nylon 9.
Nylon 5,10, made from
pentamethylene diamine and
sebacic acid, was studied by Carothers even before nylon 6,6 and has superior properties, but is more expensive to make. In keeping with this naming convention, "nylon 6,12" (N-6,12) or "PA-6,12" is a copolymer of a 6C diamine and a 12C diacid. Similarly for N-5,10 N-6,11; N-10,12, etc. Other nylons include copolymerized dicarboxylic acid/diamine products that are
not based upon the monomers listed above. For example, some
aromatic nylons are polymerized with the addition of diacids like
terephthalic acid (â†'
Kevlar) or
isophthalic acid (â†'
Nomex), more commonly associated with polyesters. There are copolymers of N-6,6/N6; copolymers of N-6,6/N-6/N-12; and others. Because of the way polyamides are formed, nylon would seem to be limited to unbranched, straight chains. But "star" branched nylon can be produced by the condensation of dicarboxylic acids with
polyamines having three or more
amino groups.
The general reaction is:
A molecule of
water is given off and the nylon is formed. Its properties are determined by the R and R' groups in the monomers. In nylon 6,6, R' = 6C and R = 4C
alkanes, but one also has to include the two carboxyl carbons in the diacid to get the number it donates to the chain. In Kevlar, both R and R' are
benzene rings.
Above their
melting temperatures,
Tm,
thermoplastics like nylon are
amorphous solids or viscous
fluids in which the chains approximate
random coils. Below
Tm, amorphous regions alternate with regions which are
lamellar crystals.[
1] The amorphous regions contribute elasticity and the crystalline regions contribute strength and rigidity. The
planar amide (-CO-NH-) groups are very
polar, so nylon forms multiple
hydrogen bonds among adjacent strands. Because the nylon backbone is so regular and symmetrical, especially if all the amide bonds are in the
trans configuration, nylons often have high crystallinity and make excellent fibers. The amount of crystallinity depends on the details of formation, as well as on the kind of nylon. Apparently it can never be
quenched from a
melt as a completely amorphous solid.
Nylon 6,6 can have multiple parallel strands aligned with their neighboring peptide bonds at coordinated separations of exactly 6 and 4 carbons for considerable lengths, so the
carbonyl oxygens and amide
hydrogens can line up to form interchain
hydrogen bonds repeatedly, without interruption. Nylon 5,10 can have coordinated runs of 5 and 8 carbons. Thus parallel (but not antiparallel) strands can participate in extended, unbroken, multi-chain
β-pleated sheets, a strong and tough supermolecular structure similar to that found in natural
silk fibroin and the
β-keratins in
feathers. (Proteins have only an amino acid α-carbon separating sequential -CO-NH- groups.) Nylon 6 will form uninterrupted
H-bonded sheets with mixed directionalities, but the β-sheet wrinkling is somewhat different. The three-dimensional disposition of each
alkane hydrocarbon chain depends on
rotations about the 109.47°
tetrahedral bonds of singly-bonded carbon atoms.
When
extruded into fibers through pores in an
industrial spinneret, the individual polymer chains tend to align because of
viscous flow. If subjected to
cold drawing afterwards, the fibers align further, increasing their crystallinity, and the material acquires additional
tensile strength.[
2] Block nylon tends to be less crystalline, except near the surfaces due to
shearing
stresses during formation. Nylon is
clear and
colorless, or milky, but is easily
dyed. Multistranded nylon cord and rope is slippery and tends to unravel. The ends can be
melted and fused with a
flame to prevent this.
There are carbon fiber/nylon
composities with higher
density than pure nylon.
Bill Pittendreigh,
Dupont industries, and other individuals and corportations worked diligently during the first few months of
World War II to find a way to replace
Asian
silk with nylon in
parachutes. It was also used to make
tires,
tents,
ropes,
ponchos, and other
military supplies. It was even used in the production of a high-grade paper for
U.S. currency. At the outset of the war,
cotton accounted for more than 80% of all fibers used, and manufactured and
wool fibers accounted for the remaining 20%. By August,
1945, manufactured fibers had taken a market share of 25% and cotton had dropped.
Some of the terpolymers based upon nylon are used every day in packaging. Nylon has been used for
meat wrappings and
sausage sheaths.
Some people, such as
Jack Herer, surmise that
Cannabis sativa was made illegal because the fibers from the
hemp plant, used for
fabrics and
ropes, were in strong competition with nylon (along with paper, fuel, and other industries). While the production of rope from hemp requires no chemicals or industrial processes, nylon fiber is more than twice as strong as hemp and weighs 25% less. An additional problem is that hemp rope rots from the inside out, making it difficult to determine the condition of a rope at a glance. While hemp was originally used in
climbing rope, this is no longer the case, even in countries where cannabis is legal.
In
1940 John W. Eckelberry of DuPont stated that the letters "nyl" were arbitrary and the "on" was copied from the names of other fibers such as
cotton and
rayon. A later publication by DuPont (
Context, vol. 7, no. 2,
1978) explained that the name was originally intended to be "No-Run" ("run" meaning "unravel"), but was modified to avoid making such an unjustified claim and to make the word sound better. The story goes that Carothers changed one letter at a time until DuPont's management was satisfied. But he was not involved in the nylon project during the last year of his life, and committed suicide before the name was coined. There is another story (repeated in James Burke's TV series Connections) that another one of the names considered was to be Duparooh for DUpont Pulls A Rabbit Out Of a Hat. Nylon was never trademarked.Another popular myth is that "Nylon" stands for "Now You Lousy Old Nippons". Yet another explanation is that it stands for "New York-London", the source of the chemists working on the materials sythesis, but there is no evidence that nylon was named after New York and London.
* nylon
fiber*
clothing*
pantyhose*
toothbrush bristles
*
fishing lines
*
nets
*
carpet fiber
*
airbag fiber
*
auto parts: intake
manifolds,
gas (petrol) tanks
*
slings and
rope used in
climbing gear*
machine parts, such as
gears and
bearings
*
parachutes
*
metallized nylon
balloons
*
classical and
flamenco guitar strings
*
paintball marker bolts
*
racquetball,
squash, and
tennis racquet strings*
Polymers
*
Plastic*
Nylon riots*
Cordura*
Article on making Nylon at home *
Typical physical characteristics of nylon
