Chapter 13 Polyamides and related polymers

80% of polyamide production: Nylon 6 and 66

Nylons represent roughly 25% of total fibers production and about 40% of all
engineering plastics.

Amide

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*Three condensation reactions employed in synthesis of amides: dehydration of amine salts
of carboxylic acids, the reaction of acid chlorides with amines, aminolysis of esters

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* x 6 to prevent cyclization to lactam

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* Low temperature solution methods by phosphorylation reaction

* The more basic aliphatic diamines are not suitable for this reaction
because they displace pyridine in the complex.

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* Polysulfonamides

* Polyphosphonamides

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* Polymerization of lactams: with cationic or anionic initiators or with water

* ring-opening acylation of the primary amine function

* Intramolecular cyclization reaction results the low molecular weight under cationic
conditions.

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* The induction period can be eliminated by addition of coinitiators (activators)- acyl
halides or anhydrides that ensure formation of a stabilized anion in the second step.

*Hydrolytic polymerization

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Nylon 8 Nylon 12

Nylon 4 Nylon 5

Nylon 2

polysulfonamide

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*Much higher melting temperature than polyester
*Exhibit an odd-even relationship of homologous series

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*More soluble and less crystalline ordered copolyamides with highly regular structure
solves the problem of low solubility and resultant difficulty in fabrication.

*Substitutent groups on the polymer backbone reduce the melting point of polyamides
significantly.
* Methoxymethylation, alkylation, polyetherification

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 *Polycarbamate from carbamic acid (RNHCO2H)

*Allophonate groups leading to chain branching and crosslinking

* Tm ~ 180C vs 295C of Nylon 46

* Industrial polyurethane production using low MW diols such as 1,4-butanediol and 1,6-
hexanediol as chain extenders

MDI

Polymeric isocyanate

Marked by Bayer under the trade name Perlon U

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Polyurethane fiber consist of elastomeric AB- block copolymers containing alternating
soft and hard segments (Du Ponts Spandex)

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*Condensation polyimidess

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 *Polyimidesulfone by NASA

* Two varieties of addition polyimides : bismaleimides and bisnadimides

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 *To reduce brittleness arising from the high
crosslinking density

*Michael addition of primary diamines in chain extension reduce the crosslink density
and brittleness of the finished product.

*Linear polyaspartimides by Michael addition of secondary diamines in chain extension

reaction.

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PMR: polymerization of monomeric reactants

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