Crystallographic studies of nylon 4. II. On the β and δ polymorphs of nylon 4

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Abstract
In addition to the α polymorph, two crystalline forms of nylon 4, the β and δ polymorphs, have been observed and studied.The β polymorph of nylon 4, which has not been found in a pure condition, appears to be similar to the β polymorph of nylon 6. The extended planar zigzag conformation of chains, found in the α polymorph, is present also in the β polymorph. Three models have been proposed to explain the observed data. In model 1, the staggered shear of van der Waals bonded sheets found in the α polymorph is abandoned; in model 2, the sheets are displaced by 1/2 the b axis, and in model 3 the chains are arranged in a parallel array. The β polymorph is converted to the α form in air upon heating for 11 min. at 227°C. and upon immersion in water for 2 hr. Models 1 and 2 would be converted to the α polymorph by a slippage of the van der Waals bonded sheets while the conversion from model 3 would involve a rupture of hydrogen bonds, a rotation of the chains through 90°, and the reformation of hydrogen bonds. The δ polymorph is formed by rapidly quenching extruded nylon 4 against chilled rolls. It is a metastable form which has only been observed in an unoriented condition. Upon orientation it is completely converted to the α polymorph. In addition to this, its conversion to the α form occurs under conditions similar to the β–α transition. The observed diffraction pattern can be indexed on the basis of a hexagonal packing of chains. High‐temperature x‐ray diffraction studies of the α polymorph suggest that the δ form, or a structure similar to it, is the high‐temperature form of nylon 4.

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