Melt-crystallized nylon-6 nucleated by the constrained chains of its non-stoichiometric cyclodextrin inclusion compounds and the nylon-6 coalesced from them

Non-covalently bonded crystalline inclusion compounds (ICs) have been formed by threading host cyclic starches, cyclodextrins (CDs), onto guest nylon-6 (N-6) chains. When excess N-6 is employed, non-stoichiometric (n-s)-N-6-CD-ICs, with partially uncovered and “dangling” N-6 chains, result. While the host crystalline CD lattice is stable to ∼300 °C, the uncovered, yet constrained, portions of the N-6 chains emanating from the CD-IC surfaces may crystallize below, or be molten above ∼225 °C, and confer upon them shape-memory. When heated between the Tm of N-6 and the decomposition temperature of the (n-s)-N-6-CD-IC, they may be deformed into a new shape, which is retained following a rapid quench below Tm. When this newly-shaped sample is heated above the Tm of the un-included and crystalline portions of N-6, it reverts back to its original shape in response to the constraining CD-IC crystals. When added at low concentrations, the non-toxic (n-s)-N-6-CD-ICs serve as effective nucleating agents for the bulk crystallization of N-6 from the melt. This is a consequence of the ability of the N-6 chains protruding from their (n-s)-CD-ICs to crystallize more rapidly and at higher temperatures than bulk N-6 chains when their molten mixture is cooled, thereby providing finely dispersed crystalline nuclei for the subsequent crystallization of the bulk N-6 chains. Melt-crystallized N-6 nucleated with (n-s)-N-6-CD-ICs have finer grained more homogeneous morphologies than un-nucleated N-6 samples. Furthermore, N-6s coalesced from their CD-ICs by appropriate removal of the host CD are also found to effectively nucleate the melt-crystallization of bulk N-6, even after long periods of annealing above the Tm of N-6. N-6 coalesced from stoichiometric CD-ICs, with full N-6 coverage, and from (n-s)-N-6-CD-ICs, with only partial N-6 coverage, show very similar crystallization behaviors and both are effective as nucleants, and this is reflected by their higher densities and improved mechanical properties. Stress-strain responses of thin melt-pressed neat bulk N-6 films (as-received and annealed), and N-6 film nucleated with N-6 coalesced from its 1:1 stoichiometric α-CD-IC. [Display omitted]