Polyrotaxane fibers prepared with wet spinning of polyrotaxane consisting of poly(ethylene glycol) and cyclodextrins (CDs) were cross-linked with two different cross-linking reagents, i.e., divinyl sulfone (DVS) and ethylene glycol diglycidyl ether (EGDE), to improve tensile properties of the fibers. By cross-linking with DVS, the values for the tenacity at break and the initial modulus were increased with cross-linking time, while the elongation at break was improved only moderately. On the other hand, drastic improvements in elongation at break were observed after EGDE cross-linking, up to 645% of its original length, although the tenacity at break and the initial modulus showed only slight improvements. After cross-linking, only minor changes in the degree of crystallinity fibers were observed by wide-angle X-ray scattering (WAXS) measurements.Keywords: polyrotaxane fibers, cyclodextrins, cross-linking, tensile measurements -2 -
IntroductionIn our previous paper [1] on the functional polyrotaxane fibers, we reported a successful preparation of pure polyrotaxane fibers by wet spinning from polyrotaxane dope solution in various polyrotaxane solvents, i.e., dimethylsulfoxide (DMSO), dimethylacetamide (DMAc) containing lithium chloride (LiCl), and dimethylformamide (DMF) containing LiCl. Electron microscopy observations revealed a smooth and crack-free surface texture of the as-spun polyrotaxane fibers. By tensile measurements, the fibers spun from these three solvent systems showed similar levels of initial modulus and tenacity at break, whose values were relatively lower than those of commercial fibers such as polyesters and rayons. The values for elongation at break, however, were extremely high: up to 388% at 50% RH and 972% at 95% RH. The fiber spun from the DMSO dope solution showed a higher value of the elongation at break than the fibers from DMF/LiCl and DMAc/LiCl. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 -3 -The results also imply a successful preparation of novel spandex-like fibers exhibiting high levels of elongation at break and elastomeric properties.Cross-linking treatments of spun fibers are widely used for the preparation of functional fibers and improvements in physical properties of fibers. For example, previous studies showed remarkable improvements in wet and dry mechanical properties of chitosan fibers by cross-linking [7,8]. Poly(vinyl alcohol) fibers cross-linked with boric acid also showed improved strength and Young's modulus [9]. Cross-linking treatments are also applied to the preparation of rayons [10] and ultra-high-molecular weight polyethylene fibers [11] with improved physical properties, as well as finishing of fabrics such as crease-resistant finishing [12]. Recent investigations have utilized novel bio-mimetic cross-linking mechanisms, mediated by the action of enzymes or oxidation ...