Synthesis and characterization of polyurethanes crosslinked by polyrotaxanes consisting of half-methylated cyclodextrins and PEGs with different chain lengths

- Polyurethanes crosslinked by polyrotaxanes (PRXs) were designed and synthesized.
- Tightly packed CyDs enhances the reorganized-crystallization of the soft segment chains.
- Loosely packed CyDs act as individually dispersed crosslink points.
- Moderately packed CyDs makes slow reorganized-crystallization of the soft segment chains.

Three polyurethanes (PRX1500Me-PU, PRX4000Me-PU, and PRX6000Me-PU) crosslinked by polyrotaxanes (PRXs), which consist of half-methylated α-cyclodextrins (CyDs) and poly(oxyethylene)glycols with different chain lengths (PEG1500, PEG4000, and PEG6000), were synthesized. The filling ratios of CyD in PRX1500, PRX4000 and PRX6000 are 75, 63 and 37%, respectively. A polyurethane crosslinked by half-methylated CyD (CDMe-PU) was also prepared for comparison of their structure and properties. ATR-FT-IR spectra of the PUs showed that the formation ratio of hydrogen bond between the PU chains around PRXs increased with increase in the filling ratio. DSC and dynamic viscoelastic measurements and tensile tests for the PUs revealed that (i) reorganized-crystallization of the soft segment chains of PRX1500Me-PU easily occurred because of formation of a pure phase for them; (ii) the thermal and physical behaviors of PRX6000Me-PU are similar to those of CDMe-PU because CyDs as the crosslink points disperse in a similar fashion in the PUs; (iii) the PRX4000 with the moderate filling ratio of CyD in PRX4000Me-PU makes slow reorganized-crystallization of the soft segment chains in the PU as well as improves the tensile performance among the PUs.