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Isotactic poly(1-butene)s (iPBs) were synthesized via bulk polymerization of 1-butene in the presence of a series of nucleating agents (NAs). The effects of the NAs on the polymerization, crystallization and mechanical properties of the resultant iPBs were systematically investigated. Both ⊍and ⊎-NAs effectively improve the impact resistance of iPB. Specifically, the addition of ⊎-NAs increases the molecular weight, tensile strength, elastic and flexural moduli of iPB without affecting catalytic activity during polymerization, while the ⊍-NAs have no affirmative effect on improving the tensile strength and elastic modulus of iPB. The ⊎-NAs also accelerate the crystal transition rate of iPB from form II to form I.

Using carbon dioxide-based poly(propylene ether carbonate) diol (PPCD), isophorone diisocyanate (IPDI), dimethylolbutyric acid (DMBA), ferric chloride (FeCl3), and ethylene glycol (EG) as the main raw materials, a novel thermoplastic polyurethane (TPU) is prepared through coordination of FeCl3 and DMBA to obtain TPU containing coordination enhancement directly. The Fourier transform infrared spectroscopy, 1H NMR, gel permeation chromatography, UV−Vis spectroscopy, tensile testing, dynamic mechanical analysis, X-ray diffraction, differential scanning calorimetry, and thermogravimetric analysis were explored to characterize chemical structures and mechanical properties of as-prepared TPU. With the increasing addition of FeCl3, the tensile strength and modulus of TPU increase. Although the elongation at break decreases, it still maintains a high level. Dynamic mechanical analysis shows that the glass-transition temperature moves to a high temperature gradually along with the increasing addition of FeCl3. X-ray diffraction results indicate that TPUs reinforced with FeCl3 or not are amorphous polymers. That FeCl3 coordinates with DMBA first is an effective strategy of getting TPU, which is effective and convenient in the industry without the separation of intermediate products. This work confirms that such Lewis acids as FeCl3 can improve and adjust the properties of TPU contenting coordination structures with an in-situ reaction in a low addition amount, which expands their applications in industry and engineering areas.

With the increase in awareness of environmental protection and the shortage of oil resources, bio-based polyurethane has attracted increasing attention due to its ecological friendliness, low cost and easy degradation. In this paper, using Eugenol (Eug) derived from plant essential oils as the raw resource, syringyl ethanol (Syol) was prepared, and three monomers were obtained by the reaction of the Eug or Syol with Hexamethylene diisocyanate (HDI)or 4,4′-methylene di (phenyl isocyanate) (MDI), respectively. Then, three novel bio-based polyurethanes, P(Eug-HDI), P(Syol-HDI) and P(Syol-MDI), were synthesized by olefin metathesis polymerization. The effects of the catalyst type, reaction solvent, reaction temperature, reaction time, molar ratio of catalyst dosage and metal salts on the Eug-HDI olefin metathesis polymerization were investigated in detail. Under the optimal conditions, the yield reached 64.7%. It is worth noting that the addition of metal Ni salts could significantly promote the polymerization, in which NiI2 could increase the yield to 86.6%. Furthermore, the thermal decomposition behaviors of these bio-based polyurethanes were explored by DSC and variable temperature infrared spectroscopy. The test results showed that P(Eug-HDI) had a reversible thermal decomposition and a certain self-healing performance. This paper provided a new method for the preparation of bio-based polyurethane.