Reactive processing of poly(lactic acid)/poly(ethylene octene) blend film with tailored interfacial intermolecular entanglement and toughening mechanism

doi:10.1016/j.jmst.2021.04.051

Abstract

Abstract:

In order to obtain a uniform and effectively toughened poly (lactic acid) film by blending with low content of poly (ethylene octene) (POE) with high elasticity, the tailored interfacial intermolecular interaction and entanglement between the two phases of the PLA/POE blend was innovatively constructed via the facile reactive melt blending process through the reaction of the epoxy/anhydride groups grafted on the POE chains with the end groups of PLA chains (PLA/GPOE-MPOE). It was observed that POE domains were embedded tightly in PLA matrix with a fuzzy interface and abundant interface transition area, and the impact fractured surface of the blend showed an obvious plastic deformation with less occurrence of fibrillation of PLA matrix or interfacial de-bonding. Compared with neat PLA and directly blended PLA/POE blends, the PLA/GPOE-MPOE blend exhibited much higher complex viscosity/storage modulus, much lower tanδ values in the terminal region, and obvious strain-hardening behavior. The deviation in viscoelastic behavior of PLA/GPOE-MPOE from linear PLA indicated the enhanced molecular entanglement between the long-branched chains, resulting in an enhancement of the stretching ability during biaxial drawing of the blend. Uniform PLA/GPOE-MPOE films with draw ratio as high as 7 × 7 were obtained through biaxial stretching, which showed much higher tensile strength and the elongation at break than that of neat PLA and PLA/POE film. This work provides a facile method for fabricating toughening PLA films with application potentials.

Key words: Poly (lactic acid)/poly (ethylene octene) (PLA/POE) blend film, Reactive processing, Tailored interfacial intermolecular interaction, Long-chain branched structure, Toughening mechanism

Wenjun He, Lin Ye, Phil Coates, Fin Caton-Rose, Xiaowen Zhao. Reactive processing of poly(lactic acid)/poly(ethylene octene) blend film with tailored interfacial intermolecular entanglement and toughening mechanism[J]. J. Mater. Sci. Technol., 2022, 98: 186-196.

Figures/Tables 9

Fig. 1. ATR-FTIR spectra of POE, GPOE, MPOE, PLA and PLA/GPOE-MPOE in the range of 4000-500 cm-1 (a), ATR-FTIR spectra of POE, GPOE and MPOE in the range of 1900-1200 cm-1 (b) and 1100-600 cm-1 (c), ATR-FTIR spectra of PLA and PLA/GPOE-MPOE in the range of 2000-500 cm-1 (d).

Fig. 2. Schematic illustration of the formation of interfacial covalent linkage in PLA/GPOE-MPOE blend.

Fig. 3. Rheological plots for neat PLA, PLA/POE and PLA/GPOE-MPOE blends: complex viscosity versus angular frequency (a); storage modulus (G′) versus angular frequency (b); tanδ versus angular frequency (c); Han plots (d); vGP plots (e); Cole-Cole plots (f).

Fig. 4. Elongational viscosity ηE at strain rates of 0.05, 0.1, 0.5 and 1 s - 1 at 170 °C for PLA (a), PLA/POE (b), PLA/GPOE-MPOE (c) and strain hardening coefficient of neat PLA, PLA/POE and PLA/GPOE-MPOE samples (d).

Fig. 5. Stress-strain curves (a) and fracture toughness (b) of PLA, PLA/POE and PLA/GPOE-MPOE samples.

Fig. 6. The photograph and the surface 3D morphology of neat PLA, PLA/POE and PLA/GPOE-MPOE films with maximum draw ratios (a), mechanical properties of PLA, PLA/POE and PLA/GPOE-MPOE films: tensile strength (b), elongation at break (c), tensile modulus (d) and the comparison of mechanical properties of PLA films with draw ratio of 4 × 4 in reported literature (e).

Fig. 7. SEM photographs of cyro-fractured PLA/POE (a) and PLA/GPOE-MPOE (b) (magnification: 2000 ×), and Raman spectra of PLA and POE (c); The phase distribution of neat PLA, POE and interfacial transition area between PLA and POE phases (d); Raman image of PLA/POE (e) and PLA/GPOE-MPOE (f).

Fig. 8. SEM photographs of impact fracture surfaces of neat PLA (a, b), PLA/POE (c, d) and PLA/GPOE-MPOE (e, f).

Fig. 9. Illustration of the toughening mechanism of PLA/GPOE-MPOE blend film with enhanced interfacial intermolecular interaction and entanglement.

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