Structure and Morphology of Thermoplastic Polyamide Elastomer Based on Long-Chain Polyamide 1212 and Renewable Poly(trimethylene glycol)

Abstract

Novel biobased thermoplastic polyamide elastomers (TPAEs) were synthesized using a long-chain polyamide 1212 (PA1212) oligomer and 100% renewably resourced poly-(trimethylene glycol) (PPDO) via a facile "two-step" melt polycondensation. The TPAEs are lightweight, with a density of 1.04∼1.05 g cm −3 . The structure and morphology of the TPAEs with high biocontent were investigated by nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy (FT-IR), differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD), atomic force microscopy (AFM), transmission electron microscopy (TEM), and dynamic thermomechanical analysis (DMA). The results show that the new biobased TPAEs have a clearly microphase-separated structure comprising quite low crystalline PA1212 segments and an amorphous PPDO segment at room temperature. The spherical rigid PA1212 domains for PA624-PPDO with a diameter of about 100 nm can well disperse in the amorphous PPDO phase. Moreover, the rigid PA1212 segments mutually interconnect with the increasing molecular weight of the PA1212 oligomer, and the typical PA1212 spherulites about 200 nm with lamellae structures have been found in PA2200-PPDO, filled with amorphous PPDO in the interlayer. Since the structure and morphology characteristics, the storage modulus (E′) of TPAEs quickly decreases from about 3000 MPa in a glassy state to 400 MPa in a rubbery state. Furthermore, long-chain PA1212 segments contribute to the outstanding thermal stability; i.e., the initial decomposition temperatures of all TPAEs are over 360 °C. The novel biobased TPAEs with good lowtemperature elastic, high elastic recovery, and good thermally stable properties are expected to have potential applications in CO 2 separation and breathable dressing. ■ HIGHLIGHTSNovel TPAEs have a long-chain polyamide as a rigid segment and 100% renewably resourced polyether as a flexible segment. The biobased TPAE is lightweight with good thermal and mechanical properties. Microphase-separated morphology of the TPAEs is observed.

Facile Synthesis of Thermoplastic Polyamide Elastomers Based on Amorphous Polyetheramine with Damping Performance

“…The C3 building block has been hardly used in the preparation of TPAEs. In our previous work, a linear semicrystalline poly(trimethylene glycol) (PPDO) has been utilized to prepare TPAEs with high elasticity [ 22 ]. Nevertheless, for these semicrystalline blocks, the melting of the corresponding segments will cause the variation of storage modulus, which is not conducive to the use of materials in this temperature range [ 2 ].…”

Current trends in bio‐based elastomer materials

“…A polyamide 1212 (PA1212) oligomer and bio-based poly (trimethylene glycol) (PPDO) are used to prepare bio-based lightweight TPAEs with a density of 1.04-1.05 g/cm 3 . 292 The properties of the bio-based TPAEs can be controlled by the molecular weight of the PA1212 oligomer. The tensile strength and elongation at break of PA624-PPDO (the molecular weight of PA1212 is 624 g/mol) are 5.2 MPa and 1850%, respectively; while those of PA1757-PPDO are 22 MPa and about 450%, respectively (Figure 34).…”

Thermoplastic Polyamide Elastomers: Synthesis, Structures/Properties, and Applications

“…For typical TPAEs, one of the following PAs such as PA6, PA66, PA11, PA12, and PA1212 can serve as the rigid segment, while one of the polyether glycols such as generally polyethylene glycol (PEG), polypropylene glycol (PPG), and polytetramethylene glycol (PTMG) acts as the soft component. [ 12–15 ] In the later 1970s, Deleens and co‐workers [ 16 ] in Ato Chimie Company (France) employed metal alkoxide as catalyst to successfully solve the synthesis problem of TPAE block copolymer and subsequently launched the first generation of commercial TPAE products which are widely known as Pebax at present. Shortly afterward, more types of TPAEs were synthesized on the laboratory scale; some were patented and commercialized with crucial industrial applications.…”