Semi-Aromatic Polyether Amide Thermoplastic Elastomer: Nucleophilic Substitution Polymerization and Properties

Abstract

Different from the traditional electrophilic polymerization method of thermoplastic elastomer, here, we adopted a new nucleophilic reaction route, which did not need extreme high temperature and vacuum condition to prepare a novel kind of semi-aromatic thermoplastic polyether amide elastomers. First, difluoro-terminated semi-aromatic di-amide monomer containing long chain ether (or 1,12-diaminododecane) was synthesized through facile interfacial electrophilic substitution reaction. Then, they were conducted to react with hydroquinone under atmospheric pressure to yield polyether amide elastomer. Additionally, a small amount of branched structure with trifluoro-terminated semi-aromatic amide monomer was designed and further introduced into the polymer chain to adjust the mechanical property. These semi-aromatic polyamide elastomers were found to have excellent thermal properties with glass transition temperature (T g) of −39.5 to −34.8 °C, melting temperature (T m) of 227.3–260.4 °C [which is much higher than that of the commercial products such as Pebax5533 (Arkema, Paris, France) (T m = 159 °C)], the 5% weight-loss temperature (T d,5%) of 376.3–408.7 °C, and Vicat softening temperature of 73.0–223.6 °C. The mechanical properties of these resultant elastomers were good and can be controlled with different copolymerization ratios of soft, hard, and branched segments. The tensile strength, elongation at break, and elasticity modulus were in the range of 9.8–23.4 MPa, 87.6–712.3%, and 30.8–362.0 MPa, respectively. Besides, such a series of copolymers showed a relatively low water absorption of 1.57–3.67%. Interestingly, it was found that these resultant polyether amide elastomers had better organic solvent resistance and acid–base corrosion than the traditional TPAE-containing ester bond (−COO−) in the polymer molecular chain. It can be potentially applied in the chemical mechanical seal, especially in the high temperature and corrosion environment.

Reactive melt‐grafting of maleic anhydride onto olefin block copolymer toward high‐performance polar polyolefin thermoplastic elastomer

“…[1][2][3] In general, TPE has a two-phase structure in which its hard phase solidifies at room temperature and melts into fluid upon heating while its soft phase is continuous rubbery chains linked into the network structure at room temperature. 4 It is a trend to develop high-performance TPE to replace traditional crosslinked rubber so as to improve production efficiency and save energy and resources. [5][6][7][8] Ethylene-⊍ olefin copolymers are important TPE species including ethylene-octene random copolymer (POE) which is obtained by metallocene catalyzed copolymerization [9][10][11] and has a low melting point.…”

“…Thermoplastic elastomer (TPE) is a kind of rubber‐like material that integrates rubber properties with plastic processing and recyclability 1–3 . In general, TPE has a two‐phase structure in which its hard phase solidifies at room temperature and melts into fluid upon heating while its soft phase is continuous rubbery chains linked into the network structure at room temperature 4 . It is a trend to develop high‐performance TPE to replace traditional crosslinked rubber so as to improve production efficiency and save energy and resources 5–8 .…”

Virtual Special Issue on Chemical Engineering under Extreme Conditions

“…Other exciting studies in this VSI include antifreeze peptides in ultralow temperatures, asphaltene deposition under high temperatures and pressures, thermoplastics with thermal stability exceeding commercial products, materials for extreme microwave protection, thermostable porous materials, high-pressure hydrogen storage materials, low-temperature ethylene oxide production, and treatment of extremely toxic water …”