TY - JOUR
T1 - Chemically Recyclable Linear and Branched Polyethylenes Synthesized from Stoichiometrically Self-Balanced Telechelic Polyethylenes
AU - Jang, Yoon Jung
AU - Nguyen, Sam
AU - Hillmyer, Marc A.
N1 - Publisher Copyright:
© 2024 American Chemical Society.
PY - 2024/2/21
Y1 - 2024/2/21
N2 - High-density polyethylene (HDPE) is a widely used commercial plastic due to its excellent mechanical properties, chemical resistance, and water vapor barrier properties. However, less than 10% of HDPE is mechanically recycled, and the chemical recycling of HDPE is challenging due to the inherent strength of the carbon-carbon backbone bonds. Here, we report chemically recyclable linear and branched HDPE with sparse backbone ester groups synthesized from the transesterification of telechelic polyethylene macromonomers. Stoichiometrically self-balanced telechelic polyethylenes underwent transesterification polymerization to produce the PE-ester samples with high number-average molar masses of up to 111 kg/mol. Moreover, the transesterification polymerization of the telechelic polyethylenes and the multifunctional diethyl 5-(hydroxymethyl)isophthalate generated branched PE-esters. Thermal and mechanical properties of the PE-esters were comparable to those of commercial HDPE and tunable through control of the ester content in the backbone. In addition, branched PE-esters showed higher levels of melt strain hardening compared with linear versions. The PE-ester was depolymerized into telechelic macromonomers through straightforward methanolysis, and the resulting macromonomers could be effectively repolymerized to generate a high molar mass recycled PE-ester sample. This is a new and promising method for synthesizing and recycling high-molar-mass linear and branched PE-esters, which are competitive with HDPE and have easily tailorable properties.
AB - High-density polyethylene (HDPE) is a widely used commercial plastic due to its excellent mechanical properties, chemical resistance, and water vapor barrier properties. However, less than 10% of HDPE is mechanically recycled, and the chemical recycling of HDPE is challenging due to the inherent strength of the carbon-carbon backbone bonds. Here, we report chemically recyclable linear and branched HDPE with sparse backbone ester groups synthesized from the transesterification of telechelic polyethylene macromonomers. Stoichiometrically self-balanced telechelic polyethylenes underwent transesterification polymerization to produce the PE-ester samples with high number-average molar masses of up to 111 kg/mol. Moreover, the transesterification polymerization of the telechelic polyethylenes and the multifunctional diethyl 5-(hydroxymethyl)isophthalate generated branched PE-esters. Thermal and mechanical properties of the PE-esters were comparable to those of commercial HDPE and tunable through control of the ester content in the backbone. In addition, branched PE-esters showed higher levels of melt strain hardening compared with linear versions. The PE-ester was depolymerized into telechelic macromonomers through straightforward methanolysis, and the resulting macromonomers could be effectively repolymerized to generate a high molar mass recycled PE-ester sample. This is a new and promising method for synthesizing and recycling high-molar-mass linear and branched PE-esters, which are competitive with HDPE and have easily tailorable properties.
UR - http://www.scopus.com/inward/record.url?scp=85185717239&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85185717239&partnerID=8YFLogxK
U2 - 10.1021/jacs.3c12660
DO - 10.1021/jacs.3c12660
M3 - Article
C2 - 38323928
AN - SCOPUS:85185717239
SN - 0002-7863
VL - 146
SP - 4771
EP - 4782
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 7
ER -