Covalent Adaptable Networks with Associative Siloxane Exchange Enabled by Amide‐Based Internal Catalysis: Designing for Reprocessability and Extrudability by Increasing the Cross‐Link Density DOI Creative Commons
Nathan S. Purwanto, Tong Wang, Xiaoyang Liu

и другие.

Advanced Functional Materials, Год журнала: 2025, Номер unknown

Опубликована: Май 9, 2025

Abstract Replacing non‐recyclable thermosets with covalent adaptable networks (CANs) that recover cross‐link density after reprocessing will reduce waste and contribute to a circular polymer economy. Many CANs undergoing associative dynamic exchange require catalysis. External catalysis often leads harmful effects, e.g., increased creep, accelerated material aging, catalyst leaching. Herein, internally catalyzed siloxane chemistry is demonstrated resulting from amides covalently linked through alkyl chains siloxanes. Small‐molecule studies show the formation of products reaction two amide‐containing molecules. From rubbery plateau modulus, each siloxane‐exchange‐based CAN exhibits temperature‐invariant, or nearly so, characteristic CANs. The length in siloxane‐containing monomer tunes network density. Cross‐link recovery achieved, required time temperature decreasing increasing Stress relaxation also faster dynamics reprocessability arise because second order (i.e., cross‐linker) concentration. Capitalizing on this, melt extrusion highest demonstrated, achieving same extruded compression‐molded Using identical conditions, next‐highest not extrudable.

Язык: Английский

Biobased, catalyst-free non-isocyanate polythiourethane foams: Highly dynamic nature affords fast reprocessability, extrudability and refoamability DOI
Yixuan Chen, Nathan S. Purwanto, Boran Chen

и другие.

Chemical Engineering Journal, Год журнала: 2024, Номер 496, С. 154035 - 154035

Опубликована: Июль 21, 2024

Язык: Английский

Процитировано

5

Rapidly Self‐Healable and Melt‐Extrudable Polyethylene Reprocessable Network Enabled with Dialkylamino Disulfide Dynamic Chemistry DOI Creative Commons
Boran Chen, Tapas Debsharma, Logan M. Fenimore

и другие.

Macromolecular Rapid Communications, Год журнала: 2024, Номер 45(22)

Опубликована: Июль 24, 2024

Abstract Catalyst‐free, radical‐based reactive processing is used to transform low‐density polyethylene (LDPE) into covalent adaptable networks (PE CANs) using a dialkylamino disulfide crosslinker, BiTEMPS methacrylate (BTMA). Two versions of BTMA are used, BTMA‐S 2 , with nearly exclusively bridges, and n mixture oligosulfide produce S PE CAN CAN, respectively. The two CANs exhibit identical crosslink densities, but the manifests faster stress relaxation, average relaxation times ∼4.5 shorter than those over 130 160 °C temperature range. more rapid dynamics translate compression‐molding reprocessing time at only 5 min (vs 30 for CAN) achieve full recovery density. Both melt‐extrudable within experimental uncertainty density after extrusion. self‐healable, crack fully repaired original tensile properties restored or 60 slightly above LDPE melting point without assistance external forces.

Язык: Английский

Процитировано

5

Extrudable and Highly Creep-Resistant Covalent Adaptable Networks Made from Polyethylene and Ethylene/1-Octene Copolymers by Reactive Processing with Aromatic Disulfide Cross-Links DOI
Mathew Suazo, Logan M. Fenimore, Stephanie M. Barbon

и другие.

ACS Applied Polymer Materials, Год журнала: 2024, Номер unknown

Опубликована: Дек. 3, 2024

Polyolefins like polyethylene (PE) and ethylene-based copolymers are widely used in consumer industrial applications due to their versatility, the diversity tunability of properties, theoretical recyclability at elevated temperatures. However, recycling rates markedly low, and, though cross-linking PE enhances its properties through creation a networked architecture, resulting thermoset known as PEX is rendered completely unrecyclable. Incorporating associative or dissociative dynamic covalent bonds cross-links into plastics promising route both make use spent (via "upcycling" them) generate recyclable alternatives unrecyclable thermosets PEX. Such materials adaptable networks CANs (also called vitrimers if exclusively associative). Here, we present method for imbuing polymers with aromatic disulfide cross-links, robust, reprocessable CANs. Radical-based reactive processing ethylene/1-octene-based 1 wt % dicumyl peroxide 5 bis(4-methacryloyloxyphenyl) (BiPheS methacrylate BPMA) successfully resulted which fully recovered cross-link densities associated thermomechanical after multiple reprocessing cycles. These demonstrate remarkable elevated-temperature creep resistance high-temperature thermal stability high temperatures required exchanges BiPheS-based cross-links. copolymer also enable (re)processability via extrusion temperatures, property recovery demonstrated 260 °C, thereby indicating feasibility extending our approach scales processes well other rigorous applications.

Язык: Английский

Процитировано

4

Development of Mechanically Tunable Polythiourethane Elastomers for Recyclable Energetic Material DOI
Chang Liu, Ran Sun, Hao Wu

и другие.

ACS Applied Polymer Materials, Год журнала: 2025, Номер unknown

Опубликована: Фев. 20, 2025

Язык: Английский

Процитировано

0

Next-generation vitrimer composites for future mobility: Balancing sustainability and functionality – A perspective DOI

Jinhyeok Kang,

Changwoo Nam

European Polymer Journal, Год журнала: 2025, Номер unknown, С. 113967 - 113967

Опубликована: Май 1, 2025

Язык: Английский

Процитировано

0

Covalent Adaptable Networks with Associative Siloxane Exchange Enabled by Amide‐Based Internal Catalysis: Designing for Reprocessability and Extrudability by Increasing the Cross‐Link Density DOI Creative Commons
Nathan S. Purwanto, Tong Wang, Xiaoyang Liu

и другие.

Advanced Functional Materials, Год журнала: 2025, Номер unknown

Опубликована: Май 9, 2025

Abstract Replacing non‐recyclable thermosets with covalent adaptable networks (CANs) that recover cross‐link density after reprocessing will reduce waste and contribute to a circular polymer economy. Many CANs undergoing associative dynamic exchange require catalysis. External catalysis often leads harmful effects, e.g., increased creep, accelerated material aging, catalyst leaching. Herein, internally catalyzed siloxane chemistry is demonstrated resulting from amides covalently linked through alkyl chains siloxanes. Small‐molecule studies show the formation of products reaction two amide‐containing molecules. From rubbery plateau modulus, each siloxane‐exchange‐based CAN exhibits temperature‐invariant, or nearly so, characteristic CANs. The length in siloxane‐containing monomer tunes network density. Cross‐link recovery achieved, required time temperature decreasing increasing Stress relaxation also faster dynamics reprocessability arise because second order (i.e., cross‐linker) concentration. Capitalizing on this, melt extrusion highest demonstrated, achieving same extruded compression‐molded Using identical conditions, next‐highest not extrudable.

Язык: Английский

Процитировано

0