Building Tunable Degradation into High-Performance Poly(acrylate) Pressure-Sensitive Adhesives

ACS Macro Letters, Journal Year: 2023, Volume and Issue: 12(6), P. 787 - 793

Published: May 23, 2023

Pressure-sensitive adhesives (PSAs) based on poly(acrylate) chemistry are common in a wide variety of applications, but the absence backbone degradability causes issues with recycling and sustainability. Here, we report strategy to create degradable PSAs using simple, scalable, functional 1,2-dithiolanes as drop-in replacements for traditional acrylate comonomers. Our key building block is α-lipoic acid, natural, biocompatible, commercially available antioxidant found various consumer supplements. α-Lipoic acid its derivative ethyl lipoate efficiently copolymerize n-butyl under conventional free-radical conditions leading high-molecular-weight copolymers (Mn > 100 kg mol-1) containing tunable concentration disulfide bonds along backbone. The thermal viscoelastic properties these materials practically indistinguishable from nondegradable analogues, significant reduction molecular weight realized upon exposure reducing agents such tris (2-carboxyethyl) phosphine (e.g., Mn = 198 mol-1 → 2.6 mol-1). By virtue thiol chain ends produced after cleavage, degraded oligomers can be further cycled between high low weights through oxidative repolymerization reductive degradation. Transforming otherwise persistent poly(acrylates) into recyclable simple versatile could play pivotal role improving sustainability contemporary adhesives.

Language: Английский

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Photoinduced Dithiolane Crosslinking for Multiresponsive Dynamic Hydrogels

Advanced Materials, Journal Year: 2023, Volume and Issue: unknown

Published: Jan. 30, 2023

While many hydrogels are elastic networks crosslinked by covalent bonds, viscoelastic with adaptable crosslinks increasingly being developed to better recapitulate time and position-dependent processes found in tissues. In this work, 1,2-dithiolanes presented as dynamic photocrosslinkers of hydrogels, resulting disulfide bonds throughout the hydrogel that respond multiple stimuli. Using lipoic acid a model dithiolane, formed under physiological conditions, enabling cell encapsulation via an initiator-free light-induced dithiolane ring-opening photopolymerization. The allow for photoinduced responses including stress relaxation, stiffening, softening, network functionalization using single chemistry, which can be supplemented permanent reaction alkenes further control properties connectivity irreversible thioether crosslinks. Moreover, complementary photochemical approaches used achieve rapid complete sample degradation radical scission post-gelation stiffening when irradiated presence reactive gel precursor. results herein demonstrate versatility material chemistry study direct 2D 3D cell-material interactions. This work highlights dithiolane-based photocrosslinking robust method generating range biologically relevant mechanical chemical varied on demand.

Language: Английский

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Controlled-Radical Polymerization of α-Lipoic Acid: A General Route to Degradable Vinyl Copolymers

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(41), P. 22728 - 22734

Published: Oct. 9, 2023

Here, we present the synthesis and characterization of statistical block copolymers containing α-lipoic acid (LA) using reversible addition-fragmentation chain-transfer (RAFT) polymerization. LA, a readily available nutritional supplement, undergoes efficient radical ring-opening copolymerization with vinyl monomers in controlled manner predictable molecular weights low molar-mass dispersities. Because lipoic diads resulting include disulfide bonds, these materials efficiently rapidly degrade when exposed to mild reducing agents such as tris(2-carboxyethyl)phosphine (Mn = 56 → 3.6 kg mol-1). This scalable versatile polymerization method affords facile way synthesize degradable polymers architectures, weights, dispersities from acid, commercially renewable monomer.

Language: Английский

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Recyclable/degradable materials via the insertion of labile/cleavable bonds using a comonomer approach

Progress in Polymer Science, Journal Year: 2023, Volume and Issue: 147, P. 101764 - 101764

Published: Nov. 15, 2023

Language: Английский

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A renewably sourced, circular photopolymer resin for additive manufacturing

Nature, Journal Year: 2024, Volume and Issue: 629(8014), P. 1069 - 1074

Published: May 15, 2024

The additive manufacturing of photopolymer resins by means vat photopolymerization enables the rapid fabrication bespoke 3D-printed parts. Advances in methodology have continually improved resolution and speed, yet both process design resin technology remained largely consistent since its inception 1980s

Language: Английский

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Self‐Healing Materials for 3D Printing

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: 34(30)

Published: March 21, 2024

Abstract Additive manufacturing/3D printing is praised as revolutionary by many because it enables the decentralized and on‐demand manufacturing of complex shapes. With ongoing rapid development increased availability these technologies, has become crucial to develop novel materials with unique functionalities for 3D‐printed components. Advances in self‐healing have resulted structures capable recovering from physical damage through material remendability. By applying solutions 3D printing, researchers are attempting overcome current barriers such low mechanical properties, waste, printability issues, among others. This review summarizes state research on used presents recent progress The particular focus use intrinsic polymer self‐healing, which prominent published literature. mechanisms proposed systems well their composition highlighted, intended application respect focused on. scientific technological challenges involved implementation approaches potential functional applications new also discussed.

Language: Английский

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The Emergence of Reversible–Deactivation Radical Polymerization in 3D Printing

Advanced Materials Technologies, Journal Year: 2022, Volume and Issue: 8(5)

Published: Sept. 18, 2022

Abstract The majority of materials 3D printed using vat photopolymerization techniques are prepared by uncontrolled polymerization methods and cannot be easily modified to introduce additional functionality; these can considered as effectively “dead” materials. Fortunately, a suite photocontrolled reversible–deactivation radical (photoRDRP) is recently implemented in printing. In addition their fast rate oxygen tolerance, the high livingness imparted photoRDRP beginning disrupt field printing providing access with advanced properties, including on‐demand editing surface bulk self‐healing, control over nanostructuration mechanical properties. This mini‐review analyzes development photoinduced an emphasis on highly tailorable possible through techniques.

Language: Английский

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A review of adsorption materials and their application of 3D printing technology in the separation process

Chemical Engineering Journal, Journal Year: 2023, Volume and Issue: 475, P. 146247 - 146247

Published: Sept. 29, 2023

Language: Английский

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Cationic ring-opening polymerization of natural thioctic acid to chemically recyclable and self-healable poly(thioctic acid) supramolecular material

Chemical Engineering Journal, Journal Year: 2024, Volume and Issue: 482, P. 148816 - 148816

Published: Jan. 18, 2024

Language: Английский

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Bottlebrush Networks: A Primer for Advanced Architectures

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(22)

Published: April 8, 2024

Abstract Bottlebrush networks (BBNs) are an exciting new class of materials with interesting physical properties derived from their unique architecture. While great strides have been made in our fundamental understanding bottlebrush polymers and networks, interdisciplinary approach is necessary for the field to accelerate advancements. This review aims act as a primer BBN chemistry physics both current members community. In addition providing overview contemporary synthetic methods, we developed workflow desktop application (LengthScale), enabling be more approachable. We conclude by addressing several topical issues asking series pointed questions stimulate conversation within

Language: Английский

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