Synthetic upcycling of polyacrylates through organocatalyzed post-polymerization modification

Easterling, Charles P.; Kubo, Tomohiro; Orr, Zachary; Fanucci, Gail E.; Sumerlin, Brent S.

doi:10.1039/c7sc02574b

Cited by 81 publications

(90 citation statements)

References 32 publications

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“…However, despite the high catalytic activity of TBD, when low molecular weight materials (<2500 Da) were targeted, the kinetics of transesterification prevailed over the ROP process, limiting the synthetic strategy toward accessing oligomeric species . In addition, TBD has the tendency to cleave BOC‐protected functionalities, leading to a fast self‐immolative degradation of the growing polymer chain when used in the presence of functional monomers …”

Section: Introductionmentioning

confidence: 99%

Versatile, Highly Controlled Synthesis of Hybrid (Meth)acrylate–Polyester–Carbonates and their Exploitation in Tandem Post‐Polymerization–Functionalization

Pearce

Vasey

Anane-Adjei

et al. 2019

Macro Chemistry & Physics

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The use of 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU) as a mild catalyst for the ring‐opening polymerization (ROP) of the pharma‐friendly and biodegradable monomer lactide and a functionalizable tert‐butyloxycarbonyl (BOC)‐protected cyclic carbonate is explored. Successful and controlled ROP is demonstrated when employing a series of labile‐ester (bis)(meth)acrylate initiators to produce macromonomers suitable for a range of post‐polymerization modifications. Importantly, the use of DBU ensured retention of the BOC group of the carbonate monomer during the polymerization, thus facilitating the production of highly functionalizable hybrid materials unobtainable using the more reactive triazabicyclodecene (TBD). Subsequently, a variety of short homo‐ and copolymers are synthesized with good control over material properties and final polymer composition. Successful attainment of these short copolymers confirm that DBU can overcome the previously observed limitations of TBD related to its kinetic competition between ROP and transesterification side‐reactions under these reaction conditions. Furthermore, the fidelity of the hydroxyl and (meth)acrylic end groups are maintained as confirmed by a series of secondary tandem reactions. The macromonomers are also utilized in reversible addition−fragmentation chain‐transfer polymerization (RAFT) polymerization for the production of amphiphilic block or random copolymers with a hydrophilic comonomer, poly(ethyleneglycol)methacrylate. The amphiphilic copolymers produced via the tandem RAFT reaction demonstrate the ability to self‐assemble into monodisperse nanoparticles in aqueous environments.

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Section: Introductionmentioning

confidence: 99%

Versatile, Highly Controlled Synthesis of Hybrid (Meth)acrylate–Polyester–Carbonates and their Exploitation in Tandem Post‐Polymerization–Functionalization

Pearce

Vasey

Anane-Adjei

et al. 2019

Macro Chemistry & Physics

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“…For example,previous studies have demonstrated that the simple addition of ar adical initiator during extrusion of PE/iPP blends is not av iable solution for compatibilization. [186] New Figure 13. A) Photochemicalm ethods provide opportunities for the heterogeneous functionalization of polymer surfaces that can be patterned lithographically.B )Site-selective CÀHfunctionalization can greatly increase the functionald iversity of commodity materials through simple transformations.…”

Section: Outlook and Future Directionsmentioning

confidence: 99%

“…Lastly,c ontemporary methods have been developed for the post-polymerization modification of commodity acrylate, methacrylate,a nd acrylamide monomers. [186][187][188][189] Commercial polyolefins bearing alkene functional handles have previously been modified in many post-polymerization strategies. [6,190] Although these transesterification or olefin functionalization methods do not involve C À Hfunctionalization, the concept of increasing the functional diversity of commercial polymers is similar to the work presented in this Review.…”

Section: Angewandte Chemiementioning

confidence: 99%

C−H Functionalization of Commodity Polymers

et al. 2019

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Synthetic manipulation of polymer substrates is one of the oldest and most reliable methods to increase the functional diversity of soft materials. Modifying the chemical structure of polymers that are already produced on a commodity scale leverages the current high‐volume and low‐cost production of commodity plastics for the discovery of modern materials. A myriad of polymer C−H functionalization methods have been developed which enable the modification of material properties on both a laboratory and industrial scale. More recently, driven by advances in C−H activation, photoredox catalysis, and radical chemistry, chemoselective approaches have emerged as a means to impart precise functionality onto commodity polymer substrates. This Review discusses the historical significance of and contemporary advances in the C−H functionalization of commodity polymers. The conceptual approach outlined herein presents exciting new directions for the field, including increasing the value of otherwise pervasive materials, uncovering entirely new material properties, and a viable path to upcycle post‐consumer plastic waste.

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“…In addition, hydrolysis of the ester to the corresponding carboxylic acid can be exploited for organocatalyzed esterifications and amidations, and Ugi and Passerini multicomponent reactions . Nevertheless, the direct modification of polymers with unactivated pendant ester groups remains a challenging topic within polymer chemistry, as only recently reports have emerged of their quantitative conversion . Inspired by the guanidine‐catalyzed amidation and transesterification of polymers with pendant ester groups, we explored the use of guanidines as a reactant, rather than a catalyst, in order to synthesize the corresponding acyl guanidines.…”

Section: Introductionmentioning

confidence: 99%

Acyl guanidine functional poly(2‐oxazoline)s as reactive intermediates and stimuli‐responsive materials

Guyse

Hoogenboom

2019

J. Polym. Sci. Part A: Polym. Chem.

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The many postpolymerization modification opportunities of biocompatible poly(2‐alkyl/aryl‐2‐oxazoline)s (PAOx), such as thiol–ene/thiol–yne, azide–alkyne cycloadditions, amidation, and transesterification, are one of the most appealing features of this polymer class for its popularity in biomedicine. Inspired by recent reports on guanidine‐catalyzed transesterification and amidation reactions of methyl ester substrates, we explored the use of guanidines as a reactant for the modification of methyl ester functional PAOx, to obtain the respective acyl guanidines. The obtained acyl guanidines functional polymers display reactivity toward α‐haloketones, yielding imidazole functional PAOx. The obtained polymer structures are protonated in a broad pH range, and the acyl guanidine moiety is demonstrated to be a cleavable linker under basic conditions. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2616–2624

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Synthetic upcycling of polyacrylates through organocatalyzed post-polymerization modification

Abstract: A new method for converting commodity polymeric materials into value-added specialty materials was developed via site-selective and chemoselective transesterification of block copolymers, statistical copolymers, and homopolymers.

Cited by 81 publications

References 32 publications

Versatile, Highly Controlled Synthesis of Hybrid (Meth)acrylate–Polyester–Carbonates and their Exploitation in Tandem Post‐Polymerization–Functionalization

Versatile, Highly Controlled Synthesis of Hybrid (Meth)acrylate–Polyester–Carbonates and their Exploitation in Tandem Post‐Polymerization–Functionalization

C−H Functionalization of Commodity Polymers

Acyl guanidine functional poly(2‐oxazoline)s as reactive intermediates and stimuli‐responsive materials

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