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Organocatalyzed Photoredox Radical Ring-Opening Polymerization of Functionalized Vinylcyclopropanes.

ABSTRACT: Organocatalyzed photoredox radical ring-opening polymerization (rROP) of vinylcyclopropanes (VCPs) is employed for the synthesis of polymers with controlled molecular weight (MW), dispersity, and composition. Herein, we report the study on the rROP of a variety of VCP monomers bearing diverse functional groups (such as amide, alkene, ketal, urea, hemiaminal ether, and so on) under organocatalyzed conditions with varying light sources and temperature. Notably, VCP monomers bearing natural product functionality or their derivatives can be polymerized in a controlled manner to produce poly(VCPs) with predictable MW, low dispersity, tunable composition, high thermal stability, and tailored glass transition temperature (T _g), ranging 39 to 107 °C. Lastly, successful "grafting through" synthesis of molecular brush copolymers containing 1.0 or 5.0 kDa polydimethylsiloxane (PDMS) side chains from readily accessible EtVCP-PDMS macromonomers further demonstrates the robustness of this organocatalyzed photoredox rROP.

SUBMITTER: Chen DF

PROVIDER: S-EPMC8276880 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Controlling Polymer Composition in Organocatalyzed Photoredox Radical Ring-Opening Polymerization of Vinylcyclopropanes.

Project description:Although radical polymerizations are among the most prevalent methodologies for the synthesis of polymers with diverse compositions and properties, the intrinsic reactivity and selectivity of radical addition challenge the ability to impart control over the polymerization propagation and produce polymers with defined microstructure. Vinylcyclopropanes (VCPs) can be polymerized through radical ring-opening polymerization to produce polymers possessing linear (l) or cyclic (c) repeat units, providing the opportunity to control polymer structure and modify the polymer properties. Herein, we report the first organocatalyzed photoredox radical ring-opening polymerization of a variety of functionalized VCP monomers, where high monomer conversions and spatial and temporal control were achieved to produce poly(VCPs) with predictable molecular weight and low dispersity. Through manipulating polymerization concentration and temperature, tunable l or c content was realized, allowing further investigation of thermal and viscoelastic materials properties associated with these two distinct compositions. Unexpectedly, the photoredox catalysis enables a postpolymerization modification that converts l content into the c content. Combined experimental and computational studies suggested an intramolecular radical cyclization pathway, where cyclopentane and cyclohexane repeat units are likely formed.

| S-EPMC6941592 | biostudies-literature

Catechol End-Functionalized Polylactide by Organocatalyzed Ring-Opening Polymerization.

Project description:There is a great interest in incorporating catechol moieties into polymers in a controlled manner due to their interesting properties, such as the promotion of adhesion, redox activity or bioactivity. One possibility is to incorporate the catechol as end-group in a polymer chain using a functional initiator by means of controlled polymerization strategies. Nevertheless, the instability of catechol moieties under oxygen and basic pH requires tedious protection and deprotection steps to perform the polymerization in a controlled fashion. In the present work, we explore the organocatalyzed synthesis of catechol end-functional, semi-telechelic polylactide (PLLA) using non-protected dopamine, catechol molecule containing a primary amine, as initiator. NMR and SEC-IR results showed that in the presence of a weak organic base such as triethylamine, the ring-opening polymerization (ROP) of lactide takes place in a controlled manner without need of protecting the cathechol units. To further confirm the end-group fidelity the catechol containing PLLA was characterized by Cyclic Voltammetry and MALDI-TOF confirming the absence of side reaction during the polymerization. In order to exploit the potential of catechol moieties, catechol end-group of PLLA was oxidized to quinone and further reacted with aliphatic amines. In addition, we also confirmed the ability of catechol functionalized PLLA to reduce metal ions to metal nanoparticles to obtain well distributed silver nanoparticles. It is expected that this new route of preparing catechol-PLLA polymers without protection will increase the accessibility of catechol containing biodegradable polymers by ROP.

| S-EPMC6415175 | biostudies-literature

Stereoselective photoredox ring-opening polymerization of O-carboxyanhydrides.

Project description:Biodegradable polyesters with various tacticities have been synthesized by means of stereoselective ring-opening polymerization of racemic lactide and ?-lactones but with limited side-chain groups. However, stereoselective synthesis of functional polyesters remains challenging from O-carboxyanhydrides that have abundant pendant side-chain functional groups. Herein we report a powerful strategy to synthesize stereoblock polyesters by stereoselective ring-opening polymerization of racemic O-carboxyanhydrides with the use of photoredox Ni/Ir catalysts and a selected Zn complex with an achiral ligand. The obtained stereoblock copolymers are highly isotactic with high molecular weights (?>?70?kDa) and narrow molecular weight distributions (Mw/Mn?<?1.1), and they display distinct melting temperatures that are similar to their stereocomplex counterparts. Furthermore, in one-pot photoredox copolymerization of two different O-carboxyanhydrides, the use of such Zn complex mediates kinetic resolution of the comonomers during enchainment and shows a chirality preference that allows for the synthesis of gradient copolymers.

| S-EPMC5908805 | biostudies-other

Organocatalyzed Atom Transfer Radical Polymerization Using N-Aryl Phenoxazines as Photoredox Catalysts.

Project description:N-Aryl phenoxazines have been synthesized and introduced as strongly reducing metal-free photoredox catalysts in organocatalyzed atom transfer radical polymerization for the synthesis of well-defined polymers. Experiments confirmed quantum chemical predictions that, like their dihydrophenazine analogs, the photoexcited states of phenoxazine photoredox catalysts are strongly reducing and achieve superior performance when they possess charge transfer character. We compare phenoxazines to previously reported dihydrophenazines and phenothiazines as photoredox catalysts to gain insight into the performance of these catalysts and establish principles for catalyst design. A key finding reveals that maintenance of a planar conformation of the phenoxazine catalyst during the catalytic cycle encourages the synthesis of well-defined macromolecules. Using these principles, we realized a core substituted phenoxazine as a visible light photoredox catalyst that performed superior to UV-absorbing phenoxazines as well as previously reported organic photocatalysts in organocatalyzed atom transfer radical polymerization. Using this catalyst and irradiating with white LEDs resulted in the production of polymers with targeted molecular weights through achieving quantitative initiator efficiencies, which possess dispersities ranging from 1.13 to 1.31.

| S-EPMC5485656 | biostudies-literature

Removal of photoredox catalysts from polymers synthesized by organocatalyzed atom transfer radical polymerization.

Project description:Organocatalyzed atom transfer radical polymerization (O-ATRP) is a method of producing polymers with precise structures under mild conditions using organic photoredox catalysts (PCs). Due to the unknown toxicity of PCs and their propensity to introduce color in polymers synthesized by this method, removal of the PC from the polymer product can be important for certain applications of polymers produced using O-ATRP. Current purification methods largely rely on precipitation to remove the PC from the polymer, but a more effective and efficient purification method is needed. In this work, an alternative purification method relying on oxidation of the PC to PC · + followed by filtration through a plug to remove PC · + from the polymer and removal of the volatiles was developed. A range of chemical oxidants and stationary phases were tested for their ability to remove PCs from polymers, revealing chemical oxidation by N-bromosuccinimide followed by a filtration through a silica plug can remove up to 99% of the PC from poly(methyl methacrylate). Characterization of the polymer before and after purification demonstrated that polymer molecular weight, dispersity, and chain-end fidelity are not signficantly impacted by this purification method. Finally, this purification method was tested on a range of dihydrophenazine, phenoxazine, dihydroacridines, and phenothiazine PCs, revealing the strength of the chemical oxidant must match the oxidation potential of the PC for effective purification.

| S-EPMC9796344 | biostudies-literature

Synergetic binary organocatalyzed ring opening polymerization for the precision synthesis of polysiloxanes.

Project description:Organocatalytic ring-opening polymerization (ROP) is a versatile method for synthesizing well-defined polymers with controlled molecular weights, dispersities, and nonlinear macromolecular architectures. Despite spectacular advances in organocatalytic ROP, precision synthesis of polysiloxanes remains challenging due to the mismatch in polarity between highly polar initiators and nonpolar monomers and polymers and the difficulty in suppressing the formation of scrambling products via transetherification reactions during ROP of cyclic siloxanes. Here, we describe a binary organocatalytic ROP (BOROP) of hexamethylcyclotrisiloxane (D3) employing organic bases as catalysts and (thio)ureas as cocatalysts. The BOROP of D3 using triazabicyclodecene (TBD) and (thio)ureas generates polydimethylsiloxanes (PDMSs) with narrow dispersity (Mw/Mn < 1.1). Despite the similar basicities of TBD and 1,8-bis(tetramethylguanidino)naphthalene (TMGN), which is known as a proton sponge, a unitary organocatalytic system using TMGN was inactive for the ROP of D3. When the TMGN was paired with acidic urea, the BOROP of D3 yielded PDMSs with narrow dispersity (Mw/Mn < 1.1). Data suggest that the synergetic effect of TMGN and urea is results in an unprecedented activation-deactivation equilibrium between dormant and propagating species. The benefits of the present BOROP system are demonstrated by the formation of PDMS elastomers with more uniform network structures that are highly stretchy and have excellent mechanical properties.

| S-EPMC10957864 | biostudies-literature

Organocatalyzed chemoselective ring-opening polymerizations.

Project description:A novel metal-free and protecting-group-free synthesis method to prepare telechelic thiol-functionalized polyesters is developed by employing organocatalysis. A scope of Brønsted acids, including trifluoromethanesulfonic acid (1), HCl.Et2O (2), diphenyl phosphate (3), ?-resorcylic acid (4) and methanesulfonic acid (5), are evaluated to promote ring-opening polymerization of ?-caprolactone with unprotected 6-mercapto-1-hexanol as the multifunctional initiator. Among them, diphenyl phosphate (3) exhibits great chemoselectivity and efficiency, which allows for simply synthesis of thiol-terminated poly(?-caprolactone) with near-quantitative thiol fidelity, full monomer conversion, controlled molecular weight and narrow polydispersity. Kinetic study confirms living/controlled nature of the organocatalyzed chemoselective polymerizations. Density functional theory calculation illustrates that the chemoselectivity of diphenyl phosphate (3) is attributed to the stronger bifunctional activation of monomer and initiator/chain-end as well as the lower energy in hydroxyl pathway than thiol one. Moreover, series of tailor-made telechelic thiol-terminated poly(?-valerolactone) and block copolymers are efficiently generated under mild conditions.

| S-EPMC5829214 | biostudies-literature

Radical Cations of Phenoxazine and Dihydrophenazine Photoredox Catalysts and Their Role as Deactivators in Organocatalyzed Atom Transfer Radical Polymerization.

Project description:Radical cations of photoredox catalysts used in organocatalyzed atom transfer radical polymerization (O-ATRP) have been synthesized and investigated to gain insight into deactivation in O-ATRP. The stability and reactivity of these compounds were studied in two solvents, N,N-dimethylacetamide and ethyl acetate, to identify possible side reactions in O-ATRP and to investigate the ability of these radical cations to deactivate alkyl radicals. A number of other factors that could influence deactivation in O-ATRP were also probed, such as ion pairing with the radical cations, radical cation oxidation potential, and halide oxidation potential. Ultimately, these studies enabled radical cations to be employed as reagents during O-ATRP to demonstrate improvements in polymerization control with increasing radical cation concentrations. In the polymerization of acrylates, this approach enabled superior molecular weight control, a decrease in polymer dispersity from 1.90 to 1.44, and an increase in initiator efficiency from 78 to 102%. This work highlights the importance of understanding the mechanism and side reactions of O-ATRP, as well as the importance of catalyst radical cations for successful O-ATRP.

| S-EPMC8411649 | biostudies-literature

Photocatalyst-independent photoredox ring-opening polymerization of <i>O</i>-carboxyanhydrides: stereocontrol and mechanism.

Project description:Photoredox ring-opening polymerization of O-carboxyanhydrides allows for the synthesis of polyesters with precisely controlled molecular weights, molecular weight distributions, and tacticities. While powerful, obviating the use of precious metal-based photocatalysts would be attractive from the perspective of simplifying the protocol. Herein, we report the Co and Zn catalysts that are activated by external light to mediate efficient ring-opening polymerization of O-carboxyanhydrides, without the use of exogenous precious metal-based photocatalysts. Our methods allow for the synthesis of isotactic polyesters with high molecular weights (>200 kDa) and narrow molecular weight distributions (M w/M n < 1.1). Mechanistic studies indicate that light activates the oxidative status of a CoIII intermediate that is generated from the regioselective ring-opening of the O-carboxyanhydride. We also demonstrate that the use of Zn or Hf complexes together with Co can allow for stereoselective photoredox ring-opening polymerizations of multiple racemic O-carboxyanhydrides to synthesize syndiotactic and stereoblock copolymers, which vary widely in their glass transition temperatures.

| S-EPMC8179436 | biostudies-literature

Functionalized Biodegradable Polymers via Termination of Ring-Opening Polymerization by Acyl Chlorides.

Project description:Aliphatic polyesters are an important class of polymeric materials for biomedical applications due to their versatile and tunable chemistry, biocompatibility and biodegradability. A capability of direct bonding with biomedically significant molecules, provided by the presence of the reactive end functional groups (FGs), is highly desirable for prospective polymers. Among FGs, N-hydroxysuccinimidyl activated ester group (NHS) and maleimide fragment (MI) provide efficient covalent bonding with -NH- and -SH containing compounds. In our study, we found that NHS- and MI-derived acyl chlorides efficiently terminate living ring-opening polymerization of ε-caprolactone, L-lactide, ethyl ethylene phosphonate and ethyl ethylene phosphate, catalyzed by 2,6-di-tert-butyl-4-methylphenoxy magnesium complex, with a formation of NHS- and MI-functionalized polymers at a high yields. Reactivity of these polymers towards amine- and thiol-containing model substrates in organic and aqueous media was also studied.

| S-EPMC8002085 | biostudies-literature

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