Rapid, controlled ring-opening polymerization of salicylic acid <i>o</i>-carboxyanhydride for poly(salicylate) synthesis

Han, Song; Yao, Shiman; Meng, Wei; Yang, Jing

doi:10.1039/d1py01309b

Cited by 7 publications

(10 citation statements)

References 44 publications

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“…A sample was taken during the process of polymerization for FTIR analysis to determine SAOCA conversion using the ratio of the carbonyl signal intensities. 43 All the mPEG-PSA resulted in up to 25% solid content (w/w). We tracked the structural and morphological evolution of the self-assembly through polymerization reactions quickly occurring under the determined conditions (Table 1).…”

Section: Resultsmentioning

confidence: 99%

“…[33][34][35][36][37][38][39][40][41][42] Lately, our group explored a new synthesis pathway for PSA polymers via the ROP of salicylic acid O-carboxyanhydride (SAOCA). 43 To create in situ nanoparticles with a bioactive PSA core-forming block, we developed ROP-induced self-assembly (ROPISA) of SAOCA, which is facilitated by the switch from the solvophilic SAOCA to solvophobic PSA block in tetrahydrofuran (THF) during polymerization. 44 Due to the high reactivity of SAOCA, its ROP was completed in a few minutes.…”

Section: Introductionmentioning

confidence: 99%

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ROPISA of salicylic acidO-carboxyanhydride: fast polymerization followed byin situkinetics-driven self-assembly

Yao

Yang

2023

Polym. Chem.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

ROPISA of salicylic acidO-carboxyanhydride: fast polymerization followed byin situkinetics-driven self-assembly

Yao

Yang

2023

Polym. Chem.

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“…Because SAOCA is a class of monomer with high activity, its ROP was carried out in seconds in the catalysis of DBU, but the afforded MW was increased to 14.1 kDa at the most. 40 To synthesize PSA with high MW, the Lewis base of S1, entry 3). Subsequently, the feed ratios (FR) of NHC-1 to TU-1 were tuned for an investigation of the impact on the resulting PSA (Table S1, entries 4−8).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Recently, our group explored a new pathway for synthesizing PSA via ROP of six-member cyclic salicylic acid O-carboxyanhydride (SAOCA) and demonstrated the feasibility of rapidly synthesizing moderate MW (∼10 kDa) PSA (Figure 1e). 40 Despite this progress, we acknowledge that a method for preparing high-MW PSA is still elusive. This lack of a method will limit our ability to understand the properties and potential applications of PSA accurately.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Kricheldorf and Socha reported on the synthesis of PSA homopolymers via the reaction of salicylic acid with acetic anhydride under harsh reaction conditions (Figure d). , However, the resulting PSA had a broad molecular weight distribution with a molecular weight (MW) of less than 5 kDa. Recently, our group explored a new pathway for synthesizing PSA via ROP of six-member cyclic salicylic acid O -carboxyanhydride (SAOCA) and demonstrated the feasibility of rapidly synthesizing moderate MW (∼10 kDa) PSA (Figure e) . Despite this progress, we acknowledge that a method for preparing high-MW PSA is still elusive.…”

Section: Introductionmentioning

confidence: 99%

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Facile Synthesis of Aromatic Polyesters with High Molecular Weights via Lewis Pair-Mediated Ring-Opening Polymerization of Salicylic Acid-Derived O-Carboxyanhydrides

Liang,

Meng,

Yang

2023

Macromolecules

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Compared to fossil resources, which display limited degradability, exploring novel green polyesters as more sustainable alternatives is an extremely challenging task. In this study, we have developed an effective pathway from natural origin salicylic acid (SA) to poly(salicylic acid) (PSA) with high molecular weight. This was achieved by employing Lewis pair-mediated ring-opening polymerization of salicylic acid O-carboxyanhydrides (SAOCA). We identified two metal-free combinations, namely, 1,3-bis(2,6-diisopropylphenyl)imidazole (NHC-1)/N-[3,5-bis(trifluoromethyl)phenyl]-N′-cyclohexyl thiourea (TU-1) and 2-tertbutylimino-2-diethylamino-1,3-dimethyl-perhydro-1,3,2 diazaphosphorine (BEMP)/TU-1, that mediated ROP of SAOCA at room temperature within 100 min and successfully produced PSA with molecular weight greater than 150 kDa. We observed that the phase state of the polymerization solution switched from clarification to turbidity to phase separation when the PSA chain was growing up. Based on the NMR results of the interaction between organic base and TU-1, the analysis of polymerization kinetics, and DFT calculations, we found that the excess addition of TU-1 could effectively restrain unfavorable results in which very fast propagation of the polymerization chain caused phase separation in a short time. Furthermore, it improved the controllability of ROP reactions and the resulting chain length of PSA. The generality of this synthetic strategy was evaluated by the convenient preparation of other PSA-series polyesters via the ROP of SAOCA analogues varying the substituents. The obtained PSA-series polyesters exhibited good thermal stability and high glass transition temperature, outperforming some commodity polyolefins. This synthetic method paves the way for a better understanding of PSA-based polyesters as a class of future green materials applicable in the field of biomedicine and sustainable plastic packaging.

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Advances in the Synthesis of Poly(Phenolic Ester)s via Ring‐Opening Polymerization

Lin,

Lu,

Liu

et al. 2024

ChemCatChem

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The poly(phenolic ester)s are attracting growing attention due to their essential role in the application as biodegradable plastics. Thus, extensive efforts have been devoted to the development of methodology that allows facile preparation of poly(phenolic ester)s with controlled molecular weights for widespread utilities. However, it is highly challenging to introduce phenolic ester bond structure into polyesters from ring‐opening polymerization (ROP) to yield aromatic/semiaromatic poly(phenolic ester)s due to severe transesterification reactions. To synthesize poly(phenolic ester)s with desired structures and properties, scientists have developed various ring‐opening polymerization systems with distinct advantages. Here, we have summarized basic features and recent progresses of these methods, including the cyclic phenolic lactone polymerization system, the salicylic acid O‐carboxyanhydride polymerization system, and the dissymmetric cyclic phenolic lactide polymerization system, as well as other copolymerization routes. Furthermore, the advantages and unsettled problems in various synthetic ways are discussed for readers to choose fast and controllable ROP systems for poly(phenolic ester)s.

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Rapid, controlled ring-opening polymerization of salicylic acid o-carboxyanhydride for poly(salicylate) synthesis

Abstract: A fast synthesis pathway of poly(salicylate) in mild conditions was explored, in which the combination of Lewis base and alcohol enables salicylic acid o-carboxyanhydride polymerize in seconds to afford well-defined hompolymers with high Tg.

Cited by 7 publications

References 44 publications

ROPISA of salicylic acidO-carboxyanhydride: fast polymerization followed byin situkinetics-driven self-assembly

ROPISA of salicylic acidO-carboxyanhydride: fast polymerization followed byin situkinetics-driven self-assembly

Facile Synthesis of Aromatic Polyesters with High Molecular Weights via Lewis Pair-Mediated Ring-Opening Polymerization of Salicylic Acid-Derived O-Carboxyanhydrides

Advances in the Synthesis of Poly(Phenolic Ester)s via Ring‐Opening Polymerization

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