A series of novel chiral dimeric Zn(II) complexes, comprising both (S)- and (R)-isomers, were synthesized utilizing N-Boc protected proline-derived ligand scaffolds. The reaction of diethylzinc (ZnEt₂) with equimolar amounts of pro-ligands (L1H–L4H) in anhydrous toluene afforded the corresponding Zn(II) complexes (1–4) in high yields. The solid-state structures of complexes 1 and 3 were elucidated via single-crystal X-ray diffraction, revealing a distorted tetrahedral coordination geometry around the Zn(II) center. However, spectroscopic analysis indicated the presence of monomeric Zn(II) species in solution. All synthesized complexes were evaluated for their catalytic performance in the ring-opening polymerization (ROP) of racemic lactide (rac-LA) and ring-opening copolymerization (ROCOP) of phthalic anhydride (PA) with cyclohexene oxide (CHO), as well as other epoxide–anhydride combinations. All the Zn(II) complexes demonstrated activity in the ROP of rac-LA, yielding polylactide (PLA) with stereoregularity ranging from atactic (Pr = 0.51) to slightly isotactic-enriched (Pm = 0.58), influenced by the ligand architecture and chirality. The ROP is proposed to proceed via ligand-initiated coordination–insertion mechanism. All the Zn(II) complexes (1–4) were catalytically active in the presence of a cocatalyst, with bis(triphenylphosphine)iminium chloride (PPNCl) delivering optimal performance. The ROCOP of CHO with PA yielded alternating copolyesters with moderate to high number-average molecular weights (Mn ≈ 7200 g mol⁻¹) and moderate dispersity (Đ ≈ 1.33). (R)-4 catalyzed the formation of an atactic polyester, whereas (S)-2 enabled the synthesis of a perfectly alternating poly(PA-alt-CHO) with enhanced isotacticity. Kinetic studies revealed that complex (S)-1 exhibited a fourfold higher polymerization rate compared to (R)-4. DFT energy calculations revealed a favourable mechanistic pathway wherein the dimeric zinc species dissociates into monomeric active intermediates, a crucial step in facilitating the ROCOP.
利用N-Boc保护的脯氨酸衍生配体支架合成了一系列具有(S)-和(R)-异构体的新型手性二聚体Zn（II）配合物。二乙基锌（ZnEt 2）与等摩尔量的前配体（L1H-L4H）在无水甲苯中反应得到相应的Zn（II）配合物（1-4），收率高。通过单晶x射线衍射分析了配合物1和3的固态结构，发现配合物在Zn（II）中心周围呈扭曲的四面体配位几何。然而，光谱分析表明溶液中存在单体Zn（II）。对所有合成的配合物在外消旋丙交酯（rac-LA）开环聚合（ROP）、邻苯二甲酸酐（PA）与环氧己烯氧化物（CHO）开环共聚（ROCOP）以及其他环氧-酸酐组合中的催化性能进行了评价。所有Zn（II）配合物在rac-LA的ROP中都表现出活性，生成的聚乳酸（PLA）的立体规则范围从无规（Pr = 0.51）到轻度等规富集（Pm = 0.58），受配体结构和手性的影响。ROP是通过配体引发的配位插入机制进行的。所有Zn（II）配合物（1-4）在助催化剂存在下都具有催化活性，其中双（三苯基膦）氯化亚胺（PPNCl）表现出最佳的催化活性。CHO与PA的ROCOP反应得到中高数均分子量（Mn≈7200 g mol⁻¹）和中等分散性（Đ≈1.33）的交替共聚酯。(R)-4催化形成无规聚酯，而(S)-2催化合成具有增强等规性的完全交替聚（PA-alt-CHO）。动力学研究表明，配合物(S)-1的聚合速率比(R)-4高4倍。DFT能量计算揭示了一个有利的机制途径，其中二聚体锌解离成单体活性中间体，这是促进ROCOP的关键步骤。
{"title":"Chiral Proline-derived Zn(II) Complexes as Catalysts for Ring-Opening Polymerization and Ring-Opening Copolymerization Reactions","authors":"Ranay Kumar Ray, Manoj Kumari, Kartik Chandra Mondal, Debashis Chakraborty","doi":"10.1039/d5py01089f","DOIUrl":"https://doi.org/10.1039/d5py01089f","url":null,"abstract":"A series of novel chiral dimeric Zn(II) complexes, comprising both (S)- and (R)-isomers, were synthesized utilizing N-Boc protected proline-derived ligand scaffolds. The reaction of diethylzinc (ZnEt₂) with equimolar amounts of pro-ligands (L1H–L4H) in anhydrous toluene afforded the corresponding Zn(II) complexes (1–4) in high yields. The solid-state structures of complexes 1 and 3 were elucidated via single-crystal X-ray diffraction, revealing a distorted tetrahedral coordination geometry around the Zn(II) center. However, spectroscopic analysis indicated the presence of monomeric Zn(II) species in solution. All synthesized complexes were evaluated for their catalytic performance in the ring-opening polymerization (ROP) of racemic lactide (rac-LA) and ring-opening copolymerization (ROCOP) of phthalic anhydride (PA) with cyclohexene oxide (CHO), as well as other epoxide–anhydride combinations. All the Zn(II) complexes demonstrated activity in the ROP of rac-LA, yielding polylactide (PLA) with stereoregularity ranging from atactic (Pr = 0.51) to slightly isotactic-enriched (Pm = 0.58), influenced by the ligand architecture and chirality. The ROP is proposed to proceed via ligand-initiated coordination–insertion mechanism. All the Zn(II) complexes (1–4) were catalytically active in the presence of a cocatalyst, with bis(triphenylphosphine)iminium chloride (PPNCl) delivering optimal performance. The ROCOP of CHO with PA yielded alternating copolyesters with moderate to high number-average molecular weights (Mn ≈ 7200 g mol⁻¹) and moderate dispersity (Đ ≈ 1.33). (R)-4 catalyzed the formation of an atactic polyester, whereas (S)-2 enabled the synthesis of a perfectly alternating poly(PA-alt-CHO) with enhanced isotacticity. Kinetic studies revealed that complex (S)-1 exhibited a fourfold higher polymerization rate compared to (R)-4. DFT energy calculations revealed a favourable mechanistic pathway wherein the dimeric zinc species dissociates into monomeric active intermediates, a crucial step in facilitating the ROCOP.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"1 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146001440","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Base-assisted degradable methacrylic polymer microcapsules were synthesized via interfacial radical polymerizations of oil-in-water emulsions containing 4,4-dimethyl-2-methylene-1,3-dioxolan-5-one (DMDL) as a monomer to provide degradable units in the obtained microcapsule shell. Many of the current degradable polymer microcapsules use ester linkages in the polymer backbones for degradation. The ester linkages incorporated into the polymer backbones can cause the polymers to be less stable, and the polymer microcapsules may gradually degrade hydrolytically under humidity. The DMDL units provide carbon–carbon linkages in the polymer backbones. The obtained microcapsules were stable under neutral aqueous conditions with various salts and selectively degraded under basic conditions. As a demonstration, a dye was encapsulated and was gradually released over time under basic aqueous conditions. Possible long-term storage stability under neutral aqueous conditions and selective content release under basic conditions may be advantages of the DMDL microcapsules.
{"title":"Base-assisted degradable methacrylic polymer microcapsules synthesized via interfacial radical polymerization using 4,4-dimethyl-2-methylene-1,3-dioxolan-5-one (DMDL)","authors":"Tze Kwang Gerald Er, Wei Xiang Lim, Atsushi Goto","doi":"10.1039/d5py01133g","DOIUrl":"https://doi.org/10.1039/d5py01133g","url":null,"abstract":"Base-assisted degradable methacrylic polymer microcapsules were synthesized <em>via</em> interfacial radical polymerizations of oil-in-water emulsions containing 4,4-dimethyl-2-methylene-1,3-dioxolan-5-one (DMDL) as a monomer to provide degradable units in the obtained microcapsule shell. Many of the current degradable polymer microcapsules use ester linkages in the polymer backbones for degradation. The ester linkages incorporated into the polymer backbones can cause the polymers to be less stable, and the polymer microcapsules may gradually degrade hydrolytically under humidity. The DMDL units provide carbon–carbon linkages in the polymer backbones. The obtained microcapsules were stable under neutral aqueous conditions with various salts and selectively degraded under basic conditions. As a demonstration, a dye was encapsulated and was gradually released over time under basic aqueous conditions. Possible long-term storage stability under neutral aqueous conditions and selective content release under basic conditions may be advantages of the DMDL microcapsules.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"28 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146001439","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Reo Nitto, Lisa Takimoto, Yu Tokita, Yoshihiro Ohta, Tsutomu Yokozawa
Successive Kumada-Tamao catalyst-transfer condensation polymerization (CTCP) of [4-bromo-2,5-bis(hexyloxy)phenyl]magnesium chloride (1) and Suzuki-Miyaura end-functionalization with arylboronic acid (ester) is investigated for the synthesis of poly(p-phenylene) (PPP) with a base-sensitive functional group at both ends as an extension of our previous work on end-functionalized poly(3-hexylthiophene) (P3HT). We first examined Kumada-Tamao CTCP of 1 with PEPPSI-IPr Pd catalyst to see whether poly1 with Br/H ends would be obtained; the H end is expected to be derived from the poly1-Pd-Br end by hydrolysis with hydrochloric acid used for quenching the polymerization. The MALDI-TOF mass spectrum of the product obtained at 30 min showed peaks due to the desired poly1 with Br/H ends. However, peaks assignable to poly1 with Br/N-heterocarbene (NHC) ends became more intense with increasing reaction time. NHC is likely derived from the ligand of PEPPSI-IPr. Therefore, Kumada-Tamao CTCP of 1 with PEPPSI-IPr was conducted at room temperature for 30 min, followed by reaction with various boronic acid (ester)s 2 in the presence of aqueous K3PO4. 4-Trifluoromethylphenyl, 4-methoxyphenyl, 4-(methoxycarbonyl)phenyl, 4-(hydroxymethyl)phenyl, and 4-(tert-butoxycarbonylaminomethyl)phenyl groups were introduced at both ends. However, a 4-vinylphenyl group was introduced at only one end, and the reaction with pinacol 4-(a-bromoisobutyryloxymethyl)phenylboronate (2g) afforded a mixture of mono- and dicapped products. Furthermore, successive Suzuki-Miyaura block copolymerization with bromoarylboronate monomer 3 instead of 2 was conducted. The use of thiophene monomer 3a afforded diblock copolymer of poly1 and poly(3-hexylthiophene) with a narrow molecular weight distribution, whereas fluorene monomer 3b afforded copolymer with a broad molecular weight distribution, accompanied with unreacted 3b.
{"title":"Tandem Kumada–Tamao Catalyst-Transfer Condensation Polymerization and Suzuki–Miyaura Coupling for End-Functionalization and Block Copolymerization of Poly(p-phenylene)","authors":"Reo Nitto, Lisa Takimoto, Yu Tokita, Yoshihiro Ohta, Tsutomu Yokozawa","doi":"10.1039/d5py01101a","DOIUrl":"https://doi.org/10.1039/d5py01101a","url":null,"abstract":"Successive Kumada-Tamao catalyst-transfer condensation polymerization (CTCP) of [4-bromo-2,5-bis(hexyloxy)phenyl]magnesium chloride (<strong>1</strong>) and Suzuki-Miyaura end-functionalization with arylboronic acid (ester) is investigated for the synthesis of poly(<em>p</em>-phenylene) (PPP) with a base-sensitive functional group at both ends as an extension of our previous work on end-functionalized poly(3-hexylthiophene) (P3HT). We first examined Kumada-Tamao CTCP of <strong>1</strong> with PEPPSI-IPr Pd catalyst to see whether <strong>poly1</strong> with Br/H ends would be obtained; the H end is expected to be derived from the <strong>poly1</strong>-Pd-Br end by hydrolysis with hydrochloric acid used for quenching the polymerization. The MALDI-TOF mass spectrum of the product obtained at 30 min showed peaks due to the desired <strong>poly1</strong> with Br/H ends. However, peaks assignable to <strong>poly1</strong> with Br/N-heterocarbene (NHC) ends became more intense with increasing reaction time. NHC is likely derived from the ligand of PEPPSI-IPr. Therefore, Kumada-Tamao CTCP of <strong>1</strong> with PEPPSI-IPr was conducted at room temperature for 30 min, followed by reaction with various boronic acid (ester)s <strong>2</strong> in the presence of aqueous K<small><sub>3</sub></small>PO<small><sub>4</sub></small>. 4-Trifluoromethylphenyl, 4-methoxyphenyl, 4-(methoxycarbonyl)phenyl, 4-(hydroxymethyl)phenyl, and 4-(<em>tert</em>-butoxycarbonylaminomethyl)phenyl groups were introduced at both ends. However, a 4-vinylphenyl group was introduced at only one end, and the reaction with pinacol 4-(a-bromoisobutyryloxymethyl)phenylboronate (<strong>2g</strong>) afforded a mixture of mono- and dicapped products. Furthermore, successive Suzuki-Miyaura block copolymerization with bromoarylboronate monomer <strong>3</strong> instead of <strong>2</strong> was conducted. The use of thiophene monomer <strong>3a</strong> afforded diblock copolymer of <strong>poly1</strong> and poly(3-hexylthiophene) with a narrow molecular weight distribution, whereas fluorene monomer <strong>3b</strong> afforded copolymer with a broad molecular weight distribution, accompanied with unreacted <strong>3b</strong>.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146001088","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Shuai Zhang, Jiaming Hu, Lu-kun Wu, Lin Yan, Hao Huang, Jing Li, Xiaobo Wan, Kai Du
Herein, the synthesis of a novel borate ester-functionalized monomer was reported, designated mBBDA, through an esterification reaction between 1,3-benzenediboronic acid (mBBA) and glycidyl methacrylate (GMA). This monomer was subsequently formulated with pentaerythritol triacrylate (PETA) to produce a series of photocurable resins, denoted as P-mBMAx, with mBBDA content systematically varied from 0 to 100 wt%. P-mBMAx resins served as photoresists for high-resolution two-photon polymerization (TPP) lithography. Mechanical characterization revealed that the resin incorporating 60 wt% mBBDA (P-mBMA6) demonstrated a 12.5% enhancement in impact strength (5.4 kJ•m -²) relative to the unmodified PETA benchmark, while also maintaining a high Young's modulus of 6.61 GPa and a hardness of 0.395 GPa.Utilizing a 780 nm femtosecond laser, TPP fabrication with these resins achieved sub-micron feature resolution even at remarkably high scanning speeds of up to 100,000 μm•s -¹, thereby enabling rapid prototyping. Furthermore, microarchitectures fabricated via TPP using the P-mBMAx photoresists were successfully converted into porous boron carbide (B₄C) ceramics through a subsequent sintering process. The formation of B₄C was unequivocally confirmed by X-ray diffraction (XRD) analysis. Remarkably, the sintered ceramics retained their original three-dimensional architectures with high structural fidelity. This study establishes that mBBDA-modified resins provide a versatile platform, offering tunable mechanical properties, inherent self-healing capability, and dual functionality for both cross-scale additive micronanofabrication and the preparation of high-fidelity, porous boron carbide ceramics.
{"title":"Boronic Ester-Modified Resins: Dual-Function in Micro-Additive Manufacturing and Ceramization","authors":"Shuai Zhang, Jiaming Hu, Lu-kun Wu, Lin Yan, Hao Huang, Jing Li, Xiaobo Wan, Kai Du","doi":"10.1039/d5py01180a","DOIUrl":"https://doi.org/10.1039/d5py01180a","url":null,"abstract":"Herein, the synthesis of a novel borate ester-functionalized monomer was reported, designated mBBDA, through an esterification reaction between 1,3-benzenediboronic acid (mBBA) and glycidyl methacrylate (GMA). This monomer was subsequently formulated with pentaerythritol triacrylate (PETA) to produce a series of photocurable resins, denoted as P-mBMAx, with mBBDA content systematically varied from 0 to 100 wt%. P-mBMAx resins served as photoresists for high-resolution two-photon polymerization (TPP) lithography. Mechanical characterization revealed that the resin incorporating 60 wt% mBBDA (P-mBMA6) demonstrated a 12.5% enhancement in impact strength (5.4 kJ•m -²) relative to the unmodified PETA benchmark, while also maintaining a high Young's modulus of 6.61 GPa and a hardness of 0.395 GPa.Utilizing a 780 nm femtosecond laser, TPP fabrication with these resins achieved sub-micron feature resolution even at remarkably high scanning speeds of up to 100,000 μm•s -¹, thereby enabling rapid prototyping. Furthermore, microarchitectures fabricated via TPP using the P-mBMAx photoresists were successfully converted into porous boron carbide (B₄C) ceramics through a subsequent sintering process. The formation of B₄C was unequivocally confirmed by X-ray diffraction (XRD) analysis. Remarkably, the sintered ceramics retained their original three-dimensional architectures with high structural fidelity. This study establishes that mBBDA-modified resins provide a versatile platform, offering tunable mechanical properties, inherent self-healing capability, and dual functionality for both cross-scale additive micronanofabrication and the preparation of high-fidelity, porous boron carbide ceramics.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"63 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146005616","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Denis Andzheevich Sapegin, Joseph C Bear, Jeremy Karl Cockcroft, Edward J Penny, Danila A Kuznetsov
We report an expandable synthetic pathway to an obenzenedisulfonimide-bearing diol that enables the first poly(1,2disulfonimide) polymers. The non-planar highly polar disulfonimide unit in the backbone is predicted to strengthen interchain interactions while maintaining chain separation, highlighting a molecular design strategy for polymers that decouple strong interchain interactions from packing densification.
{"title":"Molecular insight into a disulfonimide-bearing diol: synthesis, characterisation and access to poly(disulfonimide)s","authors":"Denis Andzheevich Sapegin, Joseph C Bear, Jeremy Karl Cockcroft, Edward J Penny, Danila A Kuznetsov","doi":"10.1039/d5py01171j","DOIUrl":"https://doi.org/10.1039/d5py01171j","url":null,"abstract":"We report an expandable synthetic pathway to an obenzenedisulfonimide-bearing diol that enables the first poly(1,2disulfonimide) polymers. The non-planar highly polar disulfonimide unit in the backbone is predicted to strengthen interchain interactions while maintaining chain separation, highlighting a molecular design strategy for polymers that decouple strong interchain interactions from packing densification.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"5 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145993092","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Abdulrahman Bakry, Preeti Yadav, Wissem Khelifi, Julia Khusnutdinova and Christine Luscombe
Glycolated polythiophenes are of great interest for their use as organic mixed ionic-electronic conductors (OMIECs). In this study, we elucidate the polymerization mechanism for the synthesis of poly(3-((2-(2-methoxyethoxy)ethoxy)methyl)thiophene) (P3MEEMT) using Kumada catalyst transfer polymerization (KCTP). While the use of i-PrMgCl·LiCl (turbo-Grignard) for monomer activation enabled rapid polymerization within 10 min at room temperature, this resulted in lower than expected number-average molecular weight (Mn). We propose that the polymerization proceeds via a radical-mediated pathway, a mechanism not observed for poly(3-hexylthiophene) (P3HT). This was demonstrated by the complete inhibition of the reaction by the radical scavenger TEMPO and the detection of radical species by EPR spectroscopy using DMPO as a spin trap. By introducing MgCl2 after Grignard metathesis, a controlled polymerization was afforded with Mn proportional to the catalyst loading. This work establishes that KCTP of glycolated thiophenes proceeds via a radical-assisted pathway and provides a strategy to control the polymer molecular weight. These findings establish a new principle for controlling polymerizations, where the monomer's physical aggregation state is the key factor in enabling a productive, radical-mediated pathway.
{"title":"Uncovering a radical-mediated mechanism in the Kumada catalyst transfer polymerization of glycolated polythiophenes","authors":"Abdulrahman Bakry, Preeti Yadav, Wissem Khelifi, Julia Khusnutdinova and Christine Luscombe","doi":"10.1039/D5PY01139F","DOIUrl":"10.1039/D5PY01139F","url":null,"abstract":"<p >Glycolated polythiophenes are of great interest for their use as organic mixed ionic-electronic conductors (OMIECs). In this study, we elucidate the polymerization mechanism for the synthesis of poly(3-((2-(2-methoxyethoxy)ethoxy)methyl)thiophene) (P3MEEMT) using Kumada catalyst transfer polymerization (KCTP). While the use of i-PrMgCl·LiCl (turbo-Grignard) for monomer activation enabled rapid polymerization within 10 min at room temperature, this resulted in lower than expected number-average molecular weight (<em>M</em><small><sub>n</sub></small>). We propose that the polymerization proceeds <em>via</em> a radical-mediated pathway, a mechanism not observed for poly(3-hexylthiophene) (P3HT). This was demonstrated by the complete inhibition of the reaction by the radical scavenger TEMPO and the detection of radical species by EPR spectroscopy using DMPO as a spin trap. By introducing MgCl<small><sub>2</sub></small> after Grignard metathesis, a controlled polymerization was afforded with <em>M</em><small><sub>n</sub></small> proportional to the catalyst loading. This work establishes that KCTP of glycolated thiophenes proceeds <em>via</em> a radical-assisted pathway and provides a strategy to control the polymer molecular weight. These findings establish a new principle for controlling polymerizations, where the monomer's physical aggregation state is the key factor in enabling a productive, radical-mediated pathway.</p>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":" 5","pages":" 584-592"},"PeriodicalIF":3.9,"publicationDate":"2026-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2026/py/d5py01139f?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146001089","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Inverse vulcanization has been continuously studied for over 10 years and extended to a wide range of organic crosslinkers. However, most reported systems demand high temperature and hours to complete. Here, the reaction between 2-methyl-2-oxazoline or 2-ethyl-2-oxazoline and sulfur is found to complete within 6 mins at 140 oC in the absence of any catalyst, and generate sulfur-chain modified polyamides. The sulfur-oxazoline reaction proceeds well in a broad range of charging ratios (sulfur>10wt%). With a bulkier substitution, 2-phenyl-2-oxazoline was almost inert to sulfur at 160 oC, and would take 2 hours at 180 oC to reach complete conversion. Sulfur-modified polyamide networks from the crosslinking of sulfur with biobased oxazoline-ene difunctional monomers exhibited tunable mechanical properties and photothermal properties for photo triggered shape programming.
{"title":"Rapid Sulfur-Oxazoline Polymerization for Biobased Dynamic Polyamide Networks","authors":"Zhengxiang Wang, Kangle Yan, Shuo Geng, Miaomiao Sun, Chengcheng Hu, Dequan Liu, Chuanzhi Mo, Zhiqiang Peng, Youxian Yan, Liang Yuan","doi":"10.1039/d5py00729a","DOIUrl":"https://doi.org/10.1039/d5py00729a","url":null,"abstract":"Inverse vulcanization has been continuously studied for over 10 years and extended to a wide range of organic crosslinkers. However, most reported systems demand high temperature and hours to complete. Here, the reaction between 2-methyl-2-oxazoline or 2-ethyl-2-oxazoline and sulfur is found to complete within 6 mins at 140 oC in the absence of any catalyst, and generate sulfur-chain modified polyamides. The sulfur-oxazoline reaction proceeds well in a broad range of charging ratios (sulfur>10wt%). With a bulkier substitution, 2-phenyl-2-oxazoline was almost inert to sulfur at 160 oC, and would take 2 hours at 180 oC to reach complete conversion. Sulfur-modified polyamide networks from the crosslinking of sulfur with biobased oxazoline-ene difunctional monomers exhibited tunable mechanical properties and photothermal properties for photo triggered shape programming.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"5 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145962193","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Brandon Hosford, Jinxiao Li, Nora O'Connor, Jessica R Lamb
The combination of multiple polymerization mechansisms in a single polymer chain allows for the synthesis of block copolymers with blocks of significantly different chemical structures. Previously, the combination of cationic polymerization of vinyl ethers and anionic polymerization of thiiranes was enabled through the use of a thiocarbonyl thio universal mediator, albiet limited in scope to just ethyl vinyl ether for the cationic block. Herein, we utilize a Brønsted acid-catalyzed reversible-deactivation cationic polymerization and/or modified thioacyl anionic group transfer polymerization conditions to successfully chain extend six additional poly(vinyl ether)s – dramatically increasing the scope of monomers supported. Thermal analyses reveal a large range of glass transition temperatures now available (−58 to 74 °C), including those significantly above room temperature which were not accessible using the previous method.
{"title":"Accessing broader vinyl ether scope for sequential cationic-anionic block copolymers","authors":"Brandon Hosford, Jinxiao Li, Nora O'Connor, Jessica R Lamb","doi":"10.1039/d5py01164g","DOIUrl":"https://doi.org/10.1039/d5py01164g","url":null,"abstract":"The combination of multiple polymerization mechansisms in a single polymer chain allows for the synthesis of block copolymers with blocks of significantly different chemical structures. Previously, the combination of cationic polymerization of vinyl ethers and anionic polymerization of thiiranes was enabled through the use of a thiocarbonyl thio universal mediator, albiet limited in scope to just ethyl vinyl ether for the cationic block. Herein, we utilize a Brønsted acid-catalyzed reversible-deactivation cationic polymerization and/or modified thioacyl anionic group transfer polymerization conditions to successfully chain extend six additional poly(vinyl ether)s – dramatically increasing the scope of monomers supported. Thermal analyses reveal a large range of glass transition temperatures now available (−58 to 74 °C), including those significantly above room temperature which were not accessible using the previous method.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"51 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145968909","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Alexander Grimm, Amna Binte Asghar, Björn Schmidt, Christian Schmitt, Dominik Voll, Tanja Junkers, Patrick Theato
The establishment of automation of laboratory research over the past years has rapidly advanced all fields of chemical science including polymer synthesis. However, automated synthesis of polymers is largely limited to non-functional materials and post-polymerisation modification (PPM) remains underrepresented in flow polymer science. Herein, the polymerisation and PPM of pentafluorostyrene (PFSty), an established precursor polymer for PPM via para-fluoro-thiol-reaction (PFTR), in continuous flow is reported for the first time. The kinetic behaviour of the reversible addition-fragmentation chain transfer (RAFT) polymerisation of PFSty via transient timesweeping is demonstrated, yielding apparent polymerisation rate coefficients of 1.18·10-3 to 1.13·10-2 s-1 at 70 – 90 °C with 2-cyano-2-propyldodecyltrithiocarbonate (CPDT) as RAFT agent. Consequently, the PFTR of poly(PFSty) in continuous flow is investigated using 1-dodecanethiol (DT), 4-fluorobenzyl mercaptan (FBM), and 4-trifluoromethylbenzyl mercaptan (TFBM) showing quantitative conversion of FBM and TFBM after 6 min at 60 °C while DT does not exceed 53 % modification of poly(PFSty) at 70 °C. Finally, a mixed flow-PFTR concept enables predictable copolymer modification with thiol mixtures through direct syringe pump control, achieving up to 99 % precision depending on thiol reactivity. The proposed strategy offers a versatile approach for the continuous-flow synthesis and modification of reactive polymers, expanding the library of functional polymers for high-throughput methodologies.
{"title":"Controlled Synthesis and Post-Modification of Polypentafluorostyrene in Continuous Flow","authors":"Alexander Grimm, Amna Binte Asghar, Björn Schmidt, Christian Schmitt, Dominik Voll, Tanja Junkers, Patrick Theato","doi":"10.1039/d5py01142f","DOIUrl":"https://doi.org/10.1039/d5py01142f","url":null,"abstract":"The establishment of automation of laboratory research over the past years has rapidly advanced all fields of chemical science including polymer synthesis. However, automated synthesis of polymers is largely limited to non-functional materials and post-polymerisation modification (PPM) remains underrepresented in flow polymer science. Herein, the polymerisation and PPM of pentafluorostyrene (PFSty), an established precursor polymer for PPM via para-fluoro-thiol-reaction (PFTR), in continuous flow is reported for the first time. The kinetic behaviour of the reversible addition-fragmentation chain transfer (RAFT) polymerisation of PFSty via transient timesweeping is demonstrated, yielding apparent polymerisation rate coefficients of 1.18·10<small><sup>-3</sup></small> to 1.13·10<small><sup>-2</sup></small> s<small><sup>-1</sup></small> at 70 – 90 °C with 2-cyano-2-propyldodecyltrithiocarbonate (CPDT) as RAFT agent. Consequently, the PFTR of poly(PFSty) in continuous flow is investigated using 1-dodecanethiol (DT), 4-fluorobenzyl mercaptan (FBM), and 4-trifluoromethylbenzyl mercaptan (TFBM) showing quantitative conversion of FBM and TFBM after 6 min at 60 °C while DT does not exceed 53 % modification of poly(PFSty) at 70 °C. Finally, a mixed flow-PFTR concept enables predictable copolymer modification with thiol mixtures through direct syringe pump control, achieving up to 99 % precision depending on thiol reactivity. The proposed strategy offers a versatile approach for the continuous-flow synthesis and modification of reactive polymers, expanding the library of functional polymers for high-throughput methodologies.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"49 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145949909","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Radical thiocarbonyl addition–ring-opening (TARO) copolymerization has emerged as a promising method to install weak linkages into vinyl-based polymers. But the portfolio of available monomers is limited to thionolactones and cyclic thiocarbamates. Herein, a cyclic xanthate featuring an additional in-ring sufur atom, 4H-1,3-benzoxathiin-2-thione (BOT), was prepared by reacting 2-mercaptobenzyl alcohol with thiophosgene, avoiding the commonplace thionation reaction. An AIBN-initiated radical polymerization of BOT resulted in 37% conversion and approx. 75 mol% ring-opened dithiocarbonate repeat units alongside ring-retained dithioorthoester repeat units. A series of N,N-dimethylacrylamide (DMA)–BOT copolymers was prepared with copolymer BOT contents ranging from 2.5 mol% to 16 mol% with quantitative ring-opening. BOT was found to be less reactive than DMA with estimated reactivity ratios of rDMA = 2.73 and rBOT = 0.04 which led to BOT incorporation throughout the high-yielding copolymerization in the absence of vinyl homopolymerization reported for the use of other thionolactone monomers. The BOT repeat units were easily cleaved through aminolysis and basic hydrolysis. Uniquely, the dithiocarbonate repeat units featured two cleavable C—S bonds, meaning that the degradant was not retained as a fragment end group. Cyclic xanthates are therefore useful for the preparation of easily degradable acrylamide copolymers.
{"title":"Degradable Vinyl Copolymers Featuring Backbone Dithiocarbonates by Radical Copolymerization of a Cyclic Xanthate","authors":"Kyle Hepburn, Peter J. Roth","doi":"10.1039/d5py00805k","DOIUrl":"https://doi.org/10.1039/d5py00805k","url":null,"abstract":"Radical thiocarbonyl addition–ring-opening (TARO) copolymerization has emerged as a promising method to install weak linkages into vinyl-based polymers. But the portfolio of available monomers is limited to thionolactones and cyclic thiocarbamates. Herein, a cyclic xanthate featuring an additional in-ring sufur atom, 4H-1,3-benzoxathiin-2-thione (BOT), was prepared by reacting 2-mercaptobenzyl alcohol with thiophosgene, avoiding the commonplace thionation reaction. An AIBN-initiated radical polymerization of BOT resulted in 37% conversion and approx. 75 mol% ring-opened dithiocarbonate repeat units alongside ring-retained dithioorthoester repeat units. A series of N,N-dimethylacrylamide (DMA)–BOT copolymers was prepared with copolymer BOT contents ranging from 2.5 mol% to 16 mol% with quantitative ring-opening. BOT was found to be less reactive than DMA with estimated reactivity ratios of rDMA = 2.73 and rBOT = 0.04 which led to BOT incorporation throughout the high-yielding copolymerization in the absence of vinyl homopolymerization reported for the use of other thionolactone monomers. The BOT repeat units were easily cleaved through aminolysis and basic hydrolysis. Uniquely, the dithiocarbonate repeat units featured two cleavable C—S bonds, meaning that the degradant was not retained as a fragment end group. Cyclic xanthates are therefore useful for the preparation of easily degradable acrylamide copolymers.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"54 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145949908","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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