Developing simple and highly efficient organocatalytic systems for the ring-opening alternating copolymerization (ROAC) of epoxides and cyclic anhydrides remains a significant challenge. Herein, a simple phosphazenium salt, specifically tetrakis[tris(dimethylamino)phosphoranylidenamino]phosphonium chloride (P 5 + Cl -), combined with triethylborane (Et 3 B) as a cocatalyst, has been demonstrated to be an efficient binary catalytic system for the ROAC of epoxides and cyclic anhydrides. Promoted by the bulky P 5 + cation and the electrostatic effects arising from loosely associated cation-anion pairs in P 5 + Cl -, the P 5 + Cl -/Et 3 B binary system exhibited excellent catalytic performance, achieving the highest turnover frequency (TOF) of 9800 h -1 at 180 °C in the ROAC of cyclohexene oxide (CHO) and phthalic anhydride (PA). Moreover, the ROAC proceeded in a controlled manner, which was supported by kinetic studies, nuclear magnetic resonance ( 1 H NMR) and Gel permeation chromatography (GPC) spectra, and matrix-assisted laser desorption/ionization time of flight mass spectrometry (MALDI-TOF MS) analysis. The methodology produced polyester with a high molecular weight (M n ) of up to 103 kDa, which offered a rare example of poly(PA-alt-CHO) exceeding 100 kDa. A series of well-defined polyesters were synthesized by the coupling of various epoxides (CHO, PO, BO, ECH, AGE and SO) with PA using the P 5 + Cl -/Et 3 B catalytic system.
{"title":"Thermally robust and highly active phosphazenium salt/Lewis acid catalyst for the ring-opening alternating copolymerization of epoxides and cyclic anhydrides","authors":"Xiaoyu Liu, Jiaqi Song, Zheng Zhang, Chuanli Ren","doi":"10.1039/d5py00970g","DOIUrl":"https://doi.org/10.1039/d5py00970g","url":null,"abstract":"Developing simple and highly efficient organocatalytic systems for the ring-opening alternating copolymerization (ROAC) of epoxides and cyclic anhydrides remains a significant challenge. Herein, a simple phosphazenium salt, specifically tetrakis[tris(dimethylamino)phosphoranylidenamino]phosphonium chloride (P 5 + Cl -), combined with triethylborane (Et 3 B) as a cocatalyst, has been demonstrated to be an efficient binary catalytic system for the ROAC of epoxides and cyclic anhydrides. Promoted by the bulky P 5 + cation and the electrostatic effects arising from loosely associated cation-anion pairs in P 5 + Cl -, the P 5 + Cl -/Et 3 B binary system exhibited excellent catalytic performance, achieving the highest turnover frequency (TOF) of 9800 h -1 at 180 °C in the ROAC of cyclohexene oxide (CHO) and phthalic anhydride (PA). Moreover, the ROAC proceeded in a controlled manner, which was supported by kinetic studies, nuclear magnetic resonance ( 1 H NMR) and Gel permeation chromatography (GPC) spectra, and matrix-assisted laser desorption/ionization time of flight mass spectrometry (MALDI-TOF MS) analysis. The methodology produced polyester with a high molecular weight (M n ) of up to 103 kDa, which offered a rare example of poly(PA-alt-CHO) exceeding 100 kDa. A series of well-defined polyesters were synthesized by the coupling of various epoxides (CHO, PO, BO, ECH, AGE and SO) with PA using the P 5 + Cl -/Et 3 B catalytic system.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"36 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145728849","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}
In this study, poly(ethylene glycol)-based materials exhibiting pH-controllable and time-dependent lower critical solution temperature (LCST) were developed using glycidyl triazolyl polymers (GTPs) functionalized with tri(ethylene glycol) monomethyl ether (EG3) and carboxylic acid (COOH) side groups via a copper-free azide–alkyne cycloaddition reaction. The physical properties of the GTP-EG3 homopolymer and the GTP-EG3-co-COOH copolymer were characterized using NMR, IR, size exclusion chromatography, differential scanning calorimetry, and thermogravimetric analysis. The effects of copolymer composition, polymer concentration, ions in phosphate-buffered saline (PBS), and pH on LCST behavior were systematically investigated. PBS was found to promote aggregation of the GTP-EG3 homopolymer due to the salting-out effect described by the Hofmeister series. Since non-ionized COOH groups behave as hydrophobic moieties, the LCST decreased with increasing COOH content. Active control of LCST through pH variation was successfully demonstrated, revealing a linear relationship between LCST and the degree of COOH ionization. The equivalence point observed in the pH titration deviated from the theoretical value. Over time, this deviation gradually diminished. In connection with this phenomenon, a time-dependent change in LCST was also observed, even though no chemical reaction such as hydrolysis took place. The observed LCSTs ranged from 18°C to 81°C, encompassing the physiological temperature range.
{"title":"Functional Glycidyl Triazolyl Polymers Exhibiting pH-Controllable and Time-Dependent Lower Critical Solution Temperature","authors":"Taichi Ikeda","doi":"10.1039/d5py01028d","DOIUrl":"https://doi.org/10.1039/d5py01028d","url":null,"abstract":"In this study, poly(ethylene glycol)-based materials exhibiting pH-controllable and time-dependent lower critical solution temperature (LCST) were developed using glycidyl triazolyl polymers (GTPs) functionalized with tri(ethylene glycol) monomethyl ether (EG3) and carboxylic acid (COOH) side groups via a copper-free azide–alkyne cycloaddition reaction. The physical properties of the GTP-EG3 homopolymer and the GTP-EG3-co-COOH copolymer were characterized using NMR, IR, size exclusion chromatography, differential scanning calorimetry, and thermogravimetric analysis. The effects of copolymer composition, polymer concentration, ions in phosphate-buffered saline (PBS), and pH on LCST behavior were systematically investigated. PBS was found to promote aggregation of the GTP-EG3 homopolymer due to the salting-out effect described by the Hofmeister series. Since non-ionized COOH groups behave as hydrophobic moieties, the LCST decreased with increasing COOH content. Active control of LCST through pH variation was successfully demonstrated, revealing a linear relationship between LCST and the degree of COOH ionization. The equivalence point observed in the pH titration deviated from the theoretical value. Over time, this deviation gradually diminished. In connection with this phenomenon, a time-dependent change in LCST was also observed, even though no chemical reaction such as hydrolysis took place. The observed LCSTs ranged from 18°C to 81°C, encompassing the physiological temperature range.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"1 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145711239","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}
Thomas Joseph Neal, Lucas Dalmasso, Fanny Coumes, Jutta Rieger
Degradable polymer nanoparticles are attracting increasing interest for applications in cargo-release and imaging, as well as offering degradable alternatives to non-degradable nanoparticles used in various commodity applications. One promising approach is the utilisation of photo-degradable polymers such a poly(vinyl ketones). Here we report the ethanolic dispersion and aqueous emulsion polymerisation-induced self-assembly (PISA) of phenyl vinyl ketone (PVK) using a linear polyethylene glycol macromolecular reversible addition-fragmentation chain transfer (RAFT) agent (PEG5K-TTC) to produce UV-light degradable block copolymer (PEG5k-b-PPVK) nanoparticles. We demonstrate that photo-RAFT PISA in ethanol produces well-defined PEG5k-b-PPVK spherical nanoparticles (Dz = 36 – 101 nm) with high monomer conversions in 2 h. These nanoparticles were found to readily degrade under UV-light irradiation, and in natural sunlight, with a substantial loss in molar mass (26 to 1 kg.mol-1). SAXS and TEM studies demonstrated that degradation in ethanol led to a complete loss of the nanoparticle structure. However, upon degradation in water, the particle structure was maintained, although chain degradation occurred as well; presumably because the formed hydrophobic PPVK fragments remain assembled in the hydrophobic particle core due to their insolubility in water. Aqueous emulsion thermal and photo-RAFT PISA of PVK were also studied to produce degradable aqueous diblock copolymer latexes. Utilisation of a photo-RAFT polymerisation procedure led to unwanted side reactions attributed to the production of light-generated monomer radicals, which can initiate a free-radical polymerisation within the monomer droplets. However, utilisation of a classical thermal-RAFT polymerisation avoided this competing initiation and generated well-controlled PEG-b-PPVK diblock copolymers. Lastly, the possibility to copolymerise styrene with PVK through an aqueous emulsion PISA was also demonstrated. All aqueous latexes also showed significant polymer degradation when irradiated with UV-light. This work demonstrates how UV-degradable diblock copolymer nanoparticles can be efficiently synthesised via PISA in both ethanol and water.
{"title":"UV-degradable poly(phenyl vinyl ketone) particles produced by polymerisation-induced self-assembly in ethanol or water","authors":"Thomas Joseph Neal, Lucas Dalmasso, Fanny Coumes, Jutta Rieger","doi":"10.1039/d5py01020a","DOIUrl":"https://doi.org/10.1039/d5py01020a","url":null,"abstract":"Degradable polymer nanoparticles are attracting increasing interest for applications in cargo-release and imaging, as well as offering degradable alternatives to non-degradable nanoparticles used in various commodity applications. One promising approach is the utilisation of photo-degradable polymers such a poly(vinyl ketones). Here we report the ethanolic dispersion and aqueous emulsion polymerisation-induced self-assembly (PISA) of phenyl vinyl ketone (PVK) using a linear polyethylene glycol macromolecular reversible addition-fragmentation chain transfer (RAFT) agent (PEG5K-TTC) to produce UV-light degradable block copolymer (PEG5k-<em>b</em>-PPVK) nanoparticles. We demonstrate that photo-RAFT PISA in ethanol produces well-defined PEG5k-<em>b</em>-PPVK spherical nanoparticles (D<small><sub>z</sub></small> = 36 – 101 nm) with high monomer conversions in 2 h. These nanoparticles were found to readily degrade under UV-light irradiation, and in natural sunlight, with a substantial loss in molar mass (26 to 1 kg.mol<small><sup>-1</sup></small>). SAXS and TEM studies demonstrated that degradation in ethanol led to a complete loss of the nanoparticle structure. However, upon degradation in water, the particle structure was maintained, although chain degradation occurred as well; presumably because the formed hydrophobic PPVK fragments remain assembled in the hydrophobic particle core due to their insolubility in water. Aqueous emulsion thermal and photo-RAFT PISA of PVK were also studied to produce degradable aqueous diblock copolymer latexes. Utilisation of a photo-RAFT polymerisation procedure led to unwanted side reactions attributed to the production of light-generated monomer radicals, which can initiate a free-radical polymerisation within the monomer droplets. However, utilisation of a classical thermal-RAFT polymerisation avoided this competing initiation and generated well-controlled PEG-<em>b</em>-PPVK diblock copolymers. Lastly, the possibility to copolymerise styrene with PVK through an aqueous emulsion PISA was also demonstrated. All aqueous latexes also showed significant polymer degradation when irradiated with UV-light. This work demonstrates how UV-degradable diblock copolymer nanoparticles can be efficiently synthesised via PISA in both ethanol and water.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"29 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145711240","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}
Baotang Liu, Guochen Wang, Dan Zhao, Yujie Zhang, Dong Chen, Yuhong Ma, Wantai Yang
Chain extenders, usually small aliphatic diols, play great roles in thermoplastic polyurethane (TPU) in forming hard segments and increasing the molecular weights. In this study, two chain extenders, N, N-bis(2-hydroxyethyl) urea (MEA-DMC, containing a urea group) and N-(2-hydroxyethyl)-O-(2-hydroxyethyl) carbamate (MEA-EC, containing a single carbamate group), are synthesized to examine their effects on the resulting TPUs with the chain extender 1, 4-butanediol (BDO) as control. Specifically, the TPUs are prepared by reacting the extenders with a prepolymer composed of poly(tetramethylene glycol) (PTMG, M = 2000) and methylene-bis(4-cyclohexylisocyanate) (HMDI). The results show that the tensile strength and elongation at break of TPU-MEA-DMC-1, TPU-MEA-EC-1 and TPU-BDO-1 are 22.7 MPa, 12.0 MPa, 8.2 MPa and 1400%, 1600% and 1200% respectively. The influences of chain extender content, molar ratios of NCO/OH (Rvalue), and prepolymer molecular weights on the properties of as-prepared TPUs have also been studied. The tensile strength of TPU-MEA-DMC are in the range of 22.7 MPa to 50.5 MPa, and TPU-MEA-EC in the range of 12.0 MPa to 34.7 MPa, respectively. These improvements are primarily attributed to urea/urethane in the chain extender or the hard segment density. Urea groups (two hydrogen-bond donors (-NH-)) or carbamate groups (one hydrogen-bond donor (-NH-)) enhance hydrogen-bonding density within the polymer, thus reinforcing its mechanical properties. Moreover, DSC analysis shows TPU-MEA-DMC has a PTMG cold crystallization exotherm near -25°C, which weakens and shifts to higher temperatures with more hard segments or lower prepolymer molecular weight.
{"title":"High-Performance Thermoplastic Polyurethane Elastomers with Enhanced Mechanical Properties Prepared with Chain Extenders Containing Urea and Carbamate Moieties","authors":"Baotang Liu, Guochen Wang, Dan Zhao, Yujie Zhang, Dong Chen, Yuhong Ma, Wantai Yang","doi":"10.1039/d5py01062d","DOIUrl":"https://doi.org/10.1039/d5py01062d","url":null,"abstract":"Chain extenders, usually small aliphatic diols, play great roles in thermoplastic polyurethane (TPU) in forming hard segments and increasing the molecular weights. In this study, two chain extenders, N, N-bis(2-hydroxyethyl) urea (MEA-DMC, containing a urea group) and N-(2-hydroxyethyl)-O-(2-hydroxyethyl) carbamate (MEA-EC, containing a single carbamate group), are synthesized to examine their effects on the resulting TPUs with the chain extender 1, 4-butanediol (BDO) as control. Specifically, the TPUs are prepared by reacting the extenders with a prepolymer composed of poly(tetramethylene glycol) (PTMG, M = 2000) and methylene-bis(4-cyclohexylisocyanate) (HMDI). The results show that the tensile strength and elongation at break of TPU-MEA-DMC-1, TPU-MEA-EC-1 and TPU-BDO-1 are 22.7 MPa, 12.0 MPa, 8.2 MPa and 1400%, 1600% and 1200% respectively. The influences of chain extender content, molar ratios of NCO/OH (Rvalue), and prepolymer molecular weights on the properties of as-prepared TPUs have also been studied. The tensile strength of TPU-MEA-DMC are in the range of 22.7 MPa to 50.5 MPa, and TPU-MEA-EC in the range of 12.0 MPa to 34.7 MPa, respectively. These improvements are primarily attributed to urea/urethane in the chain extender or the hard segment density. Urea groups (two hydrogen-bond donors (-NH-)) or carbamate groups (one hydrogen-bond donor (-NH-)) enhance hydrogen-bonding density within the polymer, thus reinforcing its mechanical properties. Moreover, DSC analysis shows TPU-MEA-DMC has a PTMG cold crystallization exotherm near -25°C, which weakens and shifts to higher temperatures with more hard segments or lower prepolymer molecular weight.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"26 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145711250","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}
Haowei Sun, Takafumi Enomoto, Shota Michida, Takuya Katashima, Ryo Yoshida
Coacervates have emerged as promising systems for achieving dynamic compartmentalization. In particular, synthetic polymeric complex coacervates represent a well-established class. However, they often disassemble at high ionic strength condition due to charge screening effects. In contrast, simple coacervates, which form via phase separation of a single polymer species, serve as complementary systems that can exist under such conditions. Despite this advantage, the design and understanding of synthetic simple coacervates remains limited. Here, we report the thermoresponsive simple coacervation behavior of synthetic copolymers compose of lower critical solution temperature (LCST)-type and hydrophilic monomers. Through systematic investigations, we revealed that a wide variety of combinations of LCST-type monomers and hydrophilic monomers enables thermoresponsive simple coacervation in water in the presence of salts. Our findings provide a guideline for designing thermoresponsive simple coacervate systems based on synthetic LCST-type copolymers. We also highlight the importance of carefully characterizing the microphases that emerge upon phase separation of thermoresponsive copolymers under each specific usage condition.
{"title":"Thermoresponsive Simple Coacervation of Copolymers Composed of LCST-type and Hydrophilic Monomers","authors":"Haowei Sun, Takafumi Enomoto, Shota Michida, Takuya Katashima, Ryo Yoshida","doi":"10.1039/d5py00758e","DOIUrl":"https://doi.org/10.1039/d5py00758e","url":null,"abstract":"Coacervates have emerged as promising systems for achieving dynamic compartmentalization. In particular, synthetic polymeric complex coacervates represent a well-established class. However, they often disassemble at high ionic strength condition due to charge screening effects. In contrast, simple coacervates, which form via phase separation of a single polymer species, serve as complementary systems that can exist under such conditions. Despite this advantage, the design and understanding of synthetic simple coacervates remains limited. Here, we report the thermoresponsive simple coacervation behavior of synthetic copolymers compose of lower critical solution temperature (LCST)-type and hydrophilic monomers. Through systematic investigations, we revealed that a wide variety of combinations of LCST-type monomers and hydrophilic monomers enables thermoresponsive simple coacervation in water in the presence of salts. Our findings provide a guideline for designing thermoresponsive simple coacervate systems based on synthetic LCST-type copolymers. We also highlight the importance of carefully characterizing the microphases that emerge upon phase separation of thermoresponsive copolymers under each specific usage condition.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"39 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145711241","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}
Léa Jacquin, Edgar Espinosa Rodriguez, Pierre-Yves Dugas, Muriel Lansalot, Elodie Bourgeat-Lami, Vincent Monteil, Fabrice Brunel
Nanoplastics have recently been identified across diverse environmental compartments and are now considered a new class of emerging pollutants. Among them, polyethylene (PE) is the most predominant polyolefin detected in both micro- and nanoplastic forms. Accurate environmental and toxicological assessment of PE nanoplastics requires representative model particles; however, their development remains challenging due to PE's semi-crystalline nature, which hinders top-down fabrication, and the gaseous state of its monomer, which complicates bottom-up synthesis involving high pressure and temperature. In this study, we report the surfactant-free radical aqueous emulsion polymerization of ethylene as a viable route to synthesize model PE nanoparticles with tunable surface charges (anionic or cationic) and narrow size distributions (50-150 nm, extended up 200 nm via seeded polymerization). To mimic oxidative environmental aging, copolymer nanoparticles incorporating polar monomers (vinyl acetate or carbon monoxide) were also produced. These materials exhibit variable surface charges, particle sizes, and carbonyl indices, offering structurally and chemically relevant models for investigating the environmental behavior and toxicity of PE-based nanoplastics.
{"title":"Surfactant-free synthesis of polyethylene nanoparticles: toward more realistic model nanoplastics","authors":"Léa Jacquin, Edgar Espinosa Rodriguez, Pierre-Yves Dugas, Muriel Lansalot, Elodie Bourgeat-Lami, Vincent Monteil, Fabrice Brunel","doi":"10.1039/d5py01074h","DOIUrl":"https://doi.org/10.1039/d5py01074h","url":null,"abstract":"Nanoplastics have recently been identified across diverse environmental compartments and are now considered a new class of emerging pollutants. Among them, polyethylene (PE) is the most predominant polyolefin detected in both micro- and nanoplastic forms. Accurate environmental and toxicological assessment of PE nanoplastics requires representative model particles; however, their development remains challenging due to PE's semi-crystalline nature, which hinders top-down fabrication, and the gaseous state of its monomer, which complicates bottom-up synthesis involving high pressure and temperature. In this study, we report the surfactant-free radical aqueous emulsion polymerization of ethylene as a viable route to synthesize model PE nanoparticles with tunable surface charges (anionic or cationic) and narrow size distributions (50-150 nm, extended up 200 nm via seeded polymerization). To mimic oxidative environmental aging, copolymer nanoparticles incorporating polar monomers (vinyl acetate or carbon monoxide) were also produced. These materials exhibit variable surface charges, particle sizes, and carbonyl indices, offering structurally and chemically relevant models for investigating the environmental behavior and toxicity of PE-based nanoplastics.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"226 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145728912","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}
Bis(triphenylphosphine)iminium chloride, PPNCl, is an increasingly important catalyst due to its broad reactivity in both small molecule and polymer synthesis. A recently reported polymeric variant, poly(PPNCl) offers limited recyclability in small molecule synthesis, but its soluble, thermoplastic nature complicates recovery and reuse. To address this limitation, we developed a crosslinked poly(PPNCl) thermoset that dramatically improves performance and reaction scope. As a catalyst in CO2/epoxide coupling reactions the crosslinked derivative is faster and more readily recycled. In addition, the reaction scope can be extended to polymer synthesis, with soluble polyesters formed from coupling epoxides with maleic anhydrides isolated by filtration, with activity retained over multiple reaction cycles. Remarkably, the reaction scope can be further extended by anion exchange, with crosslinked poly(PPNCo(CO)4) used to catalyse the carbonylative ring expansion of epoxides to β-lactones. Together these show that crosslinked poly(PPNCl) is a promising platform for metal-free, robust, recyclable catalysis.
{"title":"Crosslinked Polymeric Bis(triphenylphosphine)iminium Chloride Gels as Recyclable Catalysts","authors":"Ziwei Xu, Michael Patrick Shaver","doi":"10.1039/d5py01143d","DOIUrl":"https://doi.org/10.1039/d5py01143d","url":null,"abstract":"Bis(triphenylphosphine)iminium chloride, PPNCl, is an increasingly important catalyst due to its broad reactivity in both small molecule and polymer synthesis. A recently reported polymeric variant, poly(PPNCl) offers limited recyclability in small molecule synthesis, but its soluble, thermoplastic nature complicates recovery and reuse. To address this limitation, we developed a crosslinked poly(PPNCl) thermoset that dramatically improves performance and reaction scope. As a catalyst in CO2/epoxide coupling reactions the crosslinked derivative is faster and more readily recycled. In addition, the reaction scope can be extended to polymer synthesis, with soluble polyesters formed from coupling epoxides with maleic anhydrides isolated by filtration, with activity retained over multiple reaction cycles. Remarkably, the reaction scope can be further extended by anion exchange, with crosslinked poly(PPNCo(CO)4) used to catalyse the carbonylative ring expansion of epoxides to β-lactones. Together these show that crosslinked poly(PPNCl) is a promising platform for metal-free, robust, recyclable catalysis.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"142 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145711242","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}
To overcome the environmental and resource constraints of petroleum-based polyisobutylene (PIB), the cationic random copolymerization of isobutylene (IB) with the sustainable and renewable monomer β-pinene (Bp) was systematically investigated using an Al2Et3Cl3/trace water initiation system. Through condition optimization (T = -80 °C, [Al2Et3Cl3] = 1.00×10-2 mol/L, nIB:nBp = 98:2), IB-co-Bp copolymers with high molecular weight (Mn was up to 7.86×104 g/mol) were successfully synthesized. This random copolymer structure and reaction mechanism were elucidated via 1H-NMR and DFT. The structural characteristics, thermal properties and mechanical properties of the copolymer were systematically investigated to clarify its composition-property relationships. More importantly, dynamic mechanical analysis of the vulcanized samples demonstrated that Bp incorporation significantly influenced the copolymer’s viscoelastic behavior and network structure. The vulcanization of IB-co-Bp copolymers was shown to effectively enhance its damping performance, thus providing a novel strategy for high molecular weight bio-based PIB and a sustainable pathway for developing advanced elastomers.
{"title":"Synthesis of High Molecular Weight Copolymers of Isobutylene and Bio-Renewable β-Pinene via Cationic Polymerization","authors":"Yanqing Feng, Penghui Guo, Jinfang Chu, Wei Ding, Yushun Jin, Ruofan Liu, Yibo Wu","doi":"10.1039/d5py00976f","DOIUrl":"https://doi.org/10.1039/d5py00976f","url":null,"abstract":"To overcome the environmental and resource constraints of petroleum-based polyisobutylene (PIB), the cationic random copolymerization of isobutylene (IB) with the sustainable and renewable monomer β-pinene (Bp) was systematically investigated using an Al2Et3Cl3/trace water initiation system. Through condition optimization (T = -80 °C, [Al2Et3Cl3] = 1.00×10-2 mol/L, nIB:nBp = 98:2), IB-co-Bp copolymers with high molecular weight (Mn was up to 7.86×104 g/mol) were successfully synthesized. This random copolymer structure and reaction mechanism were elucidated via 1H-NMR and DFT. The structural characteristics, thermal properties and mechanical properties of the copolymer were systematically investigated to clarify its composition-property relationships. More importantly, dynamic mechanical analysis of the vulcanized samples demonstrated that Bp incorporation significantly influenced the copolymer’s viscoelastic behavior and network structure. The vulcanization of IB-co-Bp copolymers was shown to effectively enhance its damping performance, thus providing a novel strategy for high molecular weight bio-based PIB and a sustainable pathway for developing advanced elastomers.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"24 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145674586","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}
Pressure sensitive adhesives (PSAs) are widely used materials in a number of applications, such as sticky notes and tapes, but for most commercial products they are derived from petrochemicals. Here, a series of pentablock polymers, with an ABABA structure featuring poly(cyclohexene oxide-alt-phthalic anhydride) ‘A’ blocks and poly(ε-decalactone) (PDL) ‘B’ blocks, are prepared as pressure-sensitive adhesives from bio-sourced monomers. The pentablock polymers are prepared by controlled polymerisation techniques, using a single catalyst, in a one-pot process. Polymer properties are tuned through varying the hard block (A) content between 16–39 wt%. Below 25 wt% hard block, the pentablock polymers show low-tack adhesive performance (0.2–0.6 N cm−1) and are removed by adhesive failure. Their adhesive performance compares favourably to low-tack commercial adhesives.
压敏胶（psa）在许多应用中被广泛使用，如粘性笔记和胶带，但对于大多数商业产品来说，它们来自石化产品。本研究以生物源单体为原料，制备了一系列具有ABABA结构的五嵌段聚合物，其结构为聚（环己烯氧化物-邻苯二酸酐）‘ a ’嵌段和聚（ε-癸内酯）‘ B ’嵌段。五嵌段聚合物是通过控制聚合技术，使用单一催化剂，在一锅过程中制备的。通过在16-39 wt%之间改变硬块(A)含量来调整聚合物的性能。在25 wt%硬块以下，五块体聚合物表现出低粘性粘附性能（0.2-0.6 N cm−1），并因粘附失败而被去除。其粘接性能优于低粘性商用粘合剂。
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Poly(olefin sulfone)s (POSs), formed via alternating copolymerizations of sulfur dioxide (SO2) and olefins, remain understudied with respect to systematic structure–property relationships. In this work, we report the synthesis and thermal characterization of five POS copolymers and 24 terpolymers derived from linear alkenes (1-hexene, 1-decene) and cycloalkenes (cyclopentene, cyclohexene, norbornene). All polymers were prepared by free radical polymerization at −30 °C initiated by tert-butyl hydroperoxide. Molecular characterization by 1H and 13C NMR spectroscopy, FTIR spectroscopy, and size-exclusion chromatography with multi-angle light scattering (SEC-MALS) confirmed polymer structures and high molecular weights (weight-average molecular weight, Mw = 100–8000 kg mol−1). Thermogravimetric analysis showed decomposition temperatures at 50% weight loss (Td,50%) for the copolymers ranged from 292 to 317 °C, with the highest stability observed in the norbornene-containing copolymers and terpolymers. Differential scanning calorimetry revealed glass transition temperatures (Tg = 46–184 °C) that increased systematically with the incorporation of cyclic comonomers. These results show systematic structure–property relationships in POS co- and terpolymers and demonstrate how polymer structure governs thermal behavior, providing guidance for the design of thermally robust sulfone-based polymers for advanced applications.
聚烯烃砜（POSs）是由二氧化硫（SO2）和烯烃交替共聚形成的，在系统结构-性能关系方面仍未得到充分研究。在这项工作中，我们报道了五种直链烯烃（1-己烯，1-癸烯）和环烯烃（环戊烯，环己烯，降冰片烯）衍生的POS共聚物和24种三元聚合物的合成和热表征。所有聚合物都是在- 30°C下由过氧化叔丁基引发自由基聚合制备的。通过1H和13C核磁共振光谱、FTIR光谱和多角度光散射（SEC-MALS）的排粒径色谱对聚合物进行了分子表征，证实了聚合物的结构和高分子量（重量-平均分子量，Mw = 100-8000 kg mol−1）。热重分析表明，在50%失重（Td,50%）下，共聚物的分解温度范围为292 ~ 317℃，含降冰片烯的共聚物和三元共聚物的稳定性最高。差示扫描量热法显示，随着环共聚单体的加入，玻璃化转变温度（Tg = 46-184℃）有系统地升高。这些结果显示了POS共聚物和三元共聚物的系统结构-性能关系，并展示了聚合物结构如何控制热行为，为设计具有高级应用的热坚固性的砜基聚合物提供了指导。
{"title":"Structure–property relationships in poly(olefin sulfone) copolymers and terpolymers derived from linear and cyclic alkenes","authors":"Isaac D. Addo, Anna Q. Steele, John B. Matson","doi":"10.1039/d5py00859j","DOIUrl":"https://doi.org/10.1039/d5py00859j","url":null,"abstract":"Poly(olefin sulfone)s (POSs), formed <em>via</em> alternating copolymerizations of sulfur dioxide (SO<small><sub>2</sub></small>) and olefins, remain understudied with respect to systematic structure–property relationships. In this work, we report the synthesis and thermal characterization of five POS copolymers and 24 terpolymers derived from linear alkenes (1-hexene, 1-decene) and cycloalkenes (cyclopentene, cyclohexene, norbornene). All polymers were prepared by free radical polymerization at −30 °C initiated by <em>tert</em>-butyl hydroperoxide. Molecular characterization by <small><sup>1</sup></small>H and <small><sup>13</sup></small>C NMR spectroscopy, FTIR spectroscopy, and size-exclusion chromatography with multi-angle light scattering (SEC-MALS) confirmed polymer structures and high molecular weights (weight-average molecular weight, <em>M</em><small><sub>w</sub></small> = 100–8000 kg mol<small><sup>−1</sup></small>). Thermogravimetric analysis showed decomposition temperatures at 50% weight loss (<em>T</em><small><sub>d,50%</sub></small>) for the copolymers ranged from 292 to 317 °C, with the highest stability observed in the norbornene-containing copolymers and terpolymers. Differential scanning calorimetry revealed glass transition temperatures (<em>T</em><small><sub>g</sub></small> = 46–184 °C) that increased systematically with the incorporation of cyclic comonomers. These results show systematic structure–property relationships in POS <em>co</em>- and terpolymers and demonstrate how polymer structure governs thermal behavior, providing guidance for the design of thermally robust sulfone-based polymers for advanced applications.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"31 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145665224","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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