Macromolecules最新文献_第9页

Polydithiocarbamates with Discontinuous Mws Synthesized via Multicomponent Tandem Polymerizations of CS2, Secondary Diamines, and Dibromide

IF 5.1 1区化学

Macromolecules Pub Date : 2025-02-17 DOI: 10.1021/acs.macromol.4c0272710.1021/acs.macromol.4c02727

Jinlei Huo, Yulian Yang, Yang Hu, Rongrong Hu* and Ben Zhong Tang,

{"title":"Polydithiocarbamates with Discontinuous Mws Synthesized via Multicomponent Tandem Polymerizations of CS2, Secondary Diamines, and Dibromide","authors":"Jinlei Huo, Yulian Yang, Yang Hu, Rongrong Hu* and Ben Zhong Tang, ","doi":"10.1021/acs.macromol.4c0272710.1021/acs.macromol.4c02727","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c02727https://doi.org/10.1021/acs.macromol.4c02727","url":null,"abstract":"Polydithiocarbamates are a group of promising functional polymer materials with unique structures, dynamic reversible properties, and photosensitivity, but the efficient, convenient, and diversified syntheses of poly(N-substituted)dithiocarbamates remain challenging. In this work, room temperature transition-metal-free multicomponent tandem polymerization (MCTP) of CS2, secondary diamines, and 1,4-di(bromomethyl)benzene was reported to construct five poly(N-substituted)dithiocarbamates with high molecular weights (Mws) of up to 60800 g/mol and high yields of up to 91% using commercially available simple monomers under mild and convenient conditions, achieving high atom economy and about 60 g-scale synthesis. Most importantly, polymers with discontinuous Mws could be obtained in one pot, depending on the amine structures and polymerization time, and the solution underwent automatic stratification during the polymerization with a low-Mw portion in the upper layer and a high-Mw portion in the bottom layer. These poly(N-substituted)dithiocarbamates generally possessed good solubility, high thermal stability and could be photodegraded efficiently upon UV irradiation to produce terephthalaldehyde. The MCTP has provided a simple and robust synthetic approach for polydithiocarbamates, and the self-stratification has been suggested as a facile method for molecular weight control of step-growth polymerizations, which could accelerate the development of polymerization methodology and sulfur-containing polymer materials.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"58 4","pages":"1867–1877 1867–1877"},"PeriodicalIF":5.1,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143478125","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Ten Problems in Polymer Reactivity Prediction

IF 5.1 1区化学

Macromolecules Pub Date : 2025-02-17 DOI: 10.1021/acs.macromol.4c0258210.1021/acs.macromol.4c02582

Nicholas E. Jackson*, and , Brett M. Savoie*,

引用次数: 0

Organocatalytic Ring-Opening (Co)polymerization of Six-Membered Monothiocarbonates for the Synthesis of Recyclable Poly(monothiocarbonate)s

IF 5.1 1区化学

Macromolecules Pub Date : 2025-02-17 DOI: 10.1021/acs.macromol.4c0302810.1021/acs.macromol.4c03028

Jianghui Li, Yingying Zhang, Yang Li*, Chengjian Zhang* and Xinghong Zhang*,

{"title":"Organocatalytic Ring-Opening (Co)polymerization of Six-Membered Monothiocarbonates for the Synthesis of Recyclable Poly(monothiocarbonate)s","authors":"Jianghui Li, Yingying Zhang, Yang Li*, Chengjian Zhang* and Xinghong Zhang*, ","doi":"10.1021/acs.macromol.4c0302810.1021/acs.macromol.4c03028","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c03028https://doi.org/10.1021/acs.macromol.4c03028","url":null,"abstract":"Developing chemically depolymerizable polymers (CDPs) that can revert back to monomers is of great significance for realizing a circular polymer economy. Poly(thiocarbonate)s, sulfur analogs of polycarbonates, are a rather under-investigated group of sulfur-enriched polymers with high potential as CDPs. Here, we report a recyclable poly(monothiocarbonate) obtained via organocatalytic ring-opening polymerization of a six-membered cyclic monothiocarbonate. The resulting polymer exhibited a melting point up to 127 °C and a Young’s modulus of 305 MPa with a tensile stress of 23.2 MPa at 8.8% strain, while the analogue polycarbonate derived from trimethylene carbonate is amorphous with a low modulus (<100 MPa) under ambient temperature. Moreover, a successful copolymerization of 1,3-oxathian-2-one and 5,5-dimethyl-1,3-oxathian-2-one provided an access to precise tunability of thermomechanical performance of the poly(monothiocarbonate)s.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"58 4","pages":"2038–2045 2038–2045"},"PeriodicalIF":5.1,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143478112","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

The Soap Opera of Metal Catalysis in Epoxy-Acid Vitrimers

IF 5.5 1区化学

Macromolecules Pub Date : 2025-02-17 DOI: 10.1021/acs.macromol.4c03067

Diego Ciardi, Ianis Retailleau, François Tournilhac

引用次数: 0

Ten Problems in Polymer Reactivity Prediction

IF 5.5 1区化学

Macromolecules Pub Date : 2025-02-17 DOI: 10.1021/acs.macromol.4c02582

Nicholas E. Jackson, Brett M. Savoie

引用次数: 0

Polyaddition of Discrete Oligo(butylene succinate)s with Divinyl Ethers for Periodic and Selectively Cleavable Main-Chain Acetal Linkages

IF 5.5 1区化学

Macromolecules Pub Date : 2025-02-16 DOI: 10.1021/acs.macromol.4c03178

Ravi Teja Ananthu, Yingjun An, Yusaku Tajima, Hironori Taguchi, Takako Kikuchi, Tomohiro Kubo, Hiroyasu Masunaga, Sono Sasaki, Atsushi Takahara, Kotaro Satoh

{"title":"Polyaddition of Discrete Oligo(butylene succinate)s with Divinyl Ethers for Periodic and Selectively Cleavable Main-Chain Acetal Linkages","authors":"Ravi Teja Ananthu, Yingjun An, Yusaku Tajima, Hironori Taguchi, Takako Kikuchi, Tomohiro Kubo, Hiroyasu Masunaga, Sono Sasaki, Atsushi Takahara, Kotaro Satoh","doi":"10.1021/acs.macromol.4c03178","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c03178","url":null,"abstract":"Poly(butylene succinate) (PBS) is a promising biodegradable and sustainable thermoplastic, but its poor degradability in marine environments is a cause for concern. In this study, we aimed to mitigate this issue by developing novel PBS derivatives with labile acetal linkages periodically distributed along the polymer backbone. An efficient protection–deprotection synthesis yielded monodisperse dihydroxy oligo(butylene succinate)s (OBS) with precisely controlled molecular weights, which were consequently employed as the telechelic macromonomers to be polymerized with divinyl ethers in a step-growth fashion. The obtained poly(OBS-acetal)s had high-molecular-weight (Mn > 100,000 Da) and showed PBS-like semicrystalline properties due to the presence of well-defined crystallizable OBS segments joined together by labile spacers. Selective cleavage of the backbone acetal linkages under acidic conditions enabled rapid depolymerization into simpler oligomers with better degradability. Therefore, this general strategy could be utilized to improve the degradability of the polymers while retaining their physical properties.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"13 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143427472","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Modulating Polyethylene Mimics with Degradability via Synthesis and Modeling

IF 5.1 1区化学

Macromolecules Pub Date : 2025-02-14 DOI: 10.1021/acs.macromol.5c0003910.1021/acs.macromol.5c00039

Xiaomeng Li, Amir Suhail, Nagarjuna A. Mahadas, Mengxue Zhang, Zhitao Hu, Morgan Stefik, Olga Kuksenok* and Chuanbing Tang*,

{"title":"Modulating Polyethylene Mimics with Degradability via Synthesis and Modeling","authors":"Xiaomeng Li, Amir Suhail, Nagarjuna A. Mahadas, Mengxue Zhang, Zhitao Hu, Morgan Stefik, Olga Kuksenok* and Chuanbing Tang*, ","doi":"10.1021/acs.macromol.5c0003910.1021/acs.macromol.5c00039","DOIUrl":"https://doi.org/10.1021/acs.macromol.5c00039https://doi.org/10.1021/acs.macromol.5c00039","url":null,"abstract":"Polyethylene (PE) is one of the most important and widely used commodity polymers in the world. It is also among the vital and notoriously nondegradable plastics. Recent efforts are revisiting different approaches to create new generations of PE mimics. We report a model system to explore mimics of functionalized high-density polyethylene (HDPE) and low-density polyethylene (LDPE) via ring-opening metathesis polymerization (ROMP) and thiol–ene click chemistry. By combining experimental and computational studies, we demonstrated that the properties of PE mimics are highly tunable by changing the ester-to-methylene ratio (E:M), with low E:M (e.g., 1:413) functional polymers having characteristics similar to those of HDPE. Controlling the branch-to-methylene ratio (B:M) from 1:159 to 1:22 provided a handle for mimicking the transformation from HDPE to LDPE characteristics. The PE mimics exhibit competitive mechanical properties, melting temperature, and high molecular weight comparable to PE while being accessible via an efficient synthetic route. Notably, the PE mimics can be degraded into oligomers and then recycled, demonstrating the potential for circularity and sustainability. This study provides valuable insights into predicting the properties of aliphatic long-chain functional polymers to mimic PE.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"58 4","pages":"2094–2105 2094–2105"},"PeriodicalIF":5.1,"publicationDate":"2025-02-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143478215","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Controllable Photo-degradability on Polyurethane from AB-Type Monomers AB 型单体聚氨酯的可控光降解性

IF 5.5 1区化学

Macromolecules Pub Date : 2025-02-14 DOI: 10.1021/acs.macromol.4c03108

Johannes Reeb, Yibo Shen, Patrick Theato, Yosuke Akae

引用次数: 0

Unraveling Structure–Reactivity and Structure–Property Relationships for the Amidation of Methyl Ester-Functionalized Poly(2-Oxazoline)s 揭示甲基酯官能化聚（2-噁唑啉）酰胺的结构-反应性和结构-性质关系

IF 5.5 1区化学

Macromolecules Pub Date : 2025-02-14 DOI: 10.1021/acs.macromol.4c02523

Annelore Podevyn, Joachim F. R. Van Guyse, Petra J. M. Bouten, Jan C. M. van Hest, Richard Hoogenboom

{"title":"Unraveling Structure–Reactivity and Structure–Property Relationships for the Amidation of Methyl Ester-Functionalized Poly(2-Oxazoline)s","authors":"Annelore Podevyn, Joachim F. R. Van Guyse, Petra J. M. Bouten, Jan C. M. van Hest, Richard Hoogenboom","doi":"10.1021/acs.macromol.4c02523","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c02523","url":null,"abstract":"Poly(2-alkyl-2-oxazoline)s (PAOx) featuring methyl ester side chains have received increasing interest in recent years, as they readily undergo various post-polymerization modification reactions, such as amidation, thereby enabling straightforward structural diversification from a single reactive precursor. Furthermore, ester functional PAOx can be generated with various spacer lengths between the ester functional group and the polymer backbone, allowing straightforward tuning of the solution and thermal properties. In this work, we subjected different methyl ester-bearing PAOx to full amidation reactions with various primary and secondary amines to establish the structure–reactivity and structure–property relationships. Kinetic investigations of the 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD)-catalyzed amidation reactions revealed that the reactivity correlates with the nucleophilicity of the amines and inversely correlates with the spacer length between the polymer backbone and the ester functionality (PC2MestOx > PC3MestOx > PC4MestOx). These results highlight the importance of macromolecular parameters in the TBD-catalyzed amidation of polymers with pendant ester groups involving intramolecular activation. Finally, we explored the thermal solution and bulk properties of a 30-membered library of amidated polymer products to derive structure–property relationships, which can serve as guidelines for the design and synthesis of functional PAOx (bio)materials.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"21 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-02-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143417991","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Unraveling Structure–Reactivity and Structure–Property Relationships for the Amidation of Methyl Ester-Functionalized Poly(2-Oxazoline)s

IF 5.1 1区化学

Macromolecules Pub Date : 2025-02-14 DOI: 10.1021/acs.macromol.4c0252310.1021/acs.macromol.4c02523

Annelore Podevyn, Joachim F. R. Van Guyse, Petra J. M. Bouten, Jan C. M. van Hest and Richard Hoogenboom*,

{"title":"Unraveling Structure–Reactivity and Structure–Property Relationships for the Amidation of Methyl Ester-Functionalized Poly(2-Oxazoline)s","authors":"Annelore Podevyn, Joachim F. R. Van Guyse, Petra J. M. Bouten, Jan C. M. van Hest and Richard Hoogenboom*, ","doi":"10.1021/acs.macromol.4c0252310.1021/acs.macromol.4c02523","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c02523https://doi.org/10.1021/acs.macromol.4c02523","url":null,"abstract":"Poly(2-alkyl-2-oxazoline)s (PAOx) featuring methyl ester side chains have received increasing interest in recent years, as they readily undergo various post-polymerization modification reactions, such as amidation, thereby enabling straightforward structural diversification from a single reactive precursor. Furthermore, ester functional PAOx can be generated with various spacer lengths between the ester functional group and the polymer backbone, allowing straightforward tuning of the solution and thermal properties. In this work, we subjected different methyl ester-bearing PAOx to full amidation reactions with various primary and secondary amines to establish the structure–reactivity and structure–property relationships. Kinetic investigations of the 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD)-catalyzed amidation reactions revealed that the reactivity correlates with the nucleophilicity of the amines and inversely correlates with the spacer length between the polymer backbone and the ester functionality (PC2MestOx > PC3MestOx > PC4MestOx). These results highlight the importance of macromolecular parameters in the TBD-catalyzed amidation of polymers with pendant ester groups involving intramolecular activation. Finally, we explored the thermal solution and bulk properties of a 30-membered library of amidated polymer products to derive structure–property relationships, which can serve as guidelines for the design and synthesis of functional PAOx (bio)materials.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"58 4","pages":"2026–2037 2026–2037"},"PeriodicalIF":5.1,"publicationDate":"2025-02-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143478104","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0