Polymer Chemistry最新文献_第10页

Polymer chemistry informed neural networks (PCINNs) for data-driven modelling of polymerization processes† 用于聚合过程数据驱动建模的聚合物化学信息神经网络（PCINNs）

IF 4.1 2区化学

Polymer Chemistry Pub Date : 2024-10-22 DOI: 10.1039/d4py00995a

Nicholas Ballard , Jon Larrañaga , Kiarash Farajzadehahary , José M. Asua

引用次数: 0

Functionalization of nano-objects in living anionic polymerization-induced self-assembly and their use for improving thermal properties of epoxy resins 活体阴离子聚合诱导自组装中纳米物体的功能化及其在改善环氧树脂热性能中的应用

IF 4.1 2区化学

Polymer Chemistry Pub Date : 2024-10-22 DOI: 10.1039/d4py01008f

Guicun Guo , Jiali Wu , Jingwei Zhang , Peng Zhou , Ding Shen , Penghan Li , Guowei Wang

{"title":"Functionalization of nano-objects in living anionic polymerization-induced self-assembly and their use for improving thermal properties of epoxy resins","authors":"Guicun Guo , Jiali Wu , Jingwei Zhang , Peng Zhou , Ding Shen , Penghan Li , Guowei Wang","doi":"10.1039/d4py01008f","DOIUrl":"10.1039/d4py01008f","url":null,"abstract":"<div><div>Nano-objects generated <em>via</em> a scalable polymerization-induced self-assembly (PISA) process can serve as organic nanofillers, replacing the widely used inorganic nanofillers in composites. In this contribution, polyisoprene (PI)-<em>b</em>-polystyrene (PS) (PI-<em>b</em>-PS) or PI-<em>b</em>-PS/PS nano-objects were prepared <em>via</em> a living anionic polymerization-induced self-assembly (LAPISA) process or a derived process of living anionic polymerization-induced cooperative assembly (LAPICA) using nonpolar <em>n</em>-heptane as a solvent, which facilitated the control over morphologies and sizes. After the living species in the core region were <em>in situ</em> crosslinked by divinylbenzene (DVB) monomers, stabilized PDVB@(PI-<em>b</em>-PS) or PDVB@(PI-<em>b</em>-PS/PS) nano-objects were generated. After hydroxylated or epoxidized nano-objects were obtained through thiol–ene or epoxidation reactions on the double bonds of the PI stabilizer, the miscibility between the nano-objects and epoxy resin was improved, and the functionalized nano-objects could be introduced into epoxy resin. Differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and thermomechanical analysis (TMA) results affirmed that the organic nano-objects could improve the thermal properties of the composites, which were obviously superior to commercial inorganic silica nano-objects. In particular, the composites with smaller spherical nano-objects had a higher glass transition temperature (<em>T</em><sub>g</sub>) than those with larger spherical ones or worm-like ones. Transmission electron microscopy (TEM) measurements verified the uniform distribution of organic nano-objects and the formation of sufficiently integrated interfaces between the epoxy resin and nano-objects, thereby improving the thermal properties of the composites.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"15 45","pages":"Pages 4637-4649"},"PeriodicalIF":4.1,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142486256","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}

引用次数: 0

Interpretable machining learning assisted insights into bifunctional squaramide catalyzed ring-opening polymerization of lactide† 双官能方酰胺催化的内酰胺开环聚合的可解释加工学习辅助见解

IF 4.1 2区化学

Polymer Chemistry Pub Date : 2024-10-22 DOI: 10.1039/d4py00866a

Shaoju Cao , Mengting Hong , Junyuan Hu , Zhenjiang Li , Jin Huang , Kai Guo

{"title":"Interpretable machining learning assisted insights into bifunctional squaramide catalyzed ring-opening polymerization of lactide†","authors":"Shaoju Cao , Mengting Hong , Junyuan Hu , Zhenjiang Li , Jin Huang , Kai Guo","doi":"10.1039/d4py00866a","DOIUrl":"10.1039/d4py00866a","url":null,"abstract":"<div><div>The structural understanding of catalysts is essential for achieving efficient and selective polymerization. In this study, we designed a series of bifunctional catalysts based on squaramide, carboxylates, and alkali cations for the ring-opening polymerization (ROP) of lactide. These catalysts exhibited controlled polymerization behavior with narrow dispersity (<em>Đ</em><sub>M</sub> = 1.08–1.12). Kinetic evaluations revealed a linear relationship between the catalyst's chain length and activity for short CH<sub>2</sub> chains (<em>X</em> = 1–4). However, as the CH<sub>2</sub> segments lengthened, an “odd-even” effect on the kinetics was found, suggesting that the chain length alternately enhances or diminishes catalytic activity. The catalytic activity was significantly influenced by the counter cation (Li<sup>+</sup>, Na<sup>+</sup>, K<sup>+</sup>, and Cs<sup>+</sup>) of carboxylate, with larger radius cations showing higher rate constants (<em>k</em><sub>obs Cs<sup>+</sup></sub> > <em>k</em><sub>obs K<sup>+</sup></sub> > <em>k</em><sub>obs Na<sup>+</sup></sub> > <em>k</em><sub>obs Li<sup>+</sup></sub>). Computational studies demonstrated that this correlation resulted from varying binding energies. Moreover, the <em>k</em><sub>obs</sub> value of the catalyst can be tuned by adding different ratios of the crown ether. An interpretable machine learning method was introduced to link physical properties and activities, guiding the further design of effective catalysts for ROP.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"15 44","pages":"Pages 4562-4569"},"PeriodicalIF":4.1,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142536840","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}

引用次数: 0

Catalytic copolymerization of carbon dioxide and cyclohexene oxide by a trinuclear cyclohexane-bridged tetradentate Schiff base chromium complex† 三核环己烷桥接四价席夫碱铬络合物催化二氧化碳与环己烯氧化物的共聚作用

IF 4.1 2区化学

Polymer Chemistry Pub Date : 2024-10-22 DOI: 10.1039/d4py00956h

Jie Huang , Boxiong Shen

{"title":"Catalytic copolymerization of carbon dioxide and cyclohexene oxide by a trinuclear cyclohexane-bridged tetradentate Schiff base chromium complex†","authors":"Jie Huang , Boxiong Shen","doi":"10.1039/d4py00956h","DOIUrl":"10.1039/d4py00956h","url":null,"abstract":"<div><div>The development of catalytic systems is a central area of research in carbon dioxide (CO<sub>2</sub>) and epoxy copolymerization. A novel trinuclear cyclohexane-bridged tetradentate Schiff base chromium complex was synthesized as a catalyst for the ring-opening copolymerization (ROCOP) of CO<sub>2</sub> and cyclohexene oxide (CHO), resulting in the formation of poly (cyclohexene carbonate) (PCHC). The impact of polymerization temperature, CO<sub>2</sub> pressure, reaction time, and catalyst loading on complex 's polymerization activity was systematically investigated. It was observed that, with the addition of the co-catalyst PPNN<sub>3</sub> (PPN = bis(triphenylphosphine)iminium), complex exhibited enhanced catalytic activity for the ROCOP of CO<sub>2</sub> and CHO under mild conditions. In contrast, the mononuclear tetradentate Schiff base chromium complex system showed low activity under the same conditions. Compared to complex , complex achieved a higher CHO conversion rate (70%) and 85% PCHC selectivity, with a turnover frequency (TOF) of 419 h<sup>−1</sup>, which is 5.3 times greater than that of complex . Additionally, the polymer produced by complex had a molecular weight of 13 790 g mol<sup>−1</sup>, which is higher than that produced by complex (8800 g mol<sup>−1</sup>) and the commercial Salen CrCl catalyst (9610 g mol<sup>−1</sup>). By varying the amounts of complex and CHO, PCHC with different molecular weights (6000 g mol<sup>−1</sup> to 14 000 g mol<sup>−1</sup>) and low dispersity can be easily obtained. Notably, the activation energy barrier for polycarbonate formation in the complex system was 21.63 kJ mol<sup>−1</sup>, compared to 32.88 kJ mol<sup>−1</sup> in the complex system.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"15 44","pages":"Pages 4519-4528"},"PeriodicalIF":4.1,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142431623","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}

引用次数: 0

Backbone editing of oxidized polyethylene: insertion of oxygen and nitrogen atoms via hydroxyalkyl azide-mediated rearrangements† 氧化聚乙烯的骨架编辑：通过羟烷基叠氮化物介导的重排插入氧原子和氮原子

IF 4.1 2区化学

Polymer Chemistry Pub Date : 2024-10-22 DOI: 10.1039/d4py00973h

Andrew J. King , Ryan P. Sherrier , Jeffrey Aubé , Aleksandr V. Zhukhovitskiy

{"title":"Backbone editing of oxidized polyethylene: insertion of oxygen and nitrogen atoms via hydroxyalkyl azide-mediated rearrangements†","authors":"Andrew J. King , Ryan P. Sherrier , Jeffrey Aubé , Aleksandr V. Zhukhovitskiy","doi":"10.1039/d4py00973h","DOIUrl":"10.1039/d4py00973h","url":null,"abstract":"<div><div>The properties, applications, and end-of-life considerations of plastics are fundamentally linked to the structure of the polymer backbones at the core of these materials. With that in mind, editing the polymer backbone composition offers exciting opportunities to transform the plastics economy; yet, few examples of such transformations utilize commodity plastics as starting materials. In this work, we describe the development of a tandem C–H oxidation/hydroxyalkyl azide mediated rearrangement strategy that converts polyethylene into “polyethylene-like” materials with iminium ethers, esters, amides, and other pendant chemical functionality. Control over formation of esters or amides is achieved by variation of the hydroxyalkyl azide reagent, as well as processing conditions. By targeting specific functionalities, a variety of thermal and mechanical properties can be accessed. For example, incorporation of iminium ethers decreases the Young's modulus of post-consumer PE from 196 MPa to 69–83 MPa, but conversion of the iminium ethers to esters and amides produces materials with moduli of 212–287 MPa—values higher than the original material. Thus, the demonstration of a modular backbone editing methodology for polyethylene showcases the broader value of this emerging strategy for polymer modification.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"15 44","pages":"Pages 4554-4561"},"PeriodicalIF":4.1,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142452353","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}

引用次数: 0

Acrylate–methacrylate radical copolymerization kinetics of sparingly water-soluble monomers in polar and nonpolar solvents† 极性和非极性溶剂中稀水溶性单体的丙烯酸酯-甲基丙烯酸酯自由基共聚动力学

IF 4.1 2区化学

Polymer Chemistry Pub Date : 2024-10-22 DOI: 10.1039/d4py01015a

Noushin Rajabalinia , Fatemeh Salarhosseini , Robin A. Hutchinson

{"title":"Acrylate–methacrylate radical copolymerization kinetics of sparingly water-soluble monomers in polar and nonpolar solvents†","authors":"Noushin Rajabalinia , Fatemeh Salarhosseini , Robin A. Hutchinson","doi":"10.1039/d4py01015a","DOIUrl":"10.1039/d4py01015a","url":null,"abstract":"<div><div>The properties of waterborne polymer dispersions synthesized by emulsion radical polymerization are influenced by reactions in both the aqueous medium and the growing particles. Mathematical models representing the process often do not consider the difference in the propagation rate coefficient (<em>k</em><sub>p</sub>) of monomers in the two phases, despite the body of evidence demonstrating that solvent polarity influences monomer–monomer and monomer-solvent hydrogen-bonding that affects both <em>k</em><sub>p</sub> homopropagation values and copolymerization reactivity ratios. Therefore, it is vital to develop experimental approaches to systematically measure the influence of solvent on the copolymerization kinetics of hydrophobic monomers under conditions that are similar to emulsion systems. In this work, we study the copolymerization of methyl acrylate (MA) with di(ethylene glycol) methyl ether methacrylate (DEGMEMA) as models for the common emulsion monomers butyl acrylate and methyl methacrylate. As well as varying solvent choice and monomer concentration, MA/DEGMEMA copolymerization kinetics are compared to those of MA with methacrylic acid (MAA) to determine the influence of monomer functionality on its relative reactivity. The findings suggest that the copolymer composition of all methacrylate–acrylate systems – whether involving functional or non-functional monomers – converge to a single curve in protic polar aqueous solution.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"15 44","pages":"Pages 4542-4553"},"PeriodicalIF":4.1,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142486255","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}

引用次数: 0

Synthesis of degradable polyester with high molecular weight and excellent mechanical properties through copolymerization modification of poly(butylene succinate)† 通过共聚改性聚丁二酸丁二醇酯合成具有高分子量和优异机械性能的可降解聚酯

IF 4.1 2区化学

Polymer Chemistry Pub Date : 2024-10-22 DOI: 10.1039/d4py01050g

Hongji Wang , Xiaojun Ma , Hanyu Yao , Haohao Chang , Yin Lv , Zhong Wei

{"title":"Synthesis of degradable polyester with high molecular weight and excellent mechanical properties through copolymerization modification of poly(butylene succinate)†","authors":"Hongji Wang , Xiaojun Ma , Hanyu Yao , Haohao Chang , Yin Lv , Zhong Wei","doi":"10.1039/d4py01050g","DOIUrl":"10.1039/d4py01050g","url":null,"abstract":"<div><div>Maintaining the high mechanical properties of degradable polyesters is crucial for their practical application. In this work, tricyclodecanedimethanol (TCD) with a rigid ring structure was introduced into the synthesis of polybutylene succinate (PBS) to form PBTCDS copolyester. The addition of TCD significantly improved the glass transition temperature (<em>T</em><sub>g</sub>), mechanical properties, and barrier properties of the copolyester. The inherent toughness of PBS is limited by its poor elongation at break, which restricts its application range. However, the tensile strength of PBTCDS5 synthesized in this study is 42 MPa, with an elongation at break of 687%. It is noteworthy that the elongation at break of PBTCDS15 reaches 860%, greatly improving the mechanical properties of PBS. Compared with PBS (<em>T</em><sub>g</sub> −31.4 °C), the <em>T</em><sub>g</sub> of the copolyester increased from −29.2 °C to −22.8 °C, thereby improving its thermal properties. The water vapor barrier test showed that the water vapor transmission rate had improved. In addition, water degradation experiments showed that changing the TCD content resulted in different degradation rates, leading to copolyesters with different degradation rates. Ultimately, this method significantly improves mechanical properties while maintaining degradability, thereby broadening the application scope of PBS.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"15 44","pages":"Pages 4570-4579"},"PeriodicalIF":4.1,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142489558","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}

引用次数: 0

Nickel-catalyzed direct synthesis of hyperbranched liquid oligoethylene† 镍催化直接合成超支化液体寡聚乙烯

IF 4.1 2区化学

Polymer Chemistry Pub Date : 2024-10-22 DOI: 10.1039/d4py00709c

Mengyao Zhang , Shengyu Dai

{"title":"Nickel-catalyzed direct synthesis of hyperbranched liquid oligoethylene†","authors":"Mengyao Zhang , Shengyu Dai","doi":"10.1039/d4py00709c","DOIUrl":"10.1039/d4py00709c","url":null,"abstract":"<div><div>Late transition metal-catalyzed ethylene chain-walking polymerization offers a remarkably convenient method for synthesizing hyperbranched polyethylene. In this study, we created a series of pyridine-imine Ni(<span>ii</span>) complexes with axially flexible cycloalkyl substituents, tailored for the production of hyperbranched oligoethylene oils (HBOEOs). These complexes exhibited moderate activity in HBOEO synthesis, reaching rates of up to 4.90 × 10<sup>5</sup> g mol<sup>−1</sup> h<sup>−1</sup>. The resulting products exhibited low molecular weights (325–523 g mol<sup>−1</sup>) and high branching densities (110–167/1000C). NMR analysis verified their diverse branching structures, with a significant proportion of hyperbranched motifs. Notably, the activity, structure, and properties of the HBOEOs produced by the catalytic system were significantly influenced by alterations in the catalyst structure and oligomerization conditions. Specifically, when compared to rigid phenyl substituents, flexible cycloalkyl substituents proved more effective in promoting the catalytic system to produce HBOEOs with a higher degree of branching and improved liquefaction properties.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"15 45","pages":"Pages 4627-4636"},"PeriodicalIF":4.1,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142384328","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}

引用次数: 0

The CF3TMS adduct of anthraquinone as a monomer for making polymers with potential as separation membranes† 将蒽醌的 CF3TMS 加合物作为一种单体，用于制造具有分离膜潜力的聚合物

IF 4.1 2区化学

Polymer Chemistry Pub Date : 2024-10-21 DOI: 10.1039/D4PY01002G

Kim Jiayi Wu, John M. Tobin, Anli Ji, Yang Shi, Chunchun Ye, Gary S. Nichol, Alessio Fuoco, Mariagiulia Longo, Johannes C. Jansen and Neil B. McKeown

引用次数: 0

Self-healable, reprocessable and anti-flammable eugenol-derived covalent adaptable thermosets based on dynamic covalent boronic esters and thiol–ene click chemistry† 基于动态共价硼酸酯和巯基烯点击化学的可自愈合、可再加工和防燃的丁香酚衍生共价适应性热固性塑料

IF 4.1 2区化学

Polymer Chemistry Pub Date : 2024-10-17 DOI: 10.1039/D4PY00684D

Haoxin Niu, Yu Li, Ping Zhang, Wenwen Guo, Xin Wang and Yuan Hu

{"title":"Self-healable, reprocessable and anti-flammable eugenol-derived covalent adaptable thermosets based on dynamic covalent boronic esters and thiol–ene click chemistry†","authors":"Haoxin Niu, Yu Li, Ping Zhang, Wenwen Guo, Xin Wang and Yuan Hu","doi":"10.1039/D4PY00684D","DOIUrl":"10.1039/D4PY00684D","url":null,"abstract":"<p >Due to their excellent properties, thermosetting polymer materials have been widely used in many fields. Owing to the restriction of the crosslinked network, traditional thermosetting polymer materials exhibit insolubility and immiscibility. Therefore, the reprocessing of thermosetting polymer materials is a great challenge. With the depletion of petroleum-based resources, the utilization of natural resources for the preparation of bio-based thermosetting polymer materials is a major trend. In this study, eugenol-based covalent adaptable thermosets were prepared <em>via</em> UV curing and thermal curing according to thiol click chemistry. The mechanical properties of the eugenol-based covalent adaptable thermosets, which are better than those of the control sample, can be regulated according to the components. The eugenol-based covalent adaptable thermosets exhibited excellent transparency and UV shielding properties. The introduction of a dynamic covalent boronic ester (BSH) promoted the formation of residual char and enhanced the fire safety of the eugenol-based covalent adaptable thermosets. Owing to the dynamic borate ester bonds in the cross-linked network, the eugenol-based covalent adaptable thermosets exhibited significant stress relaxation behavior, and excellent shape memory function and self-healing properties. The samples were reprocessed at 100 °C several times. After three cycles of pulverizing and hot pressing, the recovery ratio of tensile strength of the reprocessed samples remained above 85%. This study provides a novel strategy for preparing self-healable, reprocessable and anti-flammable covalent adaptable thermosets with tunable mechanical properties.</p>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":" 48","pages":" 4952-4961"},"PeriodicalIF":4.1,"publicationDate":"2024-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142443937","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}

引用次数: 0