Polymer Chemistry最新文献

{"title":"Unveiling the Zwitterionic Nature of Ethyl Piperazine-based Dithiocarbamate Chain Transferring Agent for Achieving High Molar Mass of Poly Vinyl Acetate: Experimental and Computational Insight","authors":"P. M. Haribabu, Prabodh Ranjan, Vijayakrishna Kari","doi":"10.1039/d4py01177e","DOIUrl":"https://doi.org/10.1039/d4py01177e","url":null,"abstract":"Vinyl acetate (VAc) is one of the least active unconjugated monomers among the less activated monomers (LAMs), giving rise to highly reactive and unstable propagating radicals. A significant obstacle in achieving well-defined high molar mass polyvinyl acetate (PVAc) is the occurrence of chain transfer reactions during radical polymerization. Towards the controlled polymerization of Vac, we have employed two different dithiocarbamate-based chain transfer agents CTA-1 and -2 bearing ethyl piperazine- and pyrrole as Z stabilizing groups respectively. In CTA-1, the lone pair of electrons on the nitrogen atom is not delocalized, reducing the double-bond character of the C=S bond and enhancing its zwitterionic nature. Conversely, in the pyrrole-based CTA-2, the nitrogen's lone pair of electrons will be delocalized within the aromatic system of the Z group, resulting in less zwitterionic nature. CTA-1 exhibited excellent control over VAc polymerization, yielding a high molar mass of 132 kDa with low dispersity 1.31. In contrast, CTA-2 showed poor control when attempting high molar mass VAc polymerization. This observable change in the polymerization behaviour with CTA-1 and -2 can be attributed to the availability of a lone pair of electrons on the nitrogen of the stabilizing Z group, towards the deactivation of thiocarbonyl group by reducing its double bond character. To understand the underlying reasons, ab-initio and DFT calculations were conducted to investigate the neutral or zwitterionic forms of CTA-1 and CTA-2. The Mulliken charges on each atom, and the β-scission of the S-R bond in these RAFT-adduct radicals of both CTAs were measured. The results revealed that CTA-1 exists in a zwitterionic form, while CTA-2 remains in a neutral form, explaining the superior performance of CTA-1 in VAc polymerization. The other thermodynamic aspects of the S-R β-scission of RAFT-adduct radicals of CTA-1 and CTA-2 also calculated to support the above hypothesis.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"81 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142782864","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}

{"title":"Glycidyl Ethers from Acyclic Terpenes: A Versatile Toolbox for Multifunctional Poly(Ethylene Glycol)s with Modification Opportunities","authors":"Sandra Schüttner, Gregor Linden, Elena Constanze C. Hoffmann, Philipp Holzmüller, Holger Frey","doi":"10.1039/d4py01201a","DOIUrl":"https://doi.org/10.1039/d4py01201a","url":null,"abstract":"Multifunctional poly(ethylene glycol) copolymers (mfPEGs) are accessible via the anionic copolymerization of functional epoxides with ethylene oxide (EO). Glycidyl ethers are conveniently synthesized from bio-renewable alcohols and epichlorohydrin (ECH). Herein, we present the synthesis of a series of acyclic terpenyl glycidyl ethers (TGEs) and their subsequent copolymerization with ethylene oxide (EO) via anionic ring-opening polymerization (AROP). The resulting library of copolymers with varied side chain length and comonomer composition comprises molar masses in the range of 4 800 to 8 300 g∙mol 1 and narrow molar mass distributions (Ð = 1.06 – 1.13). For the copolymerization of the TGEs with EO, detailed 1H NMR in situ kinetic studies revealed a change from ideally random to slight gradient copolyether microstructures with increasing chain length and hydrophobicity of the respective TGE. The living nature of AROP provides control of molar masses, and optimized reaction conditions, such as low reaction temperatures and a weakly bound cesium counterion, suppress the well-known proton abstraction of monosubstituted epoxides. Since the incorporation of the terpenyl side chains impedes crystallization, thermal properties of the copolyethers can be tailored by the monomer feed ratio. Subsequently, hydrogenation and thiol-ene click reactions at the side chain double bonds were carried out as post-polymerization modifications. The application of potassium azo¬di-carboxylate (PADA) in the diimide reduction of the polymers was demonstrated to possess vast potential for the full hydrogenation of the novel copolymers, offering facile purification options. Overall, the copolymerization of EO and TGEs gives access to biobased, tailormade polyethers with options for post-functionalization.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"37 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142782961","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}

{"title":"Dual orthogonal metal-complexes and their utilization for the versatile fabrication of smart interpenetrating polymer networks","authors":"Thomas Baetz, Michael Agyemang, Josefine Meurer, Julian Hniopek, Stefan Zechel, Michael Schmitt, Juergen Popp, Martin D. Hager, Ulrich S. Schubert","doi":"10.1039/d4py01079e","DOIUrl":"https://doi.org/10.1039/d4py01079e","url":null,"abstract":"This article presents a versatile method for the preparation of smart interpenetrating polymer networks (IPNs). Based on two different orthogonal binding motives, IPNs are generated by simply mixing ligand containing polymers and corresponding metal salts leading to a polymeric material featuring shape-memory abilities. Due to the utilization of heteroleptic complexes as crosslinks in one of the two networks, a simple tuning of the crosslinking density, as well as the generation of IPNs made out of three different main polymers is possible. The structure-property-relationships of the resulting IPNs are investigated in a detailed fashion applying FT-Raman spectroscopy, thermogravimetric analysis (TGA) as well as rheological investigations. In the scope of thermo-mechanical analysis (TMA) excellent shape-memory properties, with strain fixity rates near 100% and strain recovery rates up to 93%, could be observed.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"24 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142782872","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}

{"title":"Mechanism and modelling of thermally initiated RAFT step-growth polymerization","authors":"Samantha Marie Clouthier, Joji Tanaka, Wei You","doi":"10.1039/d4py01188k","DOIUrl":"https://doi.org/10.1039/d4py01188k","url":null,"abstract":"HERE WE REPORT THE MODELLING OF THERMALLY INITIATED RAFT STEP-GROWTH POLYMERIZATION KINETICS OF MALEIMIDE AND ACRYLATE MONOMERS WITH BIFUNCTIONAL RAFT AGENTS BEARING TERTIARY CARBOXYALKYL STABILIZED FRAGMENTABLE R GROUPS. BY ANALYTICALLY SOLVING THE GOVERNING EQUATIONS OF OUR MODEL AS DERIVED FROM THE PROPOSED MECHANISM, WE DEMONSTRATE THAT THE KINETICS FOR THESE POLYMERIZATIONS FOLLOWS FIRST ORDER WITH RESPECT TO MONOMER CONCENTRATION. FURTHERMORE, THE OBTAINED APPARENT RATE CONSTANT (KAPP) VALUES INDICATE THAT ACRYLATE MONOMERS POLYMERIZE AT SLOW RATES COMPARED TO MALEIMIDE MONOMERS DURING THERMALLY INITIATED RAFT STEP-GROWTH POLYMERIZATION.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"8 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142777117","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}

{"title":"TBD-catalyzed anionic ring-opening polymerization of hexamethylcyclotrisiloxane: a new route for controlled synthesis of PDMS","authors":"Alice Corfa, Sylvain Caillol, Julien Pinaud, Vincent Ladmiral","doi":"10.1039/d4py01254b","DOIUrl":"https://doi.org/10.1039/d4py01254b","url":null,"abstract":"Controlled anionic ring opening polymerization of hexamethylcyclotrisiloxane (D3) was optimized for commercial and easy to use organic catalyst 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) using various types of initiators. Alcohols and silanols were compared for the synthesis of monofunctional and telechelic PDMS. Polymerizations were monitored by 1H NMR spectroscopy, MALDI-TOF mass spectroscopy and SEC in order to compare the effects of the initiator structure and of the catalyst concentration. TBD was shown to control the AROP of D3 when using silanols as initiator, thus affording well-defined PDMS structures. When alcohols were used as initiators, the polymerization proceeded with lower level of control due to slower initiation. These differences in initiation rates likely originate from the differences in pKa between silanols and alcohols.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"20 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142777081","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}

{"title":"AlEt3-Catalyzed Synthesis of Circularly Polarized Luminescence Active Aggregation-Induced Emission Helical Polyisocyandies","authors":"He Li, Beiming Yu, Yufan Li, Jiaojiao Li, Jie Zheng, Junge Zhi, Xiaofang Li","doi":"10.1039/d4py01037j","DOIUrl":"https://doi.org/10.1039/d4py01037j","url":null,"abstract":"The facile construction of circularly polarized luminescence (CPL) materials through the clever combination of chirality and fluorescence is of great significance. Herein, we provide a simple and efficient synthesis of CPL-active aggregation-induced emission (AIE) helical polyisocyanides through asymmetric polymerization of commonly used chiral aryl isocyanide monomers featuring a D- or L-mentyl-ester pendant group (D/L-IMCIs) catalzyed by a novel AlEt3/[Ph3C][B(C6F5)4] binary catalytic system. The typical fluorophore-free chiral D/L-IMCI monomers, silent in circular dichroism (CD), exhibit intriguing AIE properties. After undergoing asymmetric-induced polymerization with remarkable efficiency, the synthesized poly(D/L-IMCI)s have chiral helical structures, manifesting both CD and AIE characteristics. Based on the “matching rule” of the fluorescent moieties and chiral helical polyisocyandies, these poly(D/L-IMCI)s display distinct CPL signals in both aggregated state and film state, mirroring each other across the 400−600 nm range in THF, with a luminescence dissymmetry factor (|glum|) values around 7.6–7.8 × 10–4 in THF. Moreover, the incorporation of different proportion of a achiral aryl isocyanide bearing an azobenzene pendant (IPPD) into the poly(D/L-IMCI)s through helix-sense-selective copolymerization allows for precise control over the chiroptical properties of the synthesized AIE helical poly(D/L-IMCI-ran-IPPD)s. The nonlinear relationship between the intensity of CD or CPL signals and the D/L-IMCI contents of the synthetic poly(D/L-IMCI-ran-IPPD)s clearly describes strong chiral amplification effects, achieving a maximum |glum| value exceeding 1.0 × 10-3 in THF, which is superior to those of poly(D/L-IMCI)s. These results demonstrate that the helical (co)polyisocyanide's chirality confers a chiral environment, which in turn effectively induces chirality within both the excited and ground states. This strategy provides new perspectives for the straightforward and simple construction of novel CPL-active AIE polymers through asymmetric polymerization of commonly used functional monomers.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"122 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142777078","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}

{"title":"Towards the Synthesis of Polythiazolines: A Post-polymerization Approach","authors":"Aikaterini Mathianaki, Aysha Demeler, Adrian Dömling, Federico Ferrrari, Frieda Clara M. Scheelje, Hilke Bahmann, Guillaume Delaittre","doi":"10.1039/d4py00930d","DOIUrl":"https://doi.org/10.1039/d4py00930d","url":null,"abstract":"The synthesis of novel tertiary polythioamide copolymers, analogues of poly(2-ethyl-2-oxazoline) (PEtOx), is reported. Firstly, the direct synthesis of poly(2-methyl-2-thiazoline) was attempted via the cationic ring-opening polymerization of 2-methyl-2-thiazoline, in analogy to the well-known 2-alkyl-2-oxazoline monomers. Since no conversion was monitored under several conditions – which was investigated in parallel by density functional theory calculations – the post-polymerization modification of PEtOx using the Lawesson’s reagent was successfully utilized, yielding poly(2-ethyl-2-thiazoline)-<em>co</em>-(2-ethyl-2-oxazoline) copolymers with up to 95 mol% of the thioamide unit. The newly synthesized copolymers exhibited significantly lower water solubility and thermal stability than the pristine PEtOx, as demonstrated during cloud point temperature determination and thermal gravimetric analysis respectively. Moreover, the glass transition temperature of the copolymers increases linearly with increasing oxygen-thiol exchange.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"37 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142777077","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}

{"title":"Structure-Property Relationships to Direct the Dynamic Properties of Acylsemicarbazide-Based Materials","authors":"Stefan Maessen, Siebe Lekanne Deprez, Bart van den Bersselaar, Pascal Vermeeren, Johan P. A. Heuts, Martin Lutz, Célia Fonseca Guerra, Anja Palmans","doi":"10.1039/d4py01296h","DOIUrl":"https://doi.org/10.1039/d4py01296h","url":null,"abstract":"Secondary interactions, such as hydrogen bonding or phase separation, can enhance the stability of dynamic covalent materials without compromising on desired dynamic properties. Here, we investigate the combination of multiple secondary interactions in dynamic covalent materials based on acylsemicarbazides (ASCs), with the aim of achieving tunable material properties. The effects of different ASC substituents on the dynamic covalent and hydrogen bonding capabilities were investigated in a small molecule study using a combined experimental and theoretical approach and revealed the presence of cooperative hydrogen-bonding interactions in 2 directions in one of the derivatives. The different motifs were subsequently implemented in polymeric materials. Combining ASC motifs capable of strong multiple hydrogen bonding with a polydimethylsiloxane backbone introduces structure-dependent, ordered nanophase separation in polymeric materials. The thermo-mechanical properties of these materials reveal a strong dependance on the hydrogen-bonding structure and exact nature of the ASC bond. The dynamics in bulk show that bond exchange depends on the dissociation rate obtained from ASC model compounds, as well as the strength of the secondary interactions in these materials. Differences in hydrogen-bonding structures of the ASC groups also cause differences in creep resistance of the materials. Interestingly, the materials with strong, ordered and cooperative hydrogen-bonded clusters show the highest creep resistance. Our results demonstrate that tuning both the dissociation rate and the secondary interactions by molecular design in dynamic covalent materials is important for controlling their thermal stability and creep resistance","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"37 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142763705","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}

{"title":"High Second-Order Nonlinear Optical Effect Achieved by Gradually Decreased Rotational Energy Barriers","authors":"Panpan Qiao, Wentao Yuan, Qianqian Li, Zhen Li","doi":"10.1039/d4py01238k","DOIUrl":"https://doi.org/10.1039/d4py01238k","url":null,"abstract":"With the aim to efficiently convert the microscopic second-order nonlinear optical (NLO) effect of chromophore moieties into a high macroscopic NLO performance as large as possible, this work focused on the connection groups between the chromophore moieties of NLO polymers, in which alkoxy chains with different lengths and positions were systematically incorporated. The ignorable difference of the alkoxy chain from the normally utilized alkyl one directly resulted in improved macroscopic NLO performance, and d33 values increased gradually from 105 to 131/157, then to 165 pm V-1 with the increased content of alkoxy chains, and further achieved up to 178 pm V-1 with the prolonged lengths of alkoxy chains. It was mainly due to the lower rotational barriers of ether bonds than those of the commonly used alkyl chains with carbon-carbon bonds, and the isolated effect of alkoxy chains with larger sizes. This work provides a new way to achieve high second-order NLO effect from efficient modulation of chromophore orientations by adjustment of energy barriers.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"26 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142763505","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}

{"title":"Tuning 'Ligandless' Direct Arylation Polymerization toward Less-Branching EDOT Polymers","authors":"Xilin Pei, Quan Yang, Yanlu Sun, Wu Wei, Jianyong Yu, Yong He","doi":"10.1039/d4py01212g","DOIUrl":"https://doi.org/10.1039/d4py01212g","url":null,"abstract":"Direct arylation polymerization conditions can be classified into phosphine-assisted and \"ligandless\" conditions. We compared the outcomes of five poly[thiophene-derivates-alt-EDOT]s and PEDOTF polymerized under two kinds of conditions. The results revealed that the \"ligandless\" conditions led to higher polymerization efficiency compared to phosphine-assisted conditions when employing n-hexyl functionalized EDOT as arylative substrate and various dibromoarenes as oxidative substrates. Computational studies revealed that the phosphine-assisted conditions follow the standard concerted metalation-deprotonation (CMD). In contrast, the amide-assisted conditions follow electrophilic CMD. This mechanistic difference provides a reasonable explanation for the preference of \"ligandless\" conditions towards activation of electron-donating arenes. Additionally, the use of sterically hindered amide solvents and dibromoarenes helps reduce branching defects, preserving the desired linear polymer structure.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"134 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142763709","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}