Christoph Schmidleitner, Matthias Udo Kriehuber, Roman Korotkov, Sandra Schlögl, Elisabeth Rossegger
Frontal polymerization is a curing method that is known for its high conversion, short reaction times and low energy consumption. However, the resulting materials are typical thermosets, allowing no reprocessing, reshaping nor recycling. Herein, a new approach is pursued, which combines the energy efficiency of frontal polymerization with the unique post-processability of covalent adaptable networks. Thus, selected thiol-acrylate resins, bearing a sufficiently high number of ester linkages and free hydroxyl groups, were investigated, using phosphate esters as transesterification catalysts. The amount of phosphate ester and thiol was varied and its influence on material properties and frontal polymerization kinetics were analyzed. The reaction kinetics were studied with FTIR and photo-DSC measurements, showing a trend towards lower reactivity and higher conversions with an increased thiol content. The obtained networks exhibited tunable bond exchange rates by varying either the amount of thiol or of the catalyst. DMA measurements reveal a higher network homogeneity with increasing thiol content. Moreover, reprocessing, recycling as well as reshaping of the material was successfully demonstrated. Concludingly, these findings could significantly lower energy consumption and increase circularity in future thermoset production.
{"title":"Frontal Polymerization of Thiol-Acrylate Covalent Adaptable Networks","authors":"Christoph Schmidleitner, Matthias Udo Kriehuber, Roman Korotkov, Sandra Schlögl, Elisabeth Rossegger","doi":"10.1039/d4py01106f","DOIUrl":"https://doi.org/10.1039/d4py01106f","url":null,"abstract":"Frontal polymerization is a curing method that is known for its high conversion, short reaction times and low energy consumption. However, the resulting materials are typical thermosets, allowing no reprocessing, reshaping nor recycling. Herein, a new approach is pursued, which combines the energy efficiency of frontal polymerization with the unique post-processability of covalent adaptable networks. Thus, selected thiol-acrylate resins, bearing a sufficiently high number of ester linkages and free hydroxyl groups, were investigated, using phosphate esters as transesterification catalysts. The amount of phosphate ester and thiol was varied and its influence on material properties and frontal polymerization kinetics were analyzed. The reaction kinetics were studied with FTIR and photo-DSC measurements, showing a trend towards lower reactivity and higher conversions with an increased thiol content. The obtained networks exhibited tunable bond exchange rates by varying either the amount of thiol or of the catalyst. DMA measurements reveal a higher network homogeneity with increasing thiol content. Moreover, reprocessing, recycling as well as reshaping of the material was successfully demonstrated. Concludingly, these findings could significantly lower energy consumption and increase circularity in future thermoset production.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"41 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142975280","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}
Johan Liotier, Leila Issoufou Alfari, Benoit Mahler, Thomas A Niehaus, C. Dujardin, Simon Guelen, Vincent Schanen, Véronique Dufaud, Jean Raynaud, Vincent Monteil
Upcycling of polyethersulfone (PES), a high-performance polymer based on an aromatic-rich aryl-ether-based backbone, can advantageously yield both starting Bisphenol S (BPS) comonomer and valuable OLED derivatives, providing complete atom valorization strategy for PES waste. Deprotonated selected amines proved particularly efficient at depolymerizing PES at moderate temperatures (~ 120 °C). The recycled monomer yields validate the back-to-monomer chemical recycling method for industrial compliance. The OLED derivatives afforded by the same simple process can easily be isolated and promote an innovative upcycling strategy using polymer-to-valuable chemicals, a very relevant approach to help mitigate the ever-growing plastic waste accumulation.
{"title":"Polyethersulfones upcycling to luminescent materials by aminolysis","authors":"Johan Liotier, Leila Issoufou Alfari, Benoit Mahler, Thomas A Niehaus, C. Dujardin, Simon Guelen, Vincent Schanen, Véronique Dufaud, Jean Raynaud, Vincent Monteil","doi":"10.1039/d4py01250j","DOIUrl":"https://doi.org/10.1039/d4py01250j","url":null,"abstract":"Upcycling of polyethersulfone (PES), a high-performance polymer based on an aromatic-rich aryl-ether-based backbone, can advantageously yield both starting Bisphenol S (BPS) comonomer and valuable OLED derivatives, providing complete atom valorization strategy for PES waste. Deprotonated selected amines proved particularly efficient at depolymerizing PES at moderate temperatures (~ 120 °C). The recycled monomer yields validate the back-to-monomer chemical recycling method for industrial compliance. The OLED derivatives afforded by the same simple process can easily be isolated and promote an innovative upcycling strategy using polymer-to-valuable chemicals, a very relevant approach to help mitigate the ever-growing plastic waste accumulation.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"24 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142939511","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}
Zhongxuan Chen, Xuanhua Guo, Guangqiang Xu, Huibin Zou, Qinggang Wang
The chiral (BisSalen)Al complexes have been confirmed as powerful catalysts for perfect asymmetric kinetic resolution polymerization (AKRP) of racemic phenethylglycolide (Pegl). However, the control mechanism in the AKRP mediated by (BisSalen)Al complexes is not sufficient. Herein, the polymerization of diastereomeric (rac and meso-) Pegl mixtures mediated by (BisSalen)Al complex SS-1 was investigated for the first time. The origin of AKRP in Pegl was determined to be enantiomorphic site control (ESC) through NMR-HPLC analysis, kinetic study and stereosequence analysis.
{"title":"The control mechanism of (BisSalen)Al mediated asymmetric kinetic resolution polymerization of phenethylglycolide","authors":"Zhongxuan Chen, Xuanhua Guo, Guangqiang Xu, Huibin Zou, Qinggang Wang","doi":"10.1039/d4py01439a","DOIUrl":"https://doi.org/10.1039/d4py01439a","url":null,"abstract":"The chiral (BisSalen)Al complexes have been confirmed as powerful catalysts for perfect asymmetric kinetic resolution polymerization (AKRP) of racemic phenethylglycolide (Pegl). However, the control mechanism in the AKRP mediated by (BisSalen)Al complexes is not sufficient. Herein, the polymerization of diastereomeric (<em>rac</em> and <em>meso</em>-) Pegl mixtures mediated by (BisSalen)Al complex <em>SS</em>-1 was investigated for the first time. The origin of AKRP in Pegl was determined to be enantiomorphic site control (ESC) through NMR-HPLC analysis, kinetic study and stereosequence analysis.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"13 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142939514","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}
Philipp Martschin, Timo Prölß, Andreas Hutzler, Simon Thiele, Jochen Kerres
The membrane is the heart of an electrochemical cell. Nowadays, PFSA-based materials, e.g., Nafion®, are state-of-the-art in large-scale energy applications. However, PFSAs are relatively expensive and give rise to concerns regarding toxic intermediates in the production process. Moreover, their recyclability and their biodegradability are questionable. Thus, there is a strong need to develop alternative materials with comparable or better properties. This study presents a new class of phosphonated hydrocarbon polymers based on commercially available polysulfone Udel (PSU) synthesized by a lithiation reaction. The modified PSUs were subsequently phosphonated by a Michaelis-Arbuzov reaction. All synthesized polymers/ionomers were further characterized by NMR, DSC, TGA, GPC, TEM, and titration. Moreover, the first blend membranes could be produced out of the new class of PSU derivatives. In summary, four different polymers were synthesized, of which three were successfully phosphonated. Starting from the phosphonated species, three different acid-acid blend membranes were manufactured with sufficient ionic conductivity. These novel phosphonic acid group-containing materials are promising candidates for membranes or ionomers in electrochemical applications, like (HT)-PEMFCs, (HT)-PEMWEs, or redox flow batteries.
{"title":"Preparation of a new class of phosphonated hydrocarbon polymers based on polysulfone","authors":"Philipp Martschin, Timo Prölß, Andreas Hutzler, Simon Thiele, Jochen Kerres","doi":"10.1039/d4py01289e","DOIUrl":"https://doi.org/10.1039/d4py01289e","url":null,"abstract":"The membrane is the heart of an electrochemical cell. Nowadays, PFSA-based materials, e.g., Nafion®, are state-of-the-art in large-scale energy applications. However, PFSAs are relatively expensive and give rise to concerns regarding toxic intermediates in the production process. Moreover, their recyclability and their biodegradability are questionable. Thus, there is a strong need to develop alternative materials with comparable or better properties. This study presents a new class of phosphonated hydrocarbon polymers based on commercially available polysulfone Udel (PSU) synthesized by a lithiation reaction. The modified PSUs were subsequently phosphonated by a Michaelis-Arbuzov reaction. All synthesized polymers/ionomers were further characterized by NMR, DSC, TGA, GPC, TEM, and titration. Moreover, the first blend membranes could be produced out of the new class of PSU derivatives. In summary, four different polymers were synthesized, of which three were successfully phosphonated. Starting from the phosphonated species, three different acid-acid blend membranes were manufactured with sufficient ionic conductivity. These novel phosphonic acid group-containing materials are promising candidates for membranes or ionomers in electrochemical applications, like (HT)-PEMFCs, (HT)-PEMWEs, or redox flow batteries.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"44 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142937166","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}
Ibrahim Raji, Torin Wilcox, Christopher Scott Hartley, Dominik Konkolewicz
Light- and carbodiimide-responsive hydrogels were synthesized. An “AND” gate was developed using ortho-nitrobenzyl (ONB) protected carboxylic acids in the polymer backbone. Crosslinking was only realized in the presence of both UV stimulus to photocleave the ONB group and carbodiimide fuels to induce anhydride bonds. In the presence of water, the anhydride bonds eventually hydrolyze to carboxylic acids and the system returns to the solution state. The mechanical properties of the out-of-equilibrium hydrogels were investigated using oscillatory rheology to examine the effects of deprotection efficiency, carbodiimide concentration and chain architecture on the hydrogels’ moduli and decrosslinking time. Higher moduli and longer decrosslinking times were found with increased carbodiimide concentration and deprotection efficiency. These discoveries unveil new possibilities for photoresponsive chemically fueled soft materials.
{"title":"Photoresponsive Polymers for Carbodiimide-Fueled Transient Hydrogels","authors":"Ibrahim Raji, Torin Wilcox, Christopher Scott Hartley, Dominik Konkolewicz","doi":"10.1039/d4py01244e","DOIUrl":"https://doi.org/10.1039/d4py01244e","url":null,"abstract":"Light- and carbodiimide-responsive hydrogels were synthesized. An “AND” gate was developed using ortho-nitrobenzyl (ONB) protected carboxylic acids in the polymer backbone. Crosslinking was only realized in the presence of both UV stimulus to photocleave the ONB group and carbodiimide fuels to induce anhydride bonds. In the presence of water, the anhydride bonds eventually hydrolyze to carboxylic acids and the system returns to the solution state. The mechanical properties of the out-of-equilibrium hydrogels were investigated using oscillatory rheology to examine the effects of deprotection efficiency, carbodiimide concentration and chain architecture on the hydrogels’ moduli and decrosslinking time. Higher moduli and longer decrosslinking times were found with increased carbodiimide concentration and deprotection efficiency. These discoveries unveil new possibilities for photoresponsive chemically fueled soft materials.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"19 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142939510","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}
Solvent is often indispensable for polymerization reactions, especially to circumvent the negative effects of high viscosity. Cationic ring-opening polymerization (CROP) of 2-oxazolines has been studied for decades for the bio-related characteristics and applications of the products. The commonly used solvent, acetonitrile (AN), raises sustainability concerns for its volatility and toxicity. We report here that bio-sourced, high-boiling-point, high-polarity, and nontoxic (γ-alkyl) γ-butyrolactones are valid green solvents for the CROP of 2-ethyl-2-oxazoline. Polymerization efficiency and control are found the same as in AN. Livingness of the CROP is confirmed by block copolymerization with 2-phenyl-2-oxazoline. A series of organo-initiators, including phosphorus-based acids and carboxylic acids, are employed to gain insights into the structure-activity relationship. Particularly, it is the first time to disclose the initiating activity of 2,6-dihydroxybenzoic acid. This work provides a solution for enhancing the environmental friendliness of synthesis of biomimetic poly(2-oxazoline).
{"title":"Cationic Ring-Opening Polymerization of 2-Oxazolines in γ-Butyrolactones using Various Initiators","authors":"Tingwei Chen, Chenke Zhao, Tao Lai, Junpeng Zhao","doi":"10.1039/d4py01422g","DOIUrl":"https://doi.org/10.1039/d4py01422g","url":null,"abstract":"Solvent is often indispensable for polymerization reactions, especially to circumvent the negative effects of high viscosity. Cationic ring-opening polymerization (CROP) of 2-oxazolines has been studied for decades for the bio-related characteristics and applications of the products. The commonly used solvent, acetonitrile (AN), raises sustainability concerns for its volatility and toxicity. We report here that bio-sourced, high-boiling-point, high-polarity, and nontoxic (γ-alkyl) γ-butyrolactones are valid green solvents for the CROP of 2-ethyl-2-oxazoline. Polymerization efficiency and control are found the same as in AN. Livingness of the CROP is confirmed by block copolymerization with 2-phenyl-2-oxazoline. A series of organo-initiators, including phosphorus-based acids and carboxylic acids, are employed to gain insights into the structure-activity relationship. Particularly, it is the first time to disclose the initiating activity of 2,6-dihydroxybenzoic acid. This work provides a solution for enhancing the environmental friendliness of synthesis of biomimetic poly(2-oxazoline).","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"12 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142936130","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}
Hydrogels can be used in a wide range of applications from personal care products to drug delivery vehicles. Particularly for drug delivery, it is desirable to control the release of the loaded cargo and as well as the hydrogel degradation time. Self-immolative hydrogels have been recently investigated to enable the stimulus-mediated breakdown of the hydrogel, which can also modulate to some extent the release of loaded drugs. However, when the drug was loaded into the hydrogel using non-covalent interactions, the background release rate of the drug in the absence of the stimulus was relatively rapid. Thus, we report here a new hydrogel system based on an acetal end-capped self-immolative polyglyoxylamide backbone with photo-responsive linkers as pendent groups to enable the covalent conjugation of amine-functionalized drugs. Using phenylalanine methyl ester as a model drug, we showed that hydrogels were successfully prepared with 96% equilibrium water content and a compressive modulus of 5.5 kPa. Light irradiation stimulated the rapid and traceless release of the model drug, while no detectable release was observed without irradiation. Furthermore, the PGAm backbone depolymerized selectively at mildly acidic pH. This system therefore provides a new hydrogel platform enabling a high level of control over both hydrogel breakdown and drug release.
{"title":"Polyglyoxylamide hydrogels for the traceless stimulus-mediated release of covalently-immobilized drugs","authors":"Jue Gong, Burak Tavsanli, Elizabeth R. Gillies","doi":"10.1039/d4py01214c","DOIUrl":"https://doi.org/10.1039/d4py01214c","url":null,"abstract":"Hydrogels can be used in a wide range of applications from personal care products to drug delivery vehicles. Particularly for drug delivery, it is desirable to control the release of the loaded cargo and as well as the hydrogel degradation time. Self-immolative hydrogels have been recently investigated to enable the stimulus-mediated breakdown of the hydrogel, which can also modulate to some extent the release of loaded drugs. However, when the drug was loaded into the hydrogel using non-covalent interactions, the background release rate of the drug in the absence of the stimulus was relatively rapid. Thus, we report here a new hydrogel system based on an acetal end-capped self-immolative polyglyoxylamide backbone with photo-responsive linkers as pendent groups to enable the covalent conjugation of amine-functionalized drugs. Using phenylalanine methyl ester as a model drug, we showed that hydrogels were successfully prepared with 96% equilibrium water content and a compressive modulus of 5.5 kPa. Light irradiation stimulated the rapid and traceless release of the model drug, while no detectable release was observed without irradiation. Furthermore, the PGAm backbone depolymerized selectively at mildly acidic pH. This system therefore provides a new hydrogel platform enabling a high level of control over both hydrogel breakdown and drug release.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"15 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142935402","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}
Photopolymerization using visible light represents a significant progress in the synthesis of materials, providing a more economical and ecological method. Therefore, the necessity to develop new and more effective photoinitiating systems is essential, and the use of porphyrin derivatives may become a great alternative in the coming years. According to their high absorbance, their ability to form reactive species under light irradiation, porphyrin derivatives are particularly attractive candidates for the photopolymerization process. The convenience of their functionalization, allowing optimization of their photophysical and photochemical properties, makes them particularly interesting for developing new photoinitiators/ photosensitizers that are effective under visible or IR light irradiation. This review explores the main aspects that need to be anticipated to obtain optimized photoinitiating systems based on porphyrin derivatives. The different routes for synthesizing and functionalizing porphyrins are described, and both the photophysical and photochemical properties of the modified porphyrin derivatives including the absorbance properties, the reactivity of the excited states and the redox capacities of these molecules, are highlighted. Finally, particular attention are attached to promote the use of porphyrin derivatives as photoinitiating systems for free-radical, cationic and photocontrolled radical polymerization.
{"title":"Porphyrin derivatives: promising perspectives in visible/IR light photopolymerization","authors":"Fanny Schnetz, Davy-Louis Versace, Sébastien Richeter","doi":"10.1039/d4py01245c","DOIUrl":"https://doi.org/10.1039/d4py01245c","url":null,"abstract":"Photopolymerization using visible light represents a significant progress in the synthesis of materials, providing a more economical and ecological method. Therefore, the necessity to develop new and more effective photoinitiating systems is essential, and the use of porphyrin derivatives may become a great alternative in the coming years. According to their high absorbance, their ability to form reactive species under light irradiation, porphyrin derivatives are particularly attractive candidates for the photopolymerization process. The convenience of their functionalization, allowing optimization of their photophysical and photochemical properties, makes them particularly interesting for developing new photoinitiators/ photosensitizers that are effective under visible or IR light irradiation. This review explores the main aspects that need to be anticipated to obtain optimized photoinitiating systems based on porphyrin derivatives. The different routes for synthesizing and functionalizing porphyrins are described, and both the photophysical and photochemical properties of the modified porphyrin derivatives including the absorbance properties, the reactivity of the excited states and the redox capacities of these molecules, are highlighted. Finally, particular attention are attached to promote the use of porphyrin derivatives as photoinitiating systems for free-radical, cationic and photocontrolled radical polymerization.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"98 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142935390","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}
A series of diazoacetates with an ester-type dendron unit of 1st to 3rd generation as an ester substituent were newly prepared and their Pd-initiated polymerization was conducted to afford dendronized C1 polymers with SEC-estimated number-average molecular weight (Mn,SEC) up to 16700 and a relatively narrow molecular weight distribution (Đ = 1.12–1.37). Glass transition temperature (Tg) of these dendronized polymers increased with the increasing generation of the dendron unit, where the degree of the increase (ΔTg) was much larger than that observed with their vinyl polymer counterparts (polymethacrylates with the same dendron substituents). The diazoacetate with the 3rd generation dendron unit was successfully copolymerized with benzyl diazoacetate to afford a copolymer, whose dendron-derived units were converted to those with multiple hydroxy groups via deprotection of acetonide-protecting groups at the peripheral positions.
{"title":"Synthesis of Dendronized Polymers Through Pd-Initiated C1 Polymerization of Diazoacetates with Different Generation Ester-type Dendron Groups","authors":"Hiroaki Shimomoto, Takumi Kubo, Kazunari Nishigawa, Hazuki Okuda, Makoto Ishimoto, Tomomichi Itoh, Eiji Ihara","doi":"10.1039/d4py01324g","DOIUrl":"https://doi.org/10.1039/d4py01324g","url":null,"abstract":"A series of diazoacetates with an ester-type dendron unit of 1st to 3rd generation as an ester substituent were newly prepared and their Pd-initiated polymerization was conducted to afford dendronized C1 polymers with SEC-estimated number-average molecular weight (<em>M</em><small><sub>n</sub></small>,SEC) up to 16700 and a relatively narrow molecular weight distribution (<em>Đ</em> = 1.12–1.37). Glass transition temperature (<em>T</em><small><sub>g</sub></small>) of these dendronized polymers increased with the increasing generation of the dendron unit, where the degree of the increase (Δ<em>T</em><small><sub>g</sub></small>) was much larger than that observed with their vinyl polymer counterparts (polymethacrylates with the same dendron substituents). The diazoacetate with the 3rd generation dendron unit was successfully copolymerized with benzyl diazoacetate to afford a copolymer, whose dendron-derived units were converted to those with multiple hydroxy groups via deprotection of acetonide-protecting groups at the peripheral positions.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"48 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142929057","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}
Huanyu Lei, Xing-Han Li, Han Hao, Yuchu Liu, Qing-Yun Guo and Mingjun Huang
Different from the classical self-assembly process in soft matter, we have proposed the concept of unimolecular nanoparticles (UMNPs), which act as spherical motifs and can directly pack into ordered structures (superlattices) in a single step. However, the design principles of UMNPs have been so far vague and qualitative. Here we have developed a series of giant molecules synthesized from β-cyclodextrin (βCD) and polyhedral oligomeric silsesquioxane (POSS). These samples all present spherical packing superlattices and further prove to be UMNPs. By changing the linkages between βCD and OPOSS, the volume of these UMNPs can be adjusted between 44 and 96 nm3, which is very much enlarged compared with our previous studies. We outline the rules for constructing UMNPs: a highly branched core, rigid ligands and short linkers between the core and the ligands are needed. Binary blending of these UMNPs also offers us various unusual superlattices (NaZn13, AlB2, and C14). Among them, the binary blends of two different βCD-type UMNPs lead to the first unimolecular-level binary superlattice, which can more precisely mimic the phase behaviour of nanocrystal superlattices natured with one-step self-assembly. In general, our study of βCD-type UMNPs enables customization in both size and softness, offering a valuable tool for investigating more intricate nanostructures and advanced functional materials.
{"title":"Rational design and size regulation of unimolecular nanoparticles for constructing diverse superlattices in soft matter†","authors":"Huanyu Lei, Xing-Han Li, Han Hao, Yuchu Liu, Qing-Yun Guo and Mingjun Huang","doi":"10.1039/D4PY01237B","DOIUrl":"10.1039/D4PY01237B","url":null,"abstract":"<p >Different from the classical self-assembly process in soft matter, we have proposed the concept of unimolecular nanoparticles (UMNPs), which act as spherical motifs and can directly pack into ordered structures (superlattices) in a single step. However, the design principles of UMNPs have been so far vague and qualitative. Here we have developed a series of giant molecules synthesized from β-cyclodextrin (βCD) and polyhedral oligomeric silsesquioxane (POSS). These samples all present spherical packing superlattices and further prove to be UMNPs. By changing the linkages between βCD and OPOSS, the volume of these UMNPs can be adjusted between 44 and 96 nm<small><sup>3</sup></small>, which is very much enlarged compared with our previous studies. We outline the rules for constructing UMNPs: a highly branched core, rigid ligands and short linkers between the core and the ligands are needed. Binary blending of these UMNPs also offers us various unusual superlattices (NaZn<small><sub>13</sub></small>, AlB<small><sub>2</sub></small>, and C14). Among them, the binary blends of two different βCD-type UMNPs lead to the first unimolecular-level binary superlattice, which can more precisely mimic the phase behaviour of nanocrystal superlattices natured with one-step self-assembly. In general, our study of βCD-type UMNPs enables customization in both size and softness, offering a valuable tool for investigating more intricate nanostructures and advanced functional materials.</p>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":" 4","pages":" 415-421"},"PeriodicalIF":4.1,"publicationDate":"2025-01-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142924905","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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