Functional hyperbranched polymers,as an important class of materials,are widely applied in diverse areas.Therefore,the development of simple and efficient reactions to prepare hyperbranched polymers is of great signif...Functional hyperbranched polymers,as an important class of materials,are widely applied in diverse areas.Therefore,the development of simple and efficient reactions to prepare hyperbranched polymers is of great significance.In this work,trialdehydes,diamines,and trimethylsilyl cyanide could easily undergo multicomponent polymerization under mild conditions,producing hyperbranched poly(α-aminonitrile)s with high molecular weights(M_(w) up to 4.87×10^(4))in good yields(up to 85%).The hyperbranched poly(α-aminonitrile)s have good solubility in commonly used organic solvents,high thermal stability as well as morphological stability.Furthermore,due to the numerous aldehyde groups in their branched chains,these hb-poly(α-aminonitrile)s can undergo one-pot,two-step,four-component post-polymerization with high efficiency.This work not only confirms the efficiency of our established catalyst-free multicomponent polymerization of aldehydes,amines and trimethylsilyl cyanide,but also provides a versatile and powerful platform for the preparation of functional hyperbranched polymeric materials.展开更多
Exploration of new green polymerization strategies for the construction of conjugated polymers is important but challengeable.In this work,a multicomponent polymerization of acetylarenes,alkynones and ammonium acetate...Exploration of new green polymerization strategies for the construction of conjugated polymers is important but challengeable.In this work,a multicomponent polymerization of acetylarenes,alkynones and ammonium acetate for in situ construction of conjugated poly(triarylpyridine)s was developed.The polymerization reactions of diacetylarenes,aromatic dialkynones and NH_(4)OAc were performed in dimethylsulfoxide(DMSO)under heating in the presence of potassium tert-butoxide(t-BuOK),affording four conjugated poly(2,4,6-triarylpyridine)s(PTAPs)in satisfactory yields.The resulting PTAPs have good solubility in common organic solvents and high thermal stability with 5%weight loss temperatures reaching up to 460℃.They are also electrochemically active.The PTAPs incorporating tetraphenylethene units manifest aggregation-induced emission features.Moreover,through simply being doped into poly(vinyl alcohol)(PVA)matrix,the polymer and model compound containing triphenylamine moieties exhibit room-temperature phosphorescence properties with ultralong lifetimes up to 696.2 ms and high quantum yields up to 28.7%.This work not only provides a facile green synthetic route for conjugated polymers but also offers new insights into the design of advanced materials with unique photophysical properties.展开更多
Researchers are pursuing promising chemically recyclable polymers.Here,we demonstrate a series of recyclable Se-containing polyesters from the first reported cascade multicomponent polymerization of elemental Se,H_(2)...Researchers are pursuing promising chemically recyclable polymers.Here,we demonstrate a series of recyclable Se-containing polyesters from the first reported cascade multicomponent polymerization of elemental Se,H_(2)O,CO,and diacrylate.The polymerization is considered to be through a cascade mechanism:Se is first reduced by CO to COSe;COSe is then reduced by H_(2)O to H_(2)Se;H_(2)Se is finally coupled with diacrylate to form a polymer.The method uses common organic bases as a catalyst and is performed under mild conditions with high yields.The obtained polymer is thermally stable with a tunable melting point,and can be easily depolymerized to Se and diacrylate by H_(2)O_(2) under mild conditions.Owing to the versatile synthesis,the structure/properties of the polymer are scalable,such as P4 and P5 with high-density polyethylene-like mechanical performance.Overall,the polymer is a promising material owing to its modular synthesis,practical recyclability,scalable performance,and commercial raw materials.展开更多
long-term carbon fixation and possible carbon revitalization if introduced with functionality.Yet,such conversion has long been compromised by expensive catalysts and harsh conditions due to the inactivity of CO_(2).I...long-term carbon fixation and possible carbon revitalization if introduced with functionality.Yet,such conversion has long been compromised by expensive catalysts and harsh conditions due to the inactivity of CO_(2).In this work,we establish an efficient CuCl/Ph_(3)P-catalyzed multicomponent polymerization of CO_(2),diynes,and dihalides under mild conditions of rt—60◦C and atmospheric pressure.The polymerization shows great monomer universality,producing diverse poly(alkynoate)s in yields up to 99%with weight-average molecular weights up to 94000.Poly(alkynoate)s containing tetraphenylethylene(TPE)moieties show typical aggregation-induced emission features,and can specifically and sensitively detect Fe3+ions with a low limit of detection(LOD)of 1.79×10^(−7) M.Notably,owing to lots of activated triple bonds in the main chain of poly(alkynoate)s,N-hydroxyphthalimide derivatives are facilely introduced into this polymerization in situ to establish a‘one-pot,two-step,four-component’tandem polymerization to produce poly(3a-hydroxyisoxazolo[3,2-a]isoindol-8(3aH)-ones)s(PHIIOs)with 100%grafting ratio.Interestingly,the fused heterocyclic PHIIO containing TPE could realize the specific and sensitive detection of Ag+ions with a low LOD of 4.90×10^(−6)M.This work not only innovatively achieves the direct chemical fixation of CO_(2)into functional polymeric materials under relatively low temperatures with low-cost catalysts,but also obtains a series of polymers with controllable structure-function,which can be realized for a wide range of applications.展开更多
Polythiocarbonates with similar structures to polycarbonates,have emerged as a group of promising sulfur-containing polymers with a range of practical applications,taking advantages of their excellent optical properti...Polythiocarbonates with similar structures to polycarbonates,have emerged as a group of promising sulfur-containing polymers with a range of practical applications,taking advantages of their excellent optical properties,good thermal stability and filmforming ability,and so on.However,the synthesis of polythiocarbonates generally suffered from mixed isomeric structures of repeating units,and hazardous sulfur-containing reagents.In this work,an efficient multicomponent reaction of elemental sulfur,difluoromethylene phosphobetaine(PDFA),and aryl silyl ethers was designed with the assistance of organic base 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene(MTBD)to produce 12 kinds of O,O'-monothiocarbonate compounds in up to 93%yields,taking advantages of the unique chemical property of difluorocarbene,and the deprotection of silyl group by F-generated from PDFA.Most importantly,the MTBD-assisted multicomponent polymerization of bis(aryl silyl ether)s,elemental sulfur,and PDFA was developed,affording 12 kinds of poly(O,O'-monothiocarbonate)s with well-defined structures,high Mws of up to 16900 g/mol and high yields(up to 99%).These poly(O,O'-monothiocarbonate)s possessed good film-forming properties and thermal stability,high light refractive indices and transmittance.The facile synthesis of these polymonothiocarbonates might pave the way for the development of promising sulfur-containing polymer materials.展开更多
Selenium-containing polymers with fascinating functionalities such as stimuli-responsive property,enzyme mimics,antioxidant activity,promotion of immune-cell activity,anticancer activity,and controlled delivery proper...Selenium-containing polymers with fascinating functionalities such as stimuli-responsive property,enzyme mimics,antioxidant activity,promotion of immune-cell activity,anticancer activity,and controlled delivery property,are highly desired,but rarely developed due to their underexplored synthetic methods.Herein,through careful design of monomeric structures and polymerization conditions,we report a series of catalyst-free multicomponent polymerizations(MCPs)of elemental selenium with aliphatic/aromatic diamines and diisocyanides that directly converted selenium to polyselenoureas with long-term stability,good solubility,well-characterized structures,and unique functionalities.The MCPs enjoyed broad monomer scope and fast conversion in 1 min,delivering 18 polyselenoureas with high molecular weights(M_(w)s up to 94,600 g/mol)in high yields(up to 99%).Furthermore,the polyselenoureas could be used for the extraction of Au^(3+)from mixed-metal ion solutions under practical conditions with high selectivity,sensitivity(<1μg/L),efficiency(>99.99%),and capacity(up to 665.60 mg·Au^(3+)/g)within 1 min.Further,the elemental gold was recoverable after the pyrolysis of the polymer complexes.展开更多
The efficient utilization of elemental sulfur(S8) for developing high value-added chemicals is a global concern considering its abundant sources and yearly accelerating environmental issues. However, it has been a lon...The efficient utilization of elemental sulfur(S8) for developing high value-added chemicals is a global concern considering its abundant sources and yearly accelerating environmental issues. However, it has been a long-standing challenge to directly transform elemental sulfur to sulfur-containing polymer, especially via an environmentally benign manner. Herein, a unique chemo-differentiating multicomponent polymerization(MCP) of elemental sulfur, chloroform, and diamine is reported to construct polythiourea based on amine-involved two sequential reactions including isothiocyanation and nucleophilic addition.This strategy features isocynide-free monomers as starting materials, mild conditions, high molecular weights(up to72,900 g/mol) and desired yields(up to 83%). With the advantages of inactive isocyanation and active nucleophilic addition, the stoichiometric balance of amine and isothiocyanate could be delicately controlled to afford various polythioureas with high molecular weights. The polythioureas have been further utilized in the Cu-based aqueous catalysis and Hg-based ion adsorption.展开更多
Polymers with metal coordination ability are outstanding precursors of nanocatalysts,attracting numerous attention in nanocatalysis area.It has been rarely reported for the poly(N-sulfonyl amidines)as macromolecular l...Polymers with metal coordination ability are outstanding precursors of nanocatalysts,attracting numerous attention in nanocatalysis area.It has been rarely reported for the poly(N-sulfonyl amidines)as macromolecular ligands for nanocatalysis.Herein,a catalyst-free multicomponent polymerization(MCP)strategy is developed to facilely prepare a library of amphiphilic poly(Nsulfonyl amidines)with zwitterionic properties starting from disulfonyl azide,hydrophilic dialdehyde and cyclic amino acids including proline and pipecolinic acid.Metals or additives can be thorougly avoided through this method.All the obtained polymers have well-defined structures,high yields and weight-average molecular weights(M_(w)s,up to 99,300 g/mol).The unique zwitterionic property,amphiphilicity and Cu(Ⅰ)coordination ability of the obtained poly(N-sulfonyl amidines)endow them to form the polymer-Cu(Ⅰ)complexes as nanocatalysts.Such nanocatalysts exhibit high catalytic efficiency in aqueous Cucatalyzed azide-alkyne cycloaddition(CuAAC)reaction at a low Cu(Ⅰ)loading of 50 ppm.Nanocatalysts with a high ratio of polymers to Cu(Ⅰ)have also been demonstrated with Cu(Ⅰ)stabilization ability.This work provides a“green”MCP method toward zwitterionic and amphiphilic poly(N-sulfonyl amidines),and highlights their unique potentials for nanocatalysis.展开更多
The development of a facile and efficient polymerization to prepare cyclopentadiene-containing polymers is of vital importance and highly desired. In this work, a metal-free multicomponent polymerization of activated ...The development of a facile and efficient polymerization to prepare cyclopentadiene-containing polymers is of vital importance and highly desired. In this work, a metal-free multicomponent polymerization of activated diyne, electrophilic styrene and isocyanide for the preparation of highly substituted poly(cyclopentadiene) was established. Soluble and thermally stable polymers with high molecular weights are obtained in high yields under mild conditions. By introducing the tetraphenylethene or triphenylamine moiety into polymer backbones, the resultant polymers show unique aggregation-induced emission(AIE)characteristics. Interestingly, AIE polymers can also be generated in situ from non-AIE monomers. Moreover, the prepared polymers can generate photopatterns to function as photoresists and can also serve as visualizing agents to selectively stain the lipid droplets in live cells. This efficient polymerization will open up enormous opportunities for preparing functional cyclopentadiene-containing polymers applicable in diverse areas.展开更多
Electron-deficient N-heteroaromatic polymers are crucial for the high-tech applications of organicmaterials,especially in the electronic and optoelectronic fields.Thus,the development of new polymerizations to afford ...Electron-deficient N-heteroaromatic polymers are crucial for the high-tech applications of organicmaterials,especially in the electronic and optoelectronic fields.Thus,the development of new polymerizations to afford adaptable electron-donating-accepting scaffolds in N-heteroaromatic polymers is in high demand.Herein,we have developed metal-free multicomponent polymerizations of diynes,diamines,and glyoxylates successfully for in situ generation of poly(quinoline)s with high molecular weights(Mw up to 16,900)in nearly quantitative yields.By tuning the electron distributions of the polymer backbones,the resulting poly(quinoline)s showed various aggregation-induced behaviors and photoresponsive abilities:The thin films of the poly(quinoline)s could be fabricated readily intowell-resolved photopatterns by photolithography techniques.They could be utilized as fluorescent probes to visualize themorphologies of polymer materials directly;these include spherulites and microphase separation of polymer blends.Their nanoparticles demonstrated sensitive and highly selective fluorescence quenching to hexavalent chromium ion Cr(Ⅵ),thereby providing access for biological imaging of Cr(Ⅵ)in unicellular algae.展开更多
Dimethyl sulfoxide(DMSO)possessing strong solvency and high boiling point is a very important aprotic polar solvent in organic and polymer synthesis.Notably,it is also a useful synthon in organic chemistry.However,the...Dimethyl sulfoxide(DMSO)possessing strong solvency and high boiling point is a very important aprotic polar solvent in organic and polymer synthesis.Notably,it is also a useful synthon in organic chemistry.However,the direct incorporation of DMSO in polymer synthesis remains challenging.In this work,DMSO was successfully converted to nitrogen-containing heterocyclic polymers as a monomer via multicomponent polymerizations(MCPs)with dialdehydes and diamines in the presence of K_(2)S_(2)O_(8)/t-BuOK at 120℃in 6 h.A series of poly(phenylquinoline)s with high M_(w)values(up to 5.11×10^(4))were obtained in satisfactory yields(up to 82%),performing good solubility,good thermal and morphological stability as well as excellent film-forming ability.The thin films of poly(phenylquinoline)s exhibit high refractive index value in a wide wavelength range of 400–1700 nm.Thus,this work not only enriches the family of MCPs but also provides an efficient strategy for the conversion of DMSO into functional polymeric materials that are potentially applicable in diverse areas.展开更多
Multicomponent polymerizations(MCPs)are powerful tools to synthesize functional polymers with great structural diversity,low cost and high efficiency,which usually generate single polymer product.Herein,a robust one-p...Multicomponent polymerizations(MCPs)are powerful tools to synthesize functional polymers with great structural diversity,low cost and high efficiency,which usually generate single polymer product.Herein,a robust one-pot diamines,CS_(2)and monoisocyanide-participated catalyst-free polymerization was developed at room temperature to produce polythiourea and thioformamide simultaneously in equal equivalent,which was featured with cheap monomers,simple operation and mild condition,affording various polythioureas with high Mws of up to 4.75×10^(4)g/mol in high yields of up to 98%.Polythioureas with varied chain composition and sequence-controlled structure could be synthesized in 62 g-scale from copolymerization or multicomponent tandem polymerization,enabling facile tuning of thermal property,crystallinity,mechanical property,and fluorescence.The abundant irregular hydrogen bonds endowed the polythioureas excellent glassy state self-healing property at room temperature or below 0℃.This polymerization provided an efficient and economic approach to access functional polythioureas.展开更多
Green monomers, such as carbon dioxide(CO_(2)), are closely related to our daily life and highly desirable to be transferred to functional polymers with diverse structures and versatile properties because they are abu...Green monomers, such as carbon dioxide(CO_(2)), are closely related to our daily life and highly desirable to be transferred to functional polymers with diverse structures and versatile properties because they are abundant, cheap, nontoxic, renewable, and sustainable. However, the polymerizations based on these green monomers are to be further developed. In this work, a facile CO_(2) and alkyne-based one-pot, two-step, fourcomponent tandem polymerization was successfully established. The polymerization of CO_(2), diynes, alkyl dihalides, and primary/secondary amines can proceed under mild reaction conditions and regio-and stereoregular poly(aminoacrylate)s with good solubility and thermal stability were obtained in high yields(up to 95%). Notably, distinctly different stereoregularity of resultant poly(aminoacrylate)s was realized via using primary or secondary amines. Using the former would readily generate polymers with 100% Z-isomers, whereas the latter furnished products with over 95% E-isomers. Through different monomer combination, the polymers with tunable structures and properties were obtained.Moreover, the tetraphenylethene units containing poly(aminoacrylate)s, showing the unique aggregation-induced emission characteristics,could function as a fluorescent probe for sensitive explosive detection. Thus, this work not only develops a facile CO_(2) and alkyne-based multicomponent tandem polymerization but also provides a valuable strategy to fine-tune the polymer structures and properties, which could be potentially applied in diverse areas.展开更多
Water,characterized by its safety,abundance,low cost,and sustainability,has garnered increasing attention in polymer synthesis.It has been utilized as a solvent or a comonomer in polymerizations based on triple-bond b...Water,characterized by its safety,abundance,low cost,and sustainability,has garnered increasing attention in polymer synthesis.It has been utilized as a solvent or a comonomer in polymerizations based on triple-bond building blocks for the construction of functional polymers.Currently,distinct progress has been made;however,no such review was presented.This Review aims to summarize the progress in alkyne-based polymerizations in aqueous media with the“on-water”effect,water-involved alkyne-based polymerizations,and water-involved isocyanide-based polymerizations.The catalyst systems,reaction conditions,post-modification strategies,and the properties and applications of the resulting polymers are summarized.Furthermore,the challenges and opportunities in this field are briefly discussed.展开更多
Multicomponent polymerizations have become powerful tools for the construction of sequence-defined polymers. Although the Passerini multicomponent reaction has been widely used in the synthesis of sequence-defined pol...Multicomponent polymerizations have become powerful tools for the construction of sequence-defined polymers. Although the Passerini multicomponent reaction has been widely used in the synthesis of sequence-defined polymers, the tandem usage of the Passerini multicomponent reaction and other multicomponent reactions in one-pot for the synthesis of sequence-defined polymers has not been developed until now. In this contribution, we report the tandem usage of the Passerini three-component reaction and the three-component amine-thiol-ene conjugation reaction in one pot for the synthesis of sequence-defined polymers. The Passerini reaction between methacrylic acid, adipaldehyde, and 2-isocyanobutanoate was carried out, affording a new molecule containing two alkene units. Subsequently, an amine and a thiolactone were added to the reaction system, whereupon the three-component amine-thiol-ene conjugating reaction occurred to yield a sequence-defined polymer. This method offers more rapid access to sequence-defined polymers with high molecular diversity and complexity.展开更多
Chiral-polymers with metal-coordination ability showgreat potential formediating asymmetric reactions.However,the synthesis of structurally diverse chiral polymers remains a great challenge,especially doing so efficie...Chiral-polymers with metal-coordination ability showgreat potential formediating asymmetric reactions.However,the synthesis of structurally diverse chiral polymers remains a great challenge,especially doing so efficiently.Herein,four types of Cucatalyzed multicomponent asymmetric polymerizationswere developed using a flexible combination of OBoc-alkyne.展开更多
基金financially supported by the Scientific Research Start-up Fund Project of Anhui Polytechnic University for Introducing Talents(No.2022YQQ081)Natural Science Research Project of Anhui Educational Committee(No.2024AH050133)the National Natural Science Foundation of China(No.22001078).
文摘Functional hyperbranched polymers,as an important class of materials,are widely applied in diverse areas.Therefore,the development of simple and efficient reactions to prepare hyperbranched polymers is of great significance.In this work,trialdehydes,diamines,and trimethylsilyl cyanide could easily undergo multicomponent polymerization under mild conditions,producing hyperbranched poly(α-aminonitrile)s with high molecular weights(M_(w) up to 4.87×10^(4))in good yields(up to 85%).The hyperbranched poly(α-aminonitrile)s have good solubility in commonly used organic solvents,high thermal stability as well as morphological stability.Furthermore,due to the numerous aldehyde groups in their branched chains,these hb-poly(α-aminonitrile)s can undergo one-pot,two-step,four-component post-polymerization with high efficiency.This work not only confirms the efficiency of our established catalyst-free multicomponent polymerization of aldehydes,amines and trimethylsilyl cyanide,but also provides a versatile and powerful platform for the preparation of functional hyperbranched polymeric materials.
基金supported by the National Natural Science Foundation of China(No.22071166)the Priority Academic Program Development of Jiangsu High Education Institutions(PAPD).
文摘Exploration of new green polymerization strategies for the construction of conjugated polymers is important but challengeable.In this work,a multicomponent polymerization of acetylarenes,alkynones and ammonium acetate for in situ construction of conjugated poly(triarylpyridine)s was developed.The polymerization reactions of diacetylarenes,aromatic dialkynones and NH_(4)OAc were performed in dimethylsulfoxide(DMSO)under heating in the presence of potassium tert-butoxide(t-BuOK),affording four conjugated poly(2,4,6-triarylpyridine)s(PTAPs)in satisfactory yields.The resulting PTAPs have good solubility in common organic solvents and high thermal stability with 5%weight loss temperatures reaching up to 460℃.They are also electrochemically active.The PTAPs incorporating tetraphenylethene units manifest aggregation-induced emission features.Moreover,through simply being doped into poly(vinyl alcohol)(PVA)matrix,the polymer and model compound containing triphenylamine moieties exhibit room-temperature phosphorescence properties with ultralong lifetimes up to 696.2 ms and high quantum yields up to 28.7%.This work not only provides a facile green synthetic route for conjugated polymers but also offers new insights into the design of advanced materials with unique photophysical properties.
基金support of the National Natural Science Foundation of China(grant nos.52373014,U23A2083,and 52203129).
文摘Researchers are pursuing promising chemically recyclable polymers.Here,we demonstrate a series of recyclable Se-containing polyesters from the first reported cascade multicomponent polymerization of elemental Se,H_(2)O,CO,and diacrylate.The polymerization is considered to be through a cascade mechanism:Se is first reduced by CO to COSe;COSe is then reduced by H_(2)O to H_(2)Se;H_(2)Se is finally coupled with diacrylate to form a polymer.The method uses common organic bases as a catalyst and is performed under mild conditions with high yields.The obtained polymer is thermally stable with a tunable melting point,and can be easily depolymerized to Se and diacrylate by H_(2)O_(2) under mild conditions.Owing to the versatile synthesis,the structure/properties of the polymer are scalable,such as P4 and P5 with high-density polyethylene-like mechanical performance.Overall,the polymer is a promising material owing to its modular synthesis,practical recyclability,scalable performance,and commercial raw materials.
基金supported by the National Natural Science Foundation of China(nos.22479102,22001078)the Guangdong Talent Program(no.2023TQ07L822)+1 种基金the Guangdong Basic and Applied Basic Research Foundation(no.2024A1515011716)the startup funding of Songshan Lake Materials Laboratory(no.Y1D1031H311).
文摘long-term carbon fixation and possible carbon revitalization if introduced with functionality.Yet,such conversion has long been compromised by expensive catalysts and harsh conditions due to the inactivity of CO_(2).In this work,we establish an efficient CuCl/Ph_(3)P-catalyzed multicomponent polymerization of CO_(2),diynes,and dihalides under mild conditions of rt—60◦C and atmospheric pressure.The polymerization shows great monomer universality,producing diverse poly(alkynoate)s in yields up to 99%with weight-average molecular weights up to 94000.Poly(alkynoate)s containing tetraphenylethylene(TPE)moieties show typical aggregation-induced emission features,and can specifically and sensitively detect Fe3+ions with a low limit of detection(LOD)of 1.79×10^(−7) M.Notably,owing to lots of activated triple bonds in the main chain of poly(alkynoate)s,N-hydroxyphthalimide derivatives are facilely introduced into this polymerization in situ to establish a‘one-pot,two-step,four-component’tandem polymerization to produce poly(3a-hydroxyisoxazolo[3,2-a]isoindol-8(3aH)-ones)s(PHIIOs)with 100%grafting ratio.Interestingly,the fused heterocyclic PHIIO containing TPE could realize the specific and sensitive detection of Ag+ions with a low LOD of 4.90×10^(−6)M.This work not only innovatively achieves the direct chemical fixation of CO_(2)into functional polymeric materials under relatively low temperatures with low-cost catalysts,but also obtains a series of polymers with controllable structure-function,which can be realized for a wide range of applications.
基金partially supported by the National Natural Science Foundation of China(22325102 and 52173005)the Ministry of Science and Technology of China(2021YFA1501600)+2 种基金the Guangdong Provincial Key Laboratory of Luminescence from Molecular Aggregates(2019B030301003)the Guangdong Basic and Applied Basic Research Foundation(2023B1515040003)the Fundamental Research Funds for the Central Universities(2022ZYGXZR107)。
文摘Polythiocarbonates with similar structures to polycarbonates,have emerged as a group of promising sulfur-containing polymers with a range of practical applications,taking advantages of their excellent optical properties,good thermal stability and filmforming ability,and so on.However,the synthesis of polythiocarbonates generally suffered from mixed isomeric structures of repeating units,and hazardous sulfur-containing reagents.In this work,an efficient multicomponent reaction of elemental sulfur,difluoromethylene phosphobetaine(PDFA),and aryl silyl ethers was designed with the assistance of organic base 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene(MTBD)to produce 12 kinds of O,O'-monothiocarbonate compounds in up to 93%yields,taking advantages of the unique chemical property of difluorocarbene,and the deprotection of silyl group by F-generated from PDFA.Most importantly,the MTBD-assisted multicomponent polymerization of bis(aryl silyl ether)s,elemental sulfur,and PDFA was developed,affording 12 kinds of poly(O,O'-monothiocarbonate)s with well-defined structures,high Mws of up to 16900 g/mol and high yields(up to 99%).These poly(O,O'-monothiocarbonate)s possessed good film-forming properties and thermal stability,high light refractive indices and transmittance.The facile synthesis of these polymonothiocarbonates might pave the way for the development of promising sulfur-containing polymer materials.
基金This research was made possible as a result of a generous grant from National Science Foundation of China(21822102,21774034,21490573,21490574,and 21788102)the Natural Science Foundation of Guangdong Province(2016A030306045 and 2016A030312002)the Innovation and Technology Commission of Hong Kong(ITC-CNERC14SC01)。
文摘Selenium-containing polymers with fascinating functionalities such as stimuli-responsive property,enzyme mimics,antioxidant activity,promotion of immune-cell activity,anticancer activity,and controlled delivery property,are highly desired,but rarely developed due to their underexplored synthetic methods.Herein,through careful design of monomeric structures and polymerization conditions,we report a series of catalyst-free multicomponent polymerizations(MCPs)of elemental selenium with aliphatic/aromatic diamines and diisocyanides that directly converted selenium to polyselenoureas with long-term stability,good solubility,well-characterized structures,and unique functionalities.The MCPs enjoyed broad monomer scope and fast conversion in 1 min,delivering 18 polyselenoureas with high molecular weights(M_(w)s up to 94,600 g/mol)in high yields(up to 99%).Furthermore,the polyselenoureas could be used for the extraction of Au^(3+)from mixed-metal ion solutions under practical conditions with high selectivity,sensitivity(<1μg/L),efficiency(>99.99%),and capacity(up to 665.60 mg·Au^(3+)/g)within 1 min.Further,the elemental gold was recoverable after the pyrolysis of the polymer complexes.
基金supported by the National Natural Science Foundation of China(21978039)the Natural Science Foundation of Jiangsu Province(BK20221265,BK20211100)the Fundamental Research Funds for the Central Universities(DUT21YG133,DUT22YG224).
文摘The efficient utilization of elemental sulfur(S8) for developing high value-added chemicals is a global concern considering its abundant sources and yearly accelerating environmental issues. However, it has been a long-standing challenge to directly transform elemental sulfur to sulfur-containing polymer, especially via an environmentally benign manner. Herein, a unique chemo-differentiating multicomponent polymerization(MCP) of elemental sulfur, chloroform, and diamine is reported to construct polythiourea based on amine-involved two sequential reactions including isothiocyanation and nucleophilic addition.This strategy features isocynide-free monomers as starting materials, mild conditions, high molecular weights(up to72,900 g/mol) and desired yields(up to 83%). With the advantages of inactive isocyanation and active nucleophilic addition, the stoichiometric balance of amine and isothiocyanate could be delicately controlled to afford various polythioureas with high molecular weights. The polythioureas have been further utilized in the Cu-based aqueous catalysis and Hg-based ion adsorption.
基金supported by the National Natural Science Foundation of China(21978039)the Natural Science Foundation of Jiangsu Province(BK20221265,BK20211100)the Fundamental Research Funds for the Central Universities(DUT21YG133,DUT22YG224)。
文摘Polymers with metal coordination ability are outstanding precursors of nanocatalysts,attracting numerous attention in nanocatalysis area.It has been rarely reported for the poly(N-sulfonyl amidines)as macromolecular ligands for nanocatalysis.Herein,a catalyst-free multicomponent polymerization(MCP)strategy is developed to facilely prepare a library of amphiphilic poly(Nsulfonyl amidines)with zwitterionic properties starting from disulfonyl azide,hydrophilic dialdehyde and cyclic amino acids including proline and pipecolinic acid.Metals or additives can be thorougly avoided through this method.All the obtained polymers have well-defined structures,high yields and weight-average molecular weights(M_(w)s,up to 99,300 g/mol).The unique zwitterionic property,amphiphilicity and Cu(Ⅰ)coordination ability of the obtained poly(N-sulfonyl amidines)endow them to form the polymer-Cu(Ⅰ)complexes as nanocatalysts.Such nanocatalysts exhibit high catalytic efficiency in aqueous Cucatalyzed azide-alkyne cycloaddition(CuAAC)reaction at a low Cu(Ⅰ)loading of 50 ppm.Nanocatalysts with a high ratio of polymers to Cu(Ⅰ)have also been demonstrated with Cu(Ⅰ)stabilization ability.This work provides a“green”MCP method toward zwitterionic and amphiphilic poly(N-sulfonyl amidines),and highlights their unique potentials for nanocatalysis.
基金supported by the National Natural Science Foundation of China(21788102,22101028)the Research Grants Council of Hong Kong(16304819,16305320,C6014-20W)+3 种基金the Innovation and Technology Commission(ITC-CNERC14SC01)the Natural Science Foundation of Guangdong Province(2019B121205002)Shenzhen Key laboratory of Functional Aggregate Materials(ZDSYS20212021222400001)the Nissan Chemical Industries,Ltd.
文摘The development of a facile and efficient polymerization to prepare cyclopentadiene-containing polymers is of vital importance and highly desired. In this work, a metal-free multicomponent polymerization of activated diyne, electrophilic styrene and isocyanide for the preparation of highly substituted poly(cyclopentadiene) was established. Soluble and thermally stable polymers with high molecular weights are obtained in high yields under mild conditions. By introducing the tetraphenylethene or triphenylamine moiety into polymer backbones, the resultant polymers show unique aggregation-induced emission(AIE)characteristics. Interestingly, AIE polymers can also be generated in situ from non-AIE monomers. Moreover, the prepared polymers can generate photopatterns to function as photoresists and can also serve as visualizing agents to selectively stain the lipid droplets in live cells. This efficient polymerization will open up enormous opportunities for preparing functional cyclopentadiene-containing polymers applicable in diverse areas.
基金financially supported by the National Natural Science Foundation of China(nos.21788102,21490570,and 21490574)the Research Grant Council of Hong Kong(nos.16305618,16304819,N-HKUST609/19,C6009-17G,16102918,T21-604/19-R,and C6009-17G)+2 种基金the Innovation and Technology Commission(no.ITCCNERC14SC01)the Science and Technology Plan of Shenzhen(nos.JCYJ20160229205601482,JCYJ20170818113602462,JCYJ20180306180231853,and JCYJ 20180306174910791)the Natural Science Foundation of Guangdong Province(nos.2019B121205002 and 2019B030301003).
文摘Electron-deficient N-heteroaromatic polymers are crucial for the high-tech applications of organicmaterials,especially in the electronic and optoelectronic fields.Thus,the development of new polymerizations to afford adaptable electron-donating-accepting scaffolds in N-heteroaromatic polymers is in high demand.Herein,we have developed metal-free multicomponent polymerizations of diynes,diamines,and glyoxylates successfully for in situ generation of poly(quinoline)s with high molecular weights(Mw up to 16,900)in nearly quantitative yields.By tuning the electron distributions of the polymer backbones,the resulting poly(quinoline)s showed various aggregation-induced behaviors and photoresponsive abilities:The thin films of the poly(quinoline)s could be fabricated readily intowell-resolved photopatterns by photolithography techniques.They could be utilized as fluorescent probes to visualize themorphologies of polymer materials directly;these include spherulites and microphase separation of polymer blends.Their nanoparticles demonstrated sensitive and highly selective fluorescence quenching to hexavalent chromium ion Cr(Ⅵ),thereby providing access for biological imaging of Cr(Ⅵ)in unicellular algae.
基金supported by the Scientific Research Start-up Fund Project of Anhui Polytechnic University for Introducing Talents(No.2022YQQ081)Natural Science Research Project of the Anhui Educational Committee(No.2024AH050133)the National Natural Science Foundation of China(No.22101088)。
文摘Dimethyl sulfoxide(DMSO)possessing strong solvency and high boiling point is a very important aprotic polar solvent in organic and polymer synthesis.Notably,it is also a useful synthon in organic chemistry.However,the direct incorporation of DMSO in polymer synthesis remains challenging.In this work,DMSO was successfully converted to nitrogen-containing heterocyclic polymers as a monomer via multicomponent polymerizations(MCPs)with dialdehydes and diamines in the presence of K_(2)S_(2)O_(8)/t-BuOK at 120℃in 6 h.A series of poly(phenylquinoline)s with high M_(w)values(up to 5.11×10^(4))were obtained in satisfactory yields(up to 82%),performing good solubility,good thermal and morphological stability as well as excellent film-forming ability.The thin films of poly(phenylquinoline)s exhibit high refractive index value in a wide wavelength range of 400–1700 nm.Thus,this work not only enriches the family of MCPs but also provides an efficient strategy for the conversion of DMSO into functional polymeric materials that are potentially applicable in diverse areas.
基金supported by the National Natural Science Foundation of China(Nos.52173005,21788102 and 21822102)the Ministry of Science and Technology of China(No.2021YFA1501600)+1 种基金the Guangdong Provincial Key Laboratory of Luminescence from Molecular Aggregates(No.2019B030301003)the Fundamental Research Funds for the Central Universities.
文摘Multicomponent polymerizations(MCPs)are powerful tools to synthesize functional polymers with great structural diversity,low cost and high efficiency,which usually generate single polymer product.Herein,a robust one-pot diamines,CS_(2)and monoisocyanide-participated catalyst-free polymerization was developed at room temperature to produce polythiourea and thioformamide simultaneously in equal equivalent,which was featured with cheap monomers,simple operation and mild condition,affording various polythioureas with high Mws of up to 4.75×10^(4)g/mol in high yields of up to 98%.Polythioureas with varied chain composition and sequence-controlled structure could be synthesized in 62 g-scale from copolymerization or multicomponent tandem polymerization,enabling facile tuning of thermal property,crystallinity,mechanical property,and fluorescence.The abundant irregular hydrogen bonds endowed the polythioureas excellent glassy state self-healing property at room temperature or below 0℃.This polymerization provided an efficient and economic approach to access functional polythioureas.
基金financially supported by the National Natural Science Foundation of China(Nos.21788102,21525417,and 21490571)the Natural Science Foundation of Guangdong Province(Nos.2016A030312002 and 2019B030301003)the Innovation and Technology Commission of Hong Kong(ITCCNERC14S01)。
文摘Green monomers, such as carbon dioxide(CO_(2)), are closely related to our daily life and highly desirable to be transferred to functional polymers with diverse structures and versatile properties because they are abundant, cheap, nontoxic, renewable, and sustainable. However, the polymerizations based on these green monomers are to be further developed. In this work, a facile CO_(2) and alkyne-based one-pot, two-step, fourcomponent tandem polymerization was successfully established. The polymerization of CO_(2), diynes, alkyl dihalides, and primary/secondary amines can proceed under mild reaction conditions and regio-and stereoregular poly(aminoacrylate)s with good solubility and thermal stability were obtained in high yields(up to 95%). Notably, distinctly different stereoregularity of resultant poly(aminoacrylate)s was realized via using primary or secondary amines. Using the former would readily generate polymers with 100% Z-isomers, whereas the latter furnished products with over 95% E-isomers. Through different monomer combination, the polymers with tunable structures and properties were obtained.Moreover, the tetraphenylethene units containing poly(aminoacrylate)s, showing the unique aggregation-induced emission characteristics,could function as a fluorescent probe for sensitive explosive detection. Thus, this work not only develops a facile CO_(2) and alkyne-based multicomponent tandem polymerization but also provides a valuable strategy to fine-tune the polymer structures and properties, which could be potentially applied in diverse areas.
基金supported by the National Natural Science Foundation of China(22431004 and 22101088)the Fund of Guangdong Provincial Key Laboratory of Luminescence from Molecular Aggregates(2023B1212060003)+1 种基金the Innovation and Technology Commission of Hong Kong(ITC-CNERC14SC01)the State Key Lab of Luminescent Materials and Devices,South China University of Technology(Skllmd-2024-19).
文摘Water,characterized by its safety,abundance,low cost,and sustainability,has garnered increasing attention in polymer synthesis.It has been utilized as a solvent or a comonomer in polymerizations based on triple-bond building blocks for the construction of functional polymers.Currently,distinct progress has been made;however,no such review was presented.This Review aims to summarize the progress in alkyne-based polymerizations in aqueous media with the“on-water”effect,water-involved alkyne-based polymerizations,and water-involved isocyanide-based polymerizations.The catalyst systems,reaction conditions,post-modification strategies,and the properties and applications of the resulting polymers are summarized.Furthermore,the challenges and opportunities in this field are briefly discussed.
基金supported by the National Natural Science Foundation of China(51273187,21374107)the Fundamental Research Funds for the Central Universities(WK2060200012)the Program for New Century Excellent Talents in Universities(NCET-11-0882)
文摘Multicomponent polymerizations have become powerful tools for the construction of sequence-defined polymers. Although the Passerini multicomponent reaction has been widely used in the synthesis of sequence-defined polymers, the tandem usage of the Passerini multicomponent reaction and other multicomponent reactions in one-pot for the synthesis of sequence-defined polymers has not been developed until now. In this contribution, we report the tandem usage of the Passerini three-component reaction and the three-component amine-thiol-ene conjugation reaction in one pot for the synthesis of sequence-defined polymers. The Passerini reaction between methacrylic acid, adipaldehyde, and 2-isocyanobutanoate was carried out, affording a new molecule containing two alkene units. Subsequently, an amine and a thiolactone were added to the reaction system, whereupon the three-component amine-thiol-ene conjugating reaction occurred to yield a sequence-defined polymer. This method offers more rapid access to sequence-defined polymers with high molecular diversity and complexity.
基金supported by the National Science Foundation of China(No.21978039)Special Funds of the Central Government Guiding Local Science and Technology Development(Nos.2021JH6/10500148 and 2021JH6/10500146)+1 种基金the Natural Science Foundation of Jiangsu Province(No.BK20211100)and the Fundamental Research Funds for the Central Universities(Nos.DUT20YG120 and DUT21YG133).
文摘Chiral-polymers with metal-coordination ability showgreat potential formediating asymmetric reactions.However,the synthesis of structurally diverse chiral polymers remains a great challenge,especially doing so efficiently.Herein,four types of Cucatalyzed multicomponent asymmetric polymerizationswere developed using a flexible combination of OBoc-alkyne.
