The great achievements of click chemistry have encouraged polymer scientists to use this reaction in their field. This review assembles an update of the advances of using azide-alkyne click polymerization to prepare f...The great achievements of click chemistry have encouraged polymer scientists to use this reaction in their field. This review assembles an update of the advances of using azide-alkyne click polymerization to prepare functional polytriazoles（PTAs） with linear and hyperbranched structures.The Cu（I）-mediated click polymerization furnishes 1,4-regioregular PTAs,whereas,the metal-free click polymerization of propiolates and azides produces PTAs with 1,4-regioisomer contents up to 90%.The PTAs display advanced functions,such as aggregation-induced emission,thermal stability,biocompatibility and optical nonlinearity.展开更多
Azide-alkyne click polymerization has become a powerful tool for polymer synthesis.However,the click polymerization between internal alkynes and azides is rarely utilized to prepare functional polymers.In this work,th...Azide-alkyne click polymerization has become a powerful tool for polymer synthesis.However,the click polymerization between internal alkynes and azides is rarely utilized to prepare functional polymers.In this work,the polymerization reactions of activated internal alkyne monomers of tris(2-butynoate)s(1)with tetraphenylethene-containing diazides(2)were performed in dimethylformamide(DMF)under simple heating,affording four hyperbranched poly(methyltriazolylcarboxylate)s(hb-PMTCs)with high molecular weights(A4W up to 2.4 x 104)and regioregularities(up to 83.9%)in good yields.The hb-PMTCs are soluble in common organic solvents,and thermally stable with 5%weight loss temperatures up to 400℃.They are non-emissive in dilute solution,but become highly emissive in aggregated state,exhibiting aggregationinduced emission characteristics.The polymers can generate fluorescent photopatterns with high resolution,and can work as fluorescent sensors to detect nitroaromatic explosive with high sensitivity.展开更多
Regioseletive 1,3-dipolar polycycloadditions of 4,4'-isopropylidenediphenyl dipropiolate (1) and tetraphenylethene (TPE)-containing diazides (2) are carried out in polar solvents such as DMF/toluene at a moderate ...Regioseletive 1,3-dipolar polycycloadditions of 4,4'-isopropylidenediphenyl dipropiolate (1) and tetraphenylethene (TPE)-containing diazides (2) are carried out in polar solvents such as DMF/toluene at a moderate temperature of 100℃ for 6 h,producing poly(aroxycarbonyltriazole)s (PACTs) P3 with high molecular weights (Mw up to 23900) and regioregularities (F1,4 up to ～90%) in high yields (up to ～99%).These metal-free click polymerizations can propagate smoothly in an open atmosphere without protection from oxygen and moisture.The obtained polymers are soluble in common organic solvents and thermally stable at temperatures up to 375℃.Thanks to their contained TPE moieties,the PACTs show aggregation-induced emission and can serve as fluorescent chemosensors for superamplified detection of explosives.展开更多
The last decade has witnessed the quick develop of self-healing materials. As a newborn strategy, the alternative of irreversible covalent bond formation is, however, to be further developed. In this paper, self-heali...The last decade has witnessed the quick develop of self-healing materials. As a newborn strategy, the alternative of irreversible covalent bond formation is, however, to be further developed. In this paper, self-healing hyperbranched poly(aroxycarbonyltriazole)based on such mechanism were prepared by our developed metal-free click polymerization of simplified dipropiolate and triazide. Thanks to their excellent processability and film-forming ability, high quality homogeneous films free from defects were obtained by casting. The cut films could be healed by stacking or pressing the halves together at room temperature and elevated temperature. Thus, this design concept for self-healing materials should be generally applicable to other hyperbranched polymers with reactive groups on their peripheries.展开更多
Alkyne-based click polymerizations have been nurtured into a powerful synthetic technique for the preparation of new polymers with advanced structures and versatile properties.Among them,the emerging thiol-yne,hydroxy...Alkyne-based click polymerizations have been nurtured into a powerful synthetic technique for the preparation of new polymers with advanced structures and versatile properties.Among them,the emerging thiol-yne,hydroxyl-yne,and amino-yne click polymerizations have made remarkable progress from reactions to applications.These polymerizations avoid the usage of inherently dangerous monomers and are safer to operate than the classical azide-alkyne click polymerization(AACP),making them more prospective for diverse applications.To greatly promote the new alkyne-based click polymerizations beyond AACP,a new concept of“X-yne click polymerization”is proposed to unify them,where“X”denotes the monomers that can react with alkynes under mild reaction conditions,including thiols,alcohols,amines,and other promising ones.In this review,we mainly present a brief account of the progress of X-yne click polymerization and discuss in detail the challenges and opportunities in this field.展开更多
An air-stable supported Cu(I) catalyst, Cu I@PS-Phen, was designed and synthesized. Cu I@PS-Phen can efficiently catalyze the click polymerization of diynes a and diazides b to produce soluble and thermally stable pol...An air-stable supported Cu(I) catalyst, Cu I@PS-Phen, was designed and synthesized. Cu I@PS-Phen can efficiently catalyze the click polymerization of diynes a and diazides b to produce soluble and thermally stable polytriazoles with high molecular weights(Mw up to 30800), and low copper residue content(down to 190 ppm) in high yields(up to 94.2%) under mild reaction conditions without the exclusion of oxygen.展开更多
It has been a challenge to synthesize high molecular weight and soluble conjugated hyperbranched poly（1,2,3-triazole）s （hb-PTAs）. In this paper a series of soluble hyperbranched polytriazoles, whose num- ber-avera...It has been a challenge to synthesize high molecular weight and soluble conjugated hyperbranched poly（1,2,3-triazole）s （hb-PTAs）. In this paper a series of soluble hyperbranched polytriazoles, whose num- ber-average molecular weight （Mn） and polydispersity index ranged in （1.2--3.3）× 104 and 1.7--3.0, respectively, were synthesized with A2 d-B3 approach. In the polymerization process, diazides A1--A4 and triyne B1 were used as A2 and B3 monomers; Cu（I）-catalyst, THF and water were used as their reaction system. At room temperature the final molecular weight could be controlled through reaction time, so finally we obtained soluble conjugated hyper- branched poly（1,2,3-triazole）s hb-PTAs （1--4）. The polymers were soluble in common organic solvents, and all emitted blue light; the films of polymers emitted yellow and blue light, due to the difference in the aggregation of their chromophoric units in the solid state. The thermal properties of the final copolymers were analyzed by differ- ential scanning calorimetry （DSC） and thermogravimetric analysis （TGA）.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
Organic reactions in water have attracted great attention due to their advantages such as unique reaction performance and environmental friendliness.Organic reactions as well as polymerizations in aqueous media have b...Organic reactions in water have attracted great attention due to their advantages such as unique reaction performance and environmental friendliness.Organic reactions as well as polymerizations in aqueous media have been extensively investigated,and so far,there has been a massive amount of reporting about polymerizations in water.However,reports about click polymerization in water have been rare.Herein,click polymerization of activated alkyne and aromatic amine in aqueous media is developed.The“on water”effect facilitates polymerization in aqueous media better than in organic solvents,and its mechanism is deciphered through experimental data and theoretical calculations.Water participates in the reaction and reduces the energy barrier to some extent.Besides,polymerization makes it possible for aromatic amine with low reactivity to be linked.By using this strategy,polymers with high molecular weights can be obtained in high yields(up to 95.4%).They show good thermal stability and high refractivity.They can be photodegraded.The polymers with tetraphenylethylene moieties show aggregation-induced emission and can be used as materials for generating photopatterns and visualizing agents for specific staining of lysosome in living cells.展开更多
Achieving the linear polymers with high molecular weight via step-growth polymerization of A2 and B2 monomers is significantly limited by the requirement of strict stoichiometry of two monomers when the reactivity of ...Achieving the linear polymers with high molecular weight via step-growth polymerization of A2 and B2 monomers is significantly limited by the requirement of strict stoichiometry of two monomers when the reactivity of A and B groups are not changed during the polymerization.Herein,a unique step-growth polymerization based on copper-catalyzed azide-alkyne cycloaddition(CuAAC)with reactionenhanced reactivity of intermediate(RERI)mechanism was developed for the preparation of mainchain semifluorinated polymers with high molecular weight.The CuAAC polymerization of bis-alkynyl-terminated fluorinated monomers(A2)and 2,2-bis(azidomethyl)propane-1,3-diyl bis(2-methylpropanoate)(BiAz,B2)with RERI effect at different stoichiometric ratio was systematically investigated.The results indicated that the semifluorinated polymers with ultrahigh molecular weight,Mw,MALLS>106 g/mol,could be efficiently synthesized by using excess molar of BiAz monomers.The resultant high-molecular-weight semifluorinated polymers show good thermostability and high hydrophobicity.In addition,the glass transition temperature(Tg)of these mainchain semifluorinated polymers could be tuned conveniently due to the bis-alkynyl-terminated comonomers could be consumed completely when excessive BiAz monomers were used in this this step-growth polymerization.展开更多
基金partially supported by the National Natural Science Foundation of China(Nos.50703033,20974098 and 20974028)the Ministry of Science and Technology of China(2009CB623605)+1 种基金the Research Grants Council of Hong Kong (603509,HKUST2/CRF/10)the University Grants Committee of Hong Kong(AoE/P-03/08)
文摘The great achievements of click chemistry have encouraged polymer scientists to use this reaction in their field. This review assembles an update of the advances of using azide-alkyne click polymerization to prepare functional polytriazoles（PTAs） with linear and hyperbranched structures.The Cu（I）-mediated click polymerization furnishes 1,4-regioregular PTAs,whereas,the metal-free click polymerization of propiolates and azides produces PTAs with 1,4-regioisomer contents up to 90%.The PTAs display advanced functions,such as aggregation-induced emission,thermal stability,biocompatibility and optical nonlinearity.
基金the National Natural Science Foundation of China(Nos.21875152 and 21404077)the Natural Science Foundation of the Jiangsu Higher Education Institutions of China(No.17KJB150034)+3 种基金the Open Fund of Guangdong Provincial Key Laboratory of Luminescence from Molecular Aggregates,Guangzhou 510640,China(South China University of Technology)(No.2019B030301003)the Priority Academic Program Development of Jiangsu High Education Institutions(PAPD).M.N.L.and Q.Z.Z.thank the financial support from Undergraduate Training Program for Innovation and Entrepreneurship,Soochow University(No.2018xj032)H.K.L.acknowledges the supports from Jiangsu Planned Projects for Postdoctoral Research Funds(No.1501023B)China Postdoctoral Science Foundation(No.2016M591906).
文摘Azide-alkyne click polymerization has become a powerful tool for polymer synthesis.However,the click polymerization between internal alkynes and azides is rarely utilized to prepare functional polymers.In this work,the polymerization reactions of activated internal alkyne monomers of tris(2-butynoate)s(1)with tetraphenylethene-containing diazides(2)were performed in dimethylformamide(DMF)under simple heating,affording four hyperbranched poly(methyltriazolylcarboxylate)s(hb-PMTCs)with high molecular weights(A4W up to 2.4 x 104)and regioregularities(up to 83.9%)in good yields.The hb-PMTCs are soluble in common organic solvents,and thermally stable with 5%weight loss temperatures up to 400℃.They are non-emissive in dilute solution,but become highly emissive in aggregated state,exhibiting aggregationinduced emission characteristics.The polymers can generate fluorescent photopatterns with high resolution,and can work as fluorescent sensors to detect nitroaromatic explosive with high sensitivity.
基金supported by the National Natural Science Foundation of China (20634020,50703033,20974098 and 20974028)the Ministry of Science and Technology of China (2009CB623605)+4 种基金the University Grants Committee of Hong Kong ( AoE/P-03/08)the Research Grants Council of Hong Kong (603509,601608 and 602707)the Innovation and Technology Fund of Hong Kong (ITS/168/09). A.J.Q. and B.Z.T acknowledge the supports from the Postdoctoral Research Foundation of China (20081461)the Fundamental Research Funds for the Central Universities (2010KYJD005)the CAO GuangBiao Foundation of Zhejiang University,respectively
文摘Regioseletive 1,3-dipolar polycycloadditions of 4,4'-isopropylidenediphenyl dipropiolate (1) and tetraphenylethene (TPE)-containing diazides (2) are carried out in polar solvents such as DMF/toluene at a moderate temperature of 100℃ for 6 h,producing poly(aroxycarbonyltriazole)s (PACTs) P3 with high molecular weights (Mw up to 23900) and regioregularities (F1,4 up to ～90%) in high yields (up to ～99%).These metal-free click polymerizations can propagate smoothly in an open atmosphere without protection from oxygen and moisture.The obtained polymers are soluble in common organic solvents and thermally stable at temperatures up to 375℃.Thanks to their contained TPE moieties,the PACTs show aggregation-induced emission and can serve as fluorescent chemosensors for superamplified detection of explosives.
基金supported by the National Natural Science Foundation of China(21525417,21490571,21222402)the key project of the Ministry of Science and Technology of China(2013CB834702)+2 种基金the National Program for Support of Top-Notch Young Professionals,the Fundamental Research Funds for the Central Universities(2015ZY013)the Innovation and Technology Commission of Hong Kong(ITC-CNERC14SC01)support from Guangdong Innovative Research Team Program(201101C0105067115)
文摘The last decade has witnessed the quick develop of self-healing materials. As a newborn strategy, the alternative of irreversible covalent bond formation is, however, to be further developed. In this paper, self-healing hyperbranched poly(aroxycarbonyltriazole)based on such mechanism were prepared by our developed metal-free click polymerization of simplified dipropiolate and triazide. Thanks to their excellent processability and film-forming ability, high quality homogeneous films free from defects were obtained by casting. The cut films could be healed by stacking or pressing the halves together at room temperature and elevated temperature. Thus, this design concept for self-healing materials should be generally applicable to other hyperbranched polymers with reactive groups on their peripheries.
基金National Natural Science Foundation of China,Grant/Award Numbers:21788102,21525417Natural Science Foundation of Guangdong Province,Grant/Award Numbers:2019B030301003,2016A030312002Innovation and Technology Commission of Hong Kong,Grant/Award Number:ITC-CNERC14SC01。
文摘Alkyne-based click polymerizations have been nurtured into a powerful synthetic technique for the preparation of new polymers with advanced structures and versatile properties.Among them,the emerging thiol-yne,hydroxyl-yne,and amino-yne click polymerizations have made remarkable progress from reactions to applications.These polymerizations avoid the usage of inherently dangerous monomers and are safer to operate than the classical azide-alkyne click polymerization(AACP),making them more prospective for diverse applications.To greatly promote the new alkyne-based click polymerizations beyond AACP,a new concept of“X-yne click polymerization”is proposed to unify them,where“X”denotes the monomers that can react with alkynes under mild reaction conditions,including thiols,alcohols,amines,and other promising ones.In this review,we mainly present a brief account of the progress of X-yne click polymerization and discuss in detail the challenges and opportunities in this field.
基金supported by the National Natural Science Foundation of China(21490571,21222402,21174120)the Key Project of the Ministry of Science and Technology of China(2013CB834702)+1 种基金the Research Grants Council of Hong Kong(604711,602212,604913)Anjun Qin and Benzhong Tang thank the support from Guangdong Innovative Research Team Program(201101C0105067115)
文摘An air-stable supported Cu(I) catalyst, Cu I@PS-Phen, was designed and synthesized. Cu I@PS-Phen can efficiently catalyze the click polymerization of diynes a and diazides b to produce soluble and thermally stable polytriazoles with high molecular weights(Mw up to 30800), and low copper residue content(down to 190 ppm) in high yields(up to 94.2%) under mild reaction conditions without the exclusion of oxygen.
文摘It has been a challenge to synthesize high molecular weight and soluble conjugated hyperbranched poly（1,2,3-triazole）s （hb-PTAs）. In this paper a series of soluble hyperbranched polytriazoles, whose num- ber-average molecular weight （Mn） and polydispersity index ranged in （1.2--3.3）× 104 and 1.7--3.0, respectively, were synthesized with A2 d-B3 approach. In the polymerization process, diazides A1--A4 and triyne B1 were used as A2 and B3 monomers; Cu（I）-catalyst, THF and water were used as their reaction system. At room temperature the final molecular weight could be controlled through reaction time, so finally we obtained soluble conjugated hyper- branched poly（1,2,3-triazole）s hb-PTAs （1--4）. The polymers were soluble in common organic solvents, and all emitted blue light; the films of polymers emitted yellow and blue light, due to the difference in the aggregation of their chromophoric units in the solid state. The thermal properties of the final copolymers were analyzed by differ- ential scanning calorimetry （DSC） and thermogravimetric analysis （TGA）.
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(grant nos.21788102 and 22101028)the Research Grants Council of Hong Kong(grant nos.16304819,16305320,and C6014-20W)+3 种基金the Innovation and Technology Commission(grant no.ITC-CNERC14SC01)the Natural Science Foundation of Guangdong Province(grant no.2019B121205002)the China Postdoctoral Science Foundation(grant no.2021M691414)the Scientific and Technological Innovation Team of Shaanxi Province(grant no.2022TD-36).
文摘Organic reactions in water have attracted great attention due to their advantages such as unique reaction performance and environmental friendliness.Organic reactions as well as polymerizations in aqueous media have been extensively investigated,and so far,there has been a massive amount of reporting about polymerizations in water.However,reports about click polymerization in water have been rare.Herein,click polymerization of activated alkyne and aromatic amine in aqueous media is developed.The“on water”effect facilitates polymerization in aqueous media better than in organic solvents,and its mechanism is deciphered through experimental data and theoretical calculations.Water participates in the reaction and reduces the energy barrier to some extent.Besides,polymerization makes it possible for aromatic amine with low reactivity to be linked.By using this strategy,polymers with high molecular weights can be obtained in high yields(up to 95.4%).They show good thermal stability and high refractivity.They can be photodegraded.The polymers with tetraphenylethylene moieties show aggregation-induced emission and can be used as materials for generating photopatterns and visualizing agents for specific staining of lysosome in living cells.
基金financially supported by the National Natural Science Foundation of China(No.22071271)。
文摘Achieving the linear polymers with high molecular weight via step-growth polymerization of A2 and B2 monomers is significantly limited by the requirement of strict stoichiometry of two monomers when the reactivity of A and B groups are not changed during the polymerization.Herein,a unique step-growth polymerization based on copper-catalyzed azide-alkyne cycloaddition(CuAAC)with reactionenhanced reactivity of intermediate(RERI)mechanism was developed for the preparation of mainchain semifluorinated polymers with high molecular weight.The CuAAC polymerization of bis-alkynyl-terminated fluorinated monomers(A2)and 2,2-bis(azidomethyl)propane-1,3-diyl bis(2-methylpropanoate)(BiAz,B2)with RERI effect at different stoichiometric ratio was systematically investigated.The results indicated that the semifluorinated polymers with ultrahigh molecular weight,Mw,MALLS>106 g/mol,could be efficiently synthesized by using excess molar of BiAz monomers.The resultant high-molecular-weight semifluorinated polymers show good thermostability and high hydrophobicity.In addition,the glass transition temperature(Tg)of these mainchain semifluorinated polymers could be tuned conveniently due to the bis-alkynyl-terminated comonomers could be consumed completely when excessive BiAz monomers were used in this this step-growth polymerization.
