A series of hyperbranched poly(amine-ester)polyols were synthesized by the polycondensation of N,N-diethylol-3-amine-methylpropionate(prepared by Michael addition reaction of methyl acrylate with diethanolamine)as an ...A series of hyperbranched poly(amine-ester)polyols were synthesized by the polycondensation of N,N-diethylol-3-amine-methylpropionate(prepared by Michael addition reaction of methyl acrylate with diethanolamine)as an AB2-type monomer with trimethylol propane as the core moiety,proceeding in one-step procedure in the melt with p-toluenesulfonic acid as catalyst.The obtained monomer and polymers were characterized by FTIR and 1H-NMR spectroscopy.The solubility and surface activity in aqueous solution of the polymers were also examined.The gas permeability,water vapor permeability,and moisture absorption of microfiber synthetic leather treated by hyperbranched polymer were studied.The optimum conditions were that the dosage of dye and hyperbranched polymer was 5% and 10%,respectively.The water vapor permeability and moisture absorption of microfiber synthetic leather reached to 0.525 4 mg/(10 cm2·24 h)and 0.046 7 mg/(10 cm2·24 h).Compared with blank samples,they increased by 15% and 35%,respectively.However,the dosage of hyperbranched polymer has little influence on gas permeability of microfiber synthetic leather.SEM results show that the fiber of microfiber synthetic leather treated by hyperbranched polymer is incompact.展开更多
Recent advances in organic electronics of novel materials and optoelectronic devices spark great interest in the design and synthesis of high-performance polymer semiconductors. During the last decade, isoindigo(ⅡD) ...Recent advances in organic electronics of novel materials and optoelectronic devices spark great interest in the design and synthesis of high-performance polymer semiconductors. During the last decade, isoindigo(ⅡD) and its derivatives have sprung up as common electron-deficient building blocks and obtained extensive applications in organic field-effect transistors(OFETs).In this review, we first present the current status, basic principles, and general material design strategies for OFETs. Then,multiple ⅡD-type acceptors, mature synthetic routes to monomers, and typical ⅡDs-based conjugated polymers are summarized.We also introduce side-chain engineering and cutting-edge applications, like stretchable transistors, sensing, active-matrix driving, etc., of the classic copolymer poly(isoindigo-co-bithiophene). Green polymerization approaches towards conjugated polymers incorporating ⅡDs are subsequently discussed for efficient polymerization. Finally, we conclude this review and propose in-depth prospects with respect to material synthesis and device applications. Undoubtedly, ⅡDs-based conjugated polymers would occupy a significant position in the future of organic electronics, due to diverse building blocks, mature synthetic pathways, tunable side chains, and unique optoelectronic properties.展开更多
Hyperbranched polymer structures represent a class of high-functionality building blocks with excellent three-dimensional topology for the construction of highly substituted conjugated polymers.In this contribution,an...Hyperbranched polymer structures represent a class of high-functionality building blocks with excellent three-dimensional topology for the construction of highly substituted conjugated polymers.In this contribution,an efficient microwave synthesis protocol toward the synthesis of conjugated hyperbranched polymers is presented.A novel series of soluble hyperbranched polyfluorenes (PTF1-PTF3) incorporating triazatruxene moiety as the branch units with various branching degrees have thus been successfully constructed with good yields and high molecular weight via a facile "A2+B2+C3" approach.The structures of the hyperbranched polymers were confirmed by NMR and GPC.Their thermal,optical,and electrochemical properties of the hyperbranched polymers were also investigated.The results showed that introduction of triazatruxene units into the hyperbranched structure endowed the polymer with good thermal stability and highly amorphous properties.Photophysical investigation of PTFx revealed strong blue emission in both solution and solid states.Hyperbranched polymers with higher degree of branching and proper content of linear fluorene units exhibited better photophysical properties in terms of narrow emission spectra and relatively high quantum efficiency as well as improved thermal spectral stability.The triazatruxene branching unit also played a role in raising the HOMO energy levels relative to those of polyfluorenes that would help to improve the charge injection and transport properties.The incorporation of triazatruxene unit into hyperbranched polymers has thus explored an effective avenue for constructing optoelectronic polymers with improved functional characteristics.展开更多
A new type of dendritic polymer, named dendronized hyperbranched polymer (DHP), was prepared successfully by the macro-monomer approach. Thanks to the perfect 3D isolation effects, DHPG1 exhibited good NLO property wi...A new type of dendritic polymer, named dendronized hyperbranched polymer (DHP), was prepared successfully by the macro-monomer approach. Thanks to the perfect 3D isolation effects, DHPG1 exhibited good NLO property with d 33 value of 133 pm/V, higher than its analogues of dendronized polymer and dendrimer, and its stability of NLO effect was also enhanced.展开更多
Thanks to their remarkable mechanical, electrical, thermal, and barrier properties, graphene-based nanocomposites have been a hot area of research in the past decade. Because of their simple top-down synthesis, graphe...Thanks to their remarkable mechanical, electrical, thermal, and barrier properties, graphene-based nanocomposites have been a hot area of research in the past decade. Because of their simple top-down synthesis, graphene oxide (GO) and reduced graphene oxide (rGO) have opened new possibilities for gas barrier, membrane separation, and stimuli-response characteristics in nanocomposites. Herein, we review the synthesis techniques most commonly used to produce these graphene derivatives, discuss how synthesis affects their key material properties, and highlight some examples of nanocomposites with unique and impressive properties. We specifically highlight their performances in separation applications, stimuli-responsive materials, anti-corrosion coatings, and energy storage. Finally, we discuss the outlook and remaining challenges in the field of practical industrial-scale production and use of graphene-derivative-based polymer nanocomposites.展开更多
A series of amphiphilic hyperbranched polymers(AHP-s,the“s”refers to the algebra of AHP)were synthesized by the reaction between hydroxyl-terminated hyperbranched polymers(HBP-s,the“s”refers to the algebra of HBP)...A series of amphiphilic hyperbranched polymers(AHP-s,the“s”refers to the algebra of AHP)were synthesized by the reaction between hydroxyl-terminated hyperbranched polymers(HBP-s,the“s”refers to the algebra of HBP)and palmitoyl chloride.FTIR,NMR and GPC were used to determine the structure of AHP-s,the results showed that AHP-s exhibits core-shell structure.The thermal properties of polymers were investigated by DSC and TGA.It was found that AHP-2,AHP-3 and AHP-4 display higher thermal stability than AHP-1(AHP-1,AHP-2,AHP-3 and AHP-4 represent the first,second,third and fourth generation AHP,respectively).Furthermore,the self-assembly performance of AHP-s in THF solvent was investigated by TEM and SEM.Finally,the encapsulation capacity of the AHP-s for methyl orange(MO)was explored at different concentrations of AHP-s and pH conditions.It was found that AHP-s is capable of accommodating hydrophilic guest MO.Moreover,the higher generation of AHP-s,the stronger encapsulation capacity obtained.And the encapsulation capacity closely associated with the pH of encapsulation system.展开更多
1 Results UV curing systems have been widely used in various industries such as coatings,printing inks,and photo-resists,because of their low volatile organic compound (VOC),excellent physical properties,and energy sa...1 Results UV curing systems have been widely used in various industries such as coatings,printing inks,and photo-resists,because of their low volatile organic compound (VOC),excellent physical properties,and energy saving.Recently,these systems have also been applied to electronics and information technology fields such as display,CD,DVD,optical-fiber,and optical-device. In these curing systems,(meth)acrylate oligomers are mainly used due to their high photochemical reactivity. Recently,dendritic polyme...展开更多
Through a controllable“reactivate””graft”synthetic route,two asymmetrical“Janus”dendronized polymers(DPs)were successfully synthesized.Dendrons were grafted to a linear polymer motherboard by a story-by-story co...Through a controllable“reactivate””graft”synthetic route,two asymmetrical“Janus”dendronized polymers(DPs)were successfully synthesized.Dendrons were grafted to a linear polymer motherboard by a story-by-story constructionmethod.Due to the heterogenetic“Janus”structure,with orderly arranged chromophore moieties,the polymers demonstrated extremely large second-order nonlinear optical(NLO)coefficients and excellent NLO thermal stability.DP-4l and DP-6l had high d33 values of 232 and 227 pm/V,respectively,which reached the highest value reported so far for linear-based polymers containing simple azo-chromophore moieties.The controllable synthesis sheds light on the structure–property relationships of NLO polymers and other dendronized-structure functional polymers.展开更多
Large nonlinear optical(NLO) coefficient and good stability, two essential factors to evaluate second-order NLO materials, are difficult to be achieved in one molecule simultaneously. Herein, by utilizing the concept ...Large nonlinear optical(NLO) coefficient and good stability, two essential factors to evaluate second-order NLO materials, are difficult to be achieved in one molecule simultaneously. Herein, by utilizing the concept of "isolation chromophore", "isolation group" and dendritic structure, a dendritic molecule D-NS and a dendronized hyperbranched polymer DHP-NS are prepared to investigate their structure-property relationship. For the small dendritic molecule D-NS, it exhibits a high d33 value of 140 pm/V.But this value can be easily dropped when the temperature is higher than 50 °C, which extremely limits its real application. After introducing D-NS into a dendronized hyperbranched polymer chains, the obtained DHP-NS also shows a high d33 value of101 pm/V, but much better stability than D-NS. Even when its thin film was heated to 120 °C, no obvious decay can be observed in the d33 value of DHP-NS. This work demonstrates an effective strategy to realize both large NLO effect and good stability simultaneously.展开更多
In recent decades,the continuous depletion of fossil fuels and the increasingly serious environmental issue have aroused wide attention on the development of biopolymers based on renewable biomass.Lignin is the second...In recent decades,the continuous depletion of fossil fuels and the increasingly serious environmental issue have aroused wide attention on the development of biopolymers based on renewable biomass.Lignin is the second most abundant organic bio-based macromolecule second to cellulose,and it can be widely found in plants.Furthermore,various phenol derivatives can be obtained by their depolymerization processes.The development of bio-renewable polymeric materials originating from lignin-derivative phenol monomers,such as vanillin,syringaldehyde,eugenol,vanillyl alcohol,vanillic acid,and ferulic acid,will not only valorize the bio-sourced materials but also effectively reduce petroleum resource consumption and mitigate the environmental pollution.Therefore,an updated overview of the synthesis processes of these bio-based polymers developed in the past decade,which includes both thermosets and thermoplastics such as epoxy,phenolic,polyimine,polybenzoxazine,polyurethane,and polyesters,are elucidated.In addition,the applications of these bio-based polymers and their composites in flame-retarded materials,degradable and reprocessable materials,dielectric materials,optoelectronic materials,as well as smart responsive materials are also intensively discussed.In line with the gradual development of synthesis technologies,we believe that derivatives of lignin will turn into one of the most promising materials to be considered for the preparation of high-performance and functional bio-based polymer materials.展开更多
Polyamides containing thieno[2,3-b]thiophene moiety were prepared via a simple polycondensation reaction of the diaminothieno[2,3-b]thiophene monomer la with different kinds of diacid chlorides (including oxalyl, adi...Polyamides containing thieno[2,3-b]thiophene moiety were prepared via a simple polycondensation reaction of the diaminothieno[2,3-b]thiophene monomer la with different kinds of diacid chlorides (including oxalyl, adipoyl, sebacoyl, isophthaloyl, terephthaloyl, 4,4'-azodibenzoyl, 3,3'-azodibenzoyl, p-phenylene diacryloyl) in the presence of LiC1 and NMP as a solvent through lowtemperature solution polycondensation. The chemical structures of model compound and synthesized polyamides were confirmed by FTIR, nuclear magnetic resonance spectroscopy (including 1 H-NMR and 13 C-NMR) and elemental analysis. In addition, the thermal stability, crystallinity structure and surface morphology of synthesized polyamides were characterized via thermogravametric analysis (TGA), wide-angle X-ray diffraction analysis (WAXD) and scanning electron microscopy (SEM). Also, the corrosion inhibition behavior of selected examples ofpolyamides was investigated; the inhibitive effect of the investigated polymers for carbon steel in 1.0 mol'L-1 HCI was studied using potentiodynamic polarization (PDP) and electrochemical impedance spectroscopy (EIS) methods. PDP results displayed that the polyamides containing thieno[2,3-b]thiophene moiety can be as mixed-type inhibitors. The inhibition efficiency (P, %) was found to be in the range from 67.13% to 96.01%. There is an increase in P by the synthesized polymers in comparison to the starting monomer. The adsorption of these polymers was found to obey Langmuir adsorption isotherm.展开更多
基金National High Technology Research and Development Program of China(863program)(No.200803Z309)Optional Item of Shaanxi University of Science and Technology,China(No.ZX08-06)National Natural Science Foundation of China(No.20876090)
文摘A series of hyperbranched poly(amine-ester)polyols were synthesized by the polycondensation of N,N-diethylol-3-amine-methylpropionate(prepared by Michael addition reaction of methyl acrylate with diethanolamine)as an AB2-type monomer with trimethylol propane as the core moiety,proceeding in one-step procedure in the melt with p-toluenesulfonic acid as catalyst.The obtained monomer and polymers were characterized by FTIR and 1H-NMR spectroscopy.The solubility and surface activity in aqueous solution of the polymers were also examined.The gas permeability,water vapor permeability,and moisture absorption of microfiber synthetic leather treated by hyperbranched polymer were studied.The optimum conditions were that the dosage of dye and hyperbranched polymer was 5% and 10%,respectively.The water vapor permeability and moisture absorption of microfiber synthetic leather reached to 0.525 4 mg/(10 cm2·24 h)and 0.046 7 mg/(10 cm2·24 h).Compared with blank samples,they increased by 15% and 35%,respectively.However,the dosage of hyperbranched polymer has little influence on gas permeability of microfiber synthetic leather.SEM results show that the fiber of microfiber synthetic leather treated by hyperbranched polymer is incompact.
基金supported by the National Natural Science Foundation of China (61890940)the National Key R&D Programof “Key Scientific Issues of Transformative Technology” (2018YFA0703200)the CAS-Croucher Funding Scheme for Joint Laboratories and the Chinese Academy of Sciences Research Program (121111KYSB20200036)。
文摘Recent advances in organic electronics of novel materials and optoelectronic devices spark great interest in the design and synthesis of high-performance polymer semiconductors. During the last decade, isoindigo(ⅡD) and its derivatives have sprung up as common electron-deficient building blocks and obtained extensive applications in organic field-effect transistors(OFETs).In this review, we first present the current status, basic principles, and general material design strategies for OFETs. Then,multiple ⅡD-type acceptors, mature synthetic routes to monomers, and typical ⅡDs-based conjugated polymers are summarized.We also introduce side-chain engineering and cutting-edge applications, like stretchable transistors, sensing, active-matrix driving, etc., of the classic copolymer poly(isoindigo-co-bithiophene). Green polymerization approaches towards conjugated polymers incorporating ⅡDs are subsequently discussed for efficient polymerization. Finally, we conclude this review and propose in-depth prospects with respect to material synthesis and device applications. Undoubtedly, ⅡDs-based conjugated polymers would occupy a significant position in the future of organic electronics, due to diverse building blocks, mature synthetic pathways, tunable side chains, and unique optoelectronic properties.
基金support from the National Basic Research Program of China(973 Program)(2009CB930601)the National Natural Science Foundation of China(20904024)+2 种基金the Doctoral Fund of Ministry of Education of China(20093223120004)the NUPT Scientific Foundation(NY210016)Scientific and Technological Innovation Teams of Jiangsu Province Education Committee,China (TJ209035)
文摘Hyperbranched polymer structures represent a class of high-functionality building blocks with excellent three-dimensional topology for the construction of highly substituted conjugated polymers.In this contribution,an efficient microwave synthesis protocol toward the synthesis of conjugated hyperbranched polymers is presented.A novel series of soluble hyperbranched polyfluorenes (PTF1-PTF3) incorporating triazatruxene moiety as the branch units with various branching degrees have thus been successfully constructed with good yields and high molecular weight via a facile "A2+B2+C3" approach.The structures of the hyperbranched polymers were confirmed by NMR and GPC.Their thermal,optical,and electrochemical properties of the hyperbranched polymers were also investigated.The results showed that introduction of triazatruxene units into the hyperbranched structure endowed the polymer with good thermal stability and highly amorphous properties.Photophysical investigation of PTFx revealed strong blue emission in both solution and solid states.Hyperbranched polymers with higher degree of branching and proper content of linear fluorene units exhibited better photophysical properties in terms of narrow emission spectra and relatively high quantum efficiency as well as improved thermal spectral stability.The triazatruxene branching unit also played a role in raising the HOMO energy levels relative to those of polyfluorenes that would help to improve the charge injection and transport properties.The incorporation of triazatruxene unit into hyperbranched polymers has thus explored an effective avenue for constructing optoelectronic polymers with improved functional characteristics.
基金supported by the National Natural Science Foundation of China(21034006)
文摘A new type of dendritic polymer, named dendronized hyperbranched polymer (DHP), was prepared successfully by the macro-monomer approach. Thanks to the perfect 3D isolation effects, DHPG1 exhibited good NLO property with d 33 value of 133 pm/V, higher than its analogues of dendronized polymer and dendrimer, and its stability of NLO effect was also enhanced.
基金sponsored by the National Science Foundation (NSF, CMMI-1562907)the GAANN Fellowship for financial support (No. P200A150330)the Navy STEM Fellowship and the GAANN Fellowship for financial support
文摘Thanks to their remarkable mechanical, electrical, thermal, and barrier properties, graphene-based nanocomposites have been a hot area of research in the past decade. Because of their simple top-down synthesis, graphene oxide (GO) and reduced graphene oxide (rGO) have opened new possibilities for gas barrier, membrane separation, and stimuli-response characteristics in nanocomposites. Herein, we review the synthesis techniques most commonly used to produce these graphene derivatives, discuss how synthesis affects their key material properties, and highlight some examples of nanocomposites with unique and impressive properties. We specifically highlight their performances in separation applications, stimuli-responsive materials, anti-corrosion coatings, and energy storage. Finally, we discuss the outlook and remaining challenges in the field of practical industrial-scale production and use of graphene-derivative-based polymer nanocomposites.
基金funded by National Science and Technology Major Project(No.2017YFB0308500)Shaanxi Science and Technology Project(No.2018JM5164)+1 种基金Science and Technology Plan Project of Xi'an Weiyang District(No.201907)the Youth Innovation Team of Shaanxi Universities.
文摘A series of amphiphilic hyperbranched polymers(AHP-s,the“s”refers to the algebra of AHP)were synthesized by the reaction between hydroxyl-terminated hyperbranched polymers(HBP-s,the“s”refers to the algebra of HBP)and palmitoyl chloride.FTIR,NMR and GPC were used to determine the structure of AHP-s,the results showed that AHP-s exhibits core-shell structure.The thermal properties of polymers were investigated by DSC and TGA.It was found that AHP-2,AHP-3 and AHP-4 display higher thermal stability than AHP-1(AHP-1,AHP-2,AHP-3 and AHP-4 represent the first,second,third and fourth generation AHP,respectively).Furthermore,the self-assembly performance of AHP-s in THF solvent was investigated by TEM and SEM.Finally,the encapsulation capacity of the AHP-s for methyl orange(MO)was explored at different concentrations of AHP-s and pH conditions.It was found that AHP-s is capable of accommodating hydrophilic guest MO.Moreover,the higher generation of AHP-s,the stronger encapsulation capacity obtained.And the encapsulation capacity closely associated with the pH of encapsulation system.
文摘1 Results UV curing systems have been widely used in various industries such as coatings,printing inks,and photo-resists,because of their low volatile organic compound (VOC),excellent physical properties,and energy saving.Recently,these systems have also been applied to electronics and information technology fields such as display,CD,DVD,optical-fiber,and optical-device. In these curing systems,(meth)acrylate oligomers are mainly used due to their high photochemical reactivity. Recently,dendritic polyme...
基金This research was made possible as a result of a generous grant from NSFC Foundation(Grant Number 21734007).
文摘Through a controllable“reactivate””graft”synthetic route,two asymmetrical“Janus”dendronized polymers(DPs)were successfully synthesized.Dendrons were grafted to a linear polymer motherboard by a story-by-story constructionmethod.Due to the heterogenetic“Janus”structure,with orderly arranged chromophore moieties,the polymers demonstrated extremely large second-order nonlinear optical(NLO)coefficients and excellent NLO thermal stability.DP-4l and DP-6l had high d33 values of 232 and 227 pm/V,respectively,which reached the highest value reported so far for linear-based polymers containing simple azo-chromophore moieties.The controllable synthesis sheds light on the structure–property relationships of NLO polymers and other dendronized-structure functional polymers.
基金supported by the Startup Research Fund of Zhengzhou University(1411320006)the National Natural Science Foundation of China(21325416,21274133)
文摘Large nonlinear optical(NLO) coefficient and good stability, two essential factors to evaluate second-order NLO materials, are difficult to be achieved in one molecule simultaneously. Herein, by utilizing the concept of "isolation chromophore", "isolation group" and dendritic structure, a dendritic molecule D-NS and a dendronized hyperbranched polymer DHP-NS are prepared to investigate their structure-property relationship. For the small dendritic molecule D-NS, it exhibits a high d33 value of 140 pm/V.But this value can be easily dropped when the temperature is higher than 50 °C, which extremely limits its real application. After introducing D-NS into a dendronized hyperbranched polymer chains, the obtained DHP-NS also shows a high d33 value of101 pm/V, but much better stability than D-NS. Even when its thin film was heated to 120 °C, no obvious decay can be observed in the d33 value of DHP-NS. This work demonstrates an effective strategy to realize both large NLO effect and good stability simultaneously.
基金National Natural Science Foundation of China,Grant/Award Numbers:51903106,51873082,52073123State Administration of Foreign Experts Affairs,Grant/Award Number:G2021144006L+3 种基金Distinguished Young Natural Science Foundation of Jiangsu Province,Grant/Award Number:BK20200027Key Laboratory of Bio-based Material Science&TechnologyNortheast Forestry UniversityMOE&SAFEA 111,Grant/Award Number:B13025。
文摘In recent decades,the continuous depletion of fossil fuels and the increasingly serious environmental issue have aroused wide attention on the development of biopolymers based on renewable biomass.Lignin is the second most abundant organic bio-based macromolecule second to cellulose,and it can be widely found in plants.Furthermore,various phenol derivatives can be obtained by their depolymerization processes.The development of bio-renewable polymeric materials originating from lignin-derivative phenol monomers,such as vanillin,syringaldehyde,eugenol,vanillyl alcohol,vanillic acid,and ferulic acid,will not only valorize the bio-sourced materials but also effectively reduce petroleum resource consumption and mitigate the environmental pollution.Therefore,an updated overview of the synthesis processes of these bio-based polymers developed in the past decade,which includes both thermosets and thermoplastics such as epoxy,phenolic,polyimine,polybenzoxazine,polyurethane,and polyesters,are elucidated.In addition,the applications of these bio-based polymers and their composites in flame-retarded materials,degradable and reprocessable materials,dielectric materials,optoelectronic materials,as well as smart responsive materials are also intensively discussed.In line with the gradual development of synthesis technologies,we believe that derivatives of lignin will turn into one of the most promising materials to be considered for the preparation of high-performance and functional bio-based polymer materials.
文摘Polyamides containing thieno[2,3-b]thiophene moiety were prepared via a simple polycondensation reaction of the diaminothieno[2,3-b]thiophene monomer la with different kinds of diacid chlorides (including oxalyl, adipoyl, sebacoyl, isophthaloyl, terephthaloyl, 4,4'-azodibenzoyl, 3,3'-azodibenzoyl, p-phenylene diacryloyl) in the presence of LiC1 and NMP as a solvent through lowtemperature solution polycondensation. The chemical structures of model compound and synthesized polyamides were confirmed by FTIR, nuclear magnetic resonance spectroscopy (including 1 H-NMR and 13 C-NMR) and elemental analysis. In addition, the thermal stability, crystallinity structure and surface morphology of synthesized polyamides were characterized via thermogravametric analysis (TGA), wide-angle X-ray diffraction analysis (WAXD) and scanning electron microscopy (SEM). Also, the corrosion inhibition behavior of selected examples ofpolyamides was investigated; the inhibitive effect of the investigated polymers for carbon steel in 1.0 mol'L-1 HCI was studied using potentiodynamic polarization (PDP) and electrochemical impedance spectroscopy (EIS) methods. PDP results displayed that the polyamides containing thieno[2,3-b]thiophene moiety can be as mixed-type inhibitors. The inhibition efficiency (P, %) was found to be in the range from 67.13% to 96.01%. There is an increase in P by the synthesized polymers in comparison to the starting monomer. The adsorption of these polymers was found to obey Langmuir adsorption isotherm.