Shape memory polymers used in 4D printing only had one permanent shape after molding,which limited their applications in requiring multiple reconstructions and multifunctional shapes.Furthermore,the inherent stability...Shape memory polymers used in 4D printing only had one permanent shape after molding,which limited their applications in requiring multiple reconstructions and multifunctional shapes.Furthermore,the inherent stability of the triazine ring structure within cyanate ester(CE)crosslinked networks after molding posed significant challenges for both recycling,repairing,and degradation of resin.To address these obstacles,dynamic thiocyanate ester(TCE)bonds and photocurable group were incorporated into CE,obtaining the recyclable and 3D printable CE covalent adaptable networks(CANs),denoted as PTCE1.5.This material exhibits a Young's modulus of 810 MPa and a tensile strength of 50.8 MPa.Notably,damaged printed PTCE1.5 objects can be readily repaired through reprinting and interface rejoining by thermal treatment.Leveraging the solid-state plasticity,PTCE1.5 also demonstrated attractive shape memory ability and permanent shape reconfigurability,enabling its reconfigurable 4D printing.The printed PTCE1.5 hinges and a main body were assembled into a deployable and retractable satellite model,validating its potential application as a controllable component in the aerospace field.Moreover,printed PTCE1.5 can be fully degraded into thiol-modified intermediate products.Overall,this material not only enriches the application range of CE resin,but also provides a reliable approach to addressing environmental issue.展开更多
Poly(p-phenylene-2,6-benzobisoxazole)(PBO)fibers possess excellent dielectric,mechanical properties and heat resistance.However,the surface of PBO fibers is smooth and highly chemical inert,resulting in poor interfaci...Poly(p-phenylene-2,6-benzobisoxazole)(PBO)fibers possess excellent dielectric,mechanical properties and heat resistance.However,the surface of PBO fibers is smooth and highly chemical inert,resulting in poor interfacial compatibility to polymer matrix,which severely limits its wider application in high-performance fiber-reinforced resin matrix composites.In this work,random copolymers(P(S-co-BCB-co-MMA))containing benzocyclobutene in the side-chain were synthesized by reversible addition-fragmentation chain transfer(RAFT)polymerization,which were then utilized to form dense random copolymer membrane on the surface of PBO fibers by thermally cross-linking at 250°C(PBO@P fibers).Four kinds of synthesized P(S-co-BCB-co-MMA)with different number-average molar mass(Mn)were well controlled and possessed narrow dispersity.When the Mnwas 32300,the surface roughness of PBO@P fibers was increased from 11 nm(PBO fibers)to 39 nm.In addition,PBO@P fibers presented the optimal interfacial compatibility with bisphenol A cyanate(BADCy)resins.And the single fiber pull-out strength of PBO@P fibers/BADCy micro-composites was 4.5 MPa,increasing by 45.2%in comparison with that of PBO fibers/BADCy micro-composites(3.1 MPa).Meantime,PBO@P fibers still retained excellent tensile strength(about 5.1 GPa).Overall,this work illustrates a simple and efficient surface functionalization method,which would provide a strong theoretical basis and technical support for controlling the surface structure&chemistry of inert substrates.展开更多
Electroactive shape memory composites were synthesized using polybutadiene epoxy （PBEP） and bisphenol A type cyanate ester （BACE） filled with different contents of carbon black （CB）. Dynamic mechanical analysis ...Electroactive shape memory composites were synthesized using polybutadiene epoxy （PBEP） and bisphenol A type cyanate ester （BACE） filled with different contents of carbon black （CB）. Dynamic mechanical analysis （DMA）, scanning electron microscopy （SEM）, electrical performance and electroactive shape memory behavior were systematically investigated. It is found that the volume resistivity decreased due to excellent electrical conductivity of CB, in turn resulting in good electroactive shape memory properties. The content of CB and applied voltage had significant influence on electroactive shape memory effect of developed BACE/PBEP/CB composites. Shape recovery can be observed within a few seconds with the CB content of 5 wt% and voltage of 60 V. Shape recovery time decreased with increasing content of CB and voltage. The infrared thermometer revealed that the temperature rises above the glass transition temperature faster with the increase of voltage and the decrease of resistance.展开更多
This present study deals with the reinforcement of thermosetting resin blends composed of cyanate ester(CE) and benzoxazine(BOZ) resins with natural hemp fibers(NHFs). These NHFs were initially treated by using a sila...This present study deals with the reinforcement of thermosetting resin blends composed of cyanate ester(CE) and benzoxazine(BOZ) resins with natural hemp fibers(NHFs). These NHFs were initially treated by using a silane coupling agent(SCA) in order to chiefly enhance their distributions as well as adhesions within the CE/BOZ resin matrix,then incorporated with various weight amounts ranging from 5 wt% to 20 wt% with a regular interval of 5 wt%. The obtained results showed that at the maximum treated fiber loading(20 wt%), distinctive enhancements in the mechanical properties in terms of flexural strength and microhardness were obtained. Besides, the thermal stability and glass transition temperature(Tg) were appreciably enhanced and were higher than those of the pure CE/BOZ resin properties. With respect to the astonishing properties of the NHFs, these enhancements could be possibly due to the good dispersion and adhesion of the treated NHFs inside the CE/BOZ resin achieved upon using the SCA. Therefore,we believe herein that these renewable and cheap NHFs have considerable potential to be used as reinfocer materials for CE/BOZ resin composites to be used in various industrial sectors.展开更多
The properties of resin transfer molding(RTM)cyanate ester and its T800 grade carbon fiber composites were studied with the rheometer,differential scanning calorimetry(DSC),FT-IR,dynamic mechanical analyzer(DMA),therm...The properties of resin transfer molding(RTM)cyanate ester and its T800 grade carbon fiber composites were studied with the rheometer,differential scanning calorimetry(DSC),FT-IR,dynamic mechanical analyzer(DMA),thermal gravimetric analysis(TGA),mechanical property testing,and scanning electron microscopy(SEM).The results showed that the temperature of cyanate ester suitable for RTM process was 70℃.Curing process of the resin was 130℃/2 h+160℃/2 h+200℃/2 h+220℃/4 h.Glass transition temperature and heat decomposition temperature of the cured resin are 289℃and 415℃,respectively.Mechanical properties of T800/RTM cyanate composites are 13.5%higher than that of T700/RTM cyanate composites and equal to that of T800/Prepreg cyanate composites.Tg of T800/RTM cyanate composites was proved to be 291℃.Fracture pattern of the composites was flat,which proved excellent interface properties between fiber and resin in this composite.展开更多
Fumed silica/bisphenol A dicyanate ester （BADCy） nanocomposites were prepared by introducing different contents of nano-sized fumed SiO2 into the BADCy matrix. Two different average primary particle diameters of 12 ...Fumed silica/bisphenol A dicyanate ester （BADCy） nanocomposites were prepared by introducing different contents of nano-sized fumed SiO2 into the BADCy matrix. Two different average primary particle diameters of 12 and 40 nm were chosen. Dibutyltindilaurate （DBTDL） catalyst was chosen to catalyze the cyanate ester group into triazine group via cyclotrimerization reaction. The SEM micrographs indicated that the fumed SiO2 particles were homogeneously dispersed in the poly（bisphenol A dicyanate） matrix by means of ultrasonic treatment and the addition of a coupling agent. The FTIR spectroscopy shows that, not only DBTDL catalyzes the polymerization reaction but also --OH groups of the SiO2 particles surface help the catalyst for the complete polymerization of BADCy monomer. The thermal stability of the cured BADCy can be improved by adequate addition of fumed SiO2. A slight increase in the dielectric constant and dielectric loss values were identified by testing the dielectric properties of the prepared nanocomposite samples. By increasing the SiO2 content, there was a slight increasing in the thermal conductivity values of the tested samples. The obtained results proved that the fumed silica/BADCy nanocomposites had good thermal and dielectrieal properties and can be used in many applications such as in the thermal insulation field.展开更多
Inkjet 3D printing has potential in the additive manufacturing of electronic circuits and devices.However,inks that can be used for printing layers with T5%>300℃ or hardness>200 MPa have been rarely reported.Cy...Inkjet 3D printing has potential in the additive manufacturing of electronic circuits and devices.However,inks that can be used for printing layers with T5%>300℃ or hardness>200 MPa have been rarely reported.Cyanate ester(CE)polymers have excellent thermal stability,high strength,and low shrinkage compared to other common dielectric inks for inkjet 3D printing,but cannot be quickly shaped by ultraviolet(UV)irradiation or thermal treatment.Combining CEs with UV-curable monomers may be a possible way to accelerate crosslinking,but there are challenges from the adverse effects of the dilution of both monomers.In this study,dielectric inks with acrylate and cyanate moieties were developed.The low viscosity and surface tension of the CE precursor(Bisphenol E cyanate ester)were combined with photocurable acrylate diluent monomers and cross-linker to realize an ink suitable for inkjet 3D printing.An internal dual three-dimensional cross-linked network structure resin was prepared by a combination of photocuring and thermal curing with T5%up to 326.69℃,hardness up to 431.84 MPa,dielectric constant of 2.70 at 8 GHz,and shrinkage of 1.64%.The developed dielectric inks can be applied to the 3D printing of printed circuit boards and other electronic devices that require dielectric properties.展开更多
In the field of highly integrated printed circuit board （PCB）, the heat resistant substrate with low water absorption is very important material. To get the resin composition for the high functional substrate materi...In the field of highly integrated printed circuit board （PCB）, the heat resistant substrate with low water absorption is very important material. To get the resin composition for the high functional substrate material with low moisture absorption and high glass transition temperature （Tg） simultaneously, a fluorenyl ＂Cardo＂ epoxy was incorporated into novolac cyanate ester resin. As an optimum curing agent for the fiuorenyl epoxy, methyl nadic anhydride （MNA） was selected. Silica powders as fillers were added into the resin composition. The partial replacement of the cyanate ester resin with the fluorenyl epoxy could reduce the moisture absorption with keeping high glass transition temperature over 300 ℃. The laminate, which was fabricated from prepregs made with 40 wt% silica-filled resin composition and glass fabric, showed high Tg of 317 ℃ and low moisture absorption of 0.57%.展开更多
A novel benzoxazine(BOZ)monomer is synthesized by a pot method with solvent-free to blend with cyanate ester(CE).A soluble intermediate is obtained after being cured for 20 h at 80℃.The two model compound and the ble...A novel benzoxazine(BOZ)monomer is synthesized by a pot method with solvent-free to blend with cyanate ester(CE).A soluble intermediate is obtained after being cured for 20 h at 80℃.The two model compound and the blends are analyzed with the infrared radiation(IR),nuclear magnetic resonance(NMR)spectroscopy,and differential scanning calorimetry(DSC).The results show that an intermediate of the iminocarbonate and BOZ structures is formed by the ring-open BOZ reacting with the cyanate groups and ring-unopened BOZ.Moreover,rearrangement and ring-opening occur in the postcure of the intermediate to form the alkyl isocyanurate structure with polybenzoxazine.展开更多
The thermal and dimensional stability of epoxy resin(EP)in-situ modified by cyanate ester(CE)and polydimethylsiloxane(PDMS)are investigated by means of experiments and numerical simulation.Thermal gravimetric analysis...The thermal and dimensional stability of epoxy resin(EP)in-situ modified by cyanate ester(CE)and polydimethylsiloxane(PDMS)are investigated by means of experiments and numerical simulation.Thermal gravimetric analysis(TGA)and differential scanning calorimeter(DSC)are used to analyze the heat resistance of the modified EP.The dimensional stability is characterized by the volume shrinkage of the series PDMS/CE/EP obtained by the density method.The chemical structure of the PDMS/CE/EP is analyzed by Fourier transform infrared spectroscopy(FTIR).The results of TGA and DSC indicate that the thermal stability of PDMS/CE/EP decreases firstly and then increases with the increase in the amount of CE.The addition of PDMS shows a slight effect on the thermal stability.The 40%CE makes the blending system exhibit the lowest initial decomposition temperature,which reduces by 15.5%and 40.8%compared with pure EP and CE,respectively.The FTIR results suggested that the influence of CE on the thermal stability of the modified EP is mainly ascribed to the generation of oxazolidinone ring with low thermal stability and the increase in the triazine ring with high thermal stability.The volume shrinkage measurement results show that the introduction of CE and PDMS are both beneficial to the improvement of the dimensional stability of the blending systems.The in-situ addition of 80%CE shows the lowest volume shrinkage of6.11%.The thermal stress distribution of PDMS/CE/EP generated during the solidification process is simulated by the finite element analysis.The results suggested that the introduction of 80%CE into EP results in the lowest thermal stress in the blending system,which indicates that the system has the lowest volume shrinkage,which agrees well with the experimental results.展开更多
The donor–acceptor(D–A)copolymers,which exhibit wide broad absorption and intensified light-harvesting,are highly captivating for applications in solar conversion and optoelectronics.However,designing a polymer stru...The donor–acceptor(D–A)copolymers,which exhibit wide broad absorption and intensified light-harvesting,are highly captivating for applications in solar conversion and optoelectronics.However,designing a polymer structure that can achieve these photophysical properties simultaneously remains a challenge.Herein,we report two novel cyanated units 4-cyanobenzo[1,2-b:6,5-b′:3,4-c″]trithiophene(CBT)and 4,6-dicyanobenzo[1,2-b:6,5-b′:3,4-c″]trithiophene(C2BT)and their corresponding polymers,PCBT and PC2BT.Very interestingly,the PC2BT exhibited a broad absorption band with full width at half maxima(FWHM)of its absorption spectra,almost twice wider than PCBT and benchmark polymers PM6 and D18.Moreover,the PC2BT demonstrated intensified light-harvesting and long-lived exciton.Our in-depth investigation unveiled that the presence of dicyano substitutions induced a strong intramolecular charge transfer(ICT),which,in turn,resulted in the formation of favorable photophysical properties.Therefore,PC2BT-based polymer solar cells(PSCs)exhibited an efficiency of 18.06%,which was a record-setting efficiency for cyanated polymers.This study suggests an efficient strategy for enhancing ICT to design polymers toward favorable photophysical properties and excellent photovoltaic performance.展开更多
High-performance polymer friction materials with tunable tribological behavior to fit varied work conditions remain a challenge of widespread interest for a variety of applications.Shape memory polymer exhibits morphi...High-performance polymer friction materials with tunable tribological behavior to fit varied work conditions remain a challenge of widespread interest for a variety of applications.Shape memory polymer exhibits morphing and modulus changing over temperature changing provides a promising material to adjust the friction process.Herein,we investigated the tribological properties of shape memory cyanate ester(SMCE)under different conditions.The SMCE exhibits the tribological behavior of good friction material with stable high coefficient of friction(COF)and a low wear rate.Besides,the COF increases and wear rate decreases with the temperature increasing show the tunable friction property of the SMCE.We propose a new model of wear-compensation through shape recovery to explain the adjustable friction behavior of thermal-responsive polymer from the aspect of shape recovery and energy conversion.This study provides a high-performance friction material and paves the route for the application of shape memory polymer(SMP)in tribology field with tunable property.展开更多
The selective conversion of CO_(2)and NH_(3)into valuable nitriles presents significant potential for CO_(2)utilization.In this study,we exploited the synergistic interplay between silicon and fluoride to augment the ...The selective conversion of CO_(2)and NH_(3)into valuable nitriles presents significant potential for CO_(2)utilization.In this study,we exploited the synergistic interplay between silicon and fluoride to augment the nickel-catalyzed reductive cyanation of aryl pseudohalides containing silyl groups,utilizing CO_(2)and NH_(3)as the CN source.Our methodology exhibited exceptional compatibility with diverse functional groups,such as alcohols,ketones,ethers,esters,nitriles,olefins,pyridines,and quinolines,among others,as demonstrated by the successful synthesis of 58 different nitriles.Notably,we achieved high yields in the preparation of bifunctionalized molecules,including intermediates for perampanel,derived from osilylaryl triflates,which are well-known as aryne precursors.Remarkably,no degradation of substrates or formation of aryne intermediates were observed.Mechanistic studies imply that the formation of pentacoordinated silyl isocyanate intermediates is crucial for the key C-C coupling step and the presence of vicinal silyl group in the substrate is beneficial to further make this step kinetically favorable.展开更多
Herein,we developed the first example of copper-catalyzed silicon radical-initiated 1,4-silylcyanation of unactivated 1,3-enynes,which provided an efficient method to access CN-bearing tri-and tetrasubstituted homoall...Herein,we developed the first example of copper-catalyzed silicon radical-initiated 1,4-silylcyanation of unactivated 1,3-enynes,which provided an efficient method to access CN-bearing tri-and tetrasubstituted homoallenylsilane derivatives in high yields with excellent regioselectivities.This protocol featured good functional group compatibility and broad substrate scopes,enabling the formation of C-Si bond under cheap copper catalyst with a low loading.Furthermore,this means showed potential application value in the late-stage functionalization of natural products.展开更多
Herein,a metal-free electrochemical demethoxyl-cyanation of methoxyarenes via aromatic nucleophilic substitution(S_(N)Ar) using TMSCN as a cheap cyanide source under mild conditions has been presented.This transformat...Herein,a metal-free electrochemical demethoxyl-cyanation of methoxyarenes via aromatic nucleophilic substitution(S_(N)Ar) using TMSCN as a cheap cyanide source under mild conditions has been presented.This transformation utilizes commercially available reagents,cheap electrodes,and simple equipment.Diverse aryl nitriles were successfully obtained in a direct and efficient way with broad substrate scope,excellent functional group tolerance,and selective C-O bond cleavage.Furthermore,late-stage modification of biorelevant compounds and gram-scale synthesis highlighted the potential application of the strategy.Mechanistic investigations suggest that the arene cation radical was considered as the key intermediate for the transformation,and undergoing the followed S_(N)Ar process.展开更多
Covalent triazine-based frameworks（CTFs） are important microporous materials with a wide range of applications.Here,we demonstrate an environmentally benign and economic synthetic pathway to CTFs.The monomers used f...Covalent triazine-based frameworks（CTFs） are important microporous materials with a wide range of applications.Here,we demonstrate an environmentally benign and economic synthetic pathway to CTFs.The monomers used for CTFs,aromatic nitriles,were obtained by cyanation using nontoxic potassium hexacyanoferrate（Ⅱ） in place of commonly used toxic cyanides.Then,the CTFs were synthesized by trimerization of the corresponding cyano monomers in molten zinc chloride.A series of CTFs was synthesized,and the highest Brunauer-Emmett-Teller surface area measured in this series was 2404 m^2/g.Among the synthesized CTFs,CTF_（DCP） exhibited excellent CO_2 adsorption properties,with a CO_2 uptake of 225 mg/g at 0℃.展开更多
Low dielectric in terlayer films have become an important element to ensure the development of the microelectr onics industry.A kind of flexible interlayer dielectrics,polyarylene ether nitrile/bisphenol A cyanate est...Low dielectric in terlayer films have become an important element to ensure the development of the microelectr onics industry.A kind of flexible interlayer dielectrics,polyarylene ether nitrile/bisphenol A cyanate ester(PEN/BADCy)film,with good thermal stability and low frequency dependence,has been developed by solution casting method.Herein,materials were designed to incorporate bisphenol A cyanate ester as a part of blend,contributing to the frequency stability and structural integrity.The morphological study combined with electron microscopy revealed the uniform and flexible microstructure information with controllable morphology through self-polymerization of cyanate esters with different prepolymerization time and curing temperatures.The dielectric films could present high thermal stability with Tg>180℃.Significant improvement in the dielectric properties was achieved for the dielectric constant and loss was much stabler than neat PEN over the frequency range from 100 Hz to 5 MHz.When the prepolymerization time was 3h and final curing temperature reached 230℃,the dielectric constant and dielectric loss of the films were 3.36 and 0.013 at 100 kHz,respectively.The dimensional stability(CTE=53.67×10^-6 K^-1)was confirmed and con sidered beneficial to use as an in terlayer dielectrics.展开更多
A fast and efficient method is described for the one-pot synthesis of 2,4（1H,3H）-quinazolinediones by cyclization reaction of anthranilic acid derivatives with potassium cyanate and acetic acid in PEG.Good to high y...A fast and efficient method is described for the one-pot synthesis of 2,4（1H,3H）-quinazolinediones by cyclization reaction of anthranilic acid derivatives with potassium cyanate and acetic acid in PEG.Good to high yields of the products obtain in short reaction times with simple work-up.展开更多
A new type of the nanometer particles and epoxy/bismaleimide-triazine nanocomposites were prepared using a nanometer silica(nano-SiO(_2)),a 4,5-epoxycyclohexane 1,2-dicarboxylic acid dilycidyl(TDE-85)epoxy resin,a 4,4...A new type of the nanometer particles and epoxy/bismaleimide-triazine nanocomposites were prepared using a nanometer silica(nano-SiO(_2)),a 4,5-epoxycyclohexane 1,2-dicarboxylic acid dilycidyl(TDE-85)epoxy resin,a 4,4'-bismaleimidodiphenymethane(BMI)and a bisphenol a dicyanate(BADCy).The properties of nano-SiOJTDE-85/BMI/BADCy composites,such as mechanical and thermal properties,were systemically investigated in detail by mechanical measurement,scanning electron microscope(SEM),dynamic mechanical analysis(DMA)and thermogravimetric analysis(TGA).The experimental results showed that the addition of the appropriate amount of nano-SiO(_2):could improve the impact strength and the flexural strength of the nano-SiO(_2)/TDE-85/BMI/BADCy composites.Simultaneously,the thermal stability of the blends was found to be higher than that of the TDE-85/BMI/BADCy copolymers.展开更多
基金supported by the National Natural Science Foundation of China(Nos.52473080,52403167 and 52173079)the Fundamental Research Funds for the Central Universities(Nos.xtr052023001 and xzy012023037)+1 种基金the Postdoctoral Research Project of Shaanxi Province(No.2024BSHSDZZ054)the Shaanxi Laboratory of Advanced Materials(No.2024ZY-JCYJ-04-12).
文摘Shape memory polymers used in 4D printing only had one permanent shape after molding,which limited their applications in requiring multiple reconstructions and multifunctional shapes.Furthermore,the inherent stability of the triazine ring structure within cyanate ester(CE)crosslinked networks after molding posed significant challenges for both recycling,repairing,and degradation of resin.To address these obstacles,dynamic thiocyanate ester(TCE)bonds and photocurable group were incorporated into CE,obtaining the recyclable and 3D printable CE covalent adaptable networks(CANs),denoted as PTCE1.5.This material exhibits a Young's modulus of 810 MPa and a tensile strength of 50.8 MPa.Notably,damaged printed PTCE1.5 objects can be readily repaired through reprinting and interface rejoining by thermal treatment.Leveraging the solid-state plasticity,PTCE1.5 also demonstrated attractive shape memory ability and permanent shape reconfigurability,enabling its reconfigurable 4D printing.The printed PTCE1.5 hinges and a main body were assembled into a deployable and retractable satellite model,validating its potential application as a controllable component in the aerospace field.Moreover,printed PTCE1.5 can be fully degraded into thiol-modified intermediate products.Overall,this material not only enriches the application range of CE resin,but also provides a reliable approach to addressing environmental issue.
基金support and funding from National Scientific Research ProjectSpace Supporting Fund from China Aerospace Science and Industry Corporation(2019-HT-XG)+1 种基金Fundamental Research Funds for the Central Universities(310201911qd003)China Postdoctoral Science Foundation(2019M653735)。
文摘Poly(p-phenylene-2,6-benzobisoxazole)(PBO)fibers possess excellent dielectric,mechanical properties and heat resistance.However,the surface of PBO fibers is smooth and highly chemical inert,resulting in poor interfacial compatibility to polymer matrix,which severely limits its wider application in high-performance fiber-reinforced resin matrix composites.In this work,random copolymers(P(S-co-BCB-co-MMA))containing benzocyclobutene in the side-chain were synthesized by reversible addition-fragmentation chain transfer(RAFT)polymerization,which were then utilized to form dense random copolymer membrane on the surface of PBO fibers by thermally cross-linking at 250°C(PBO@P fibers).Four kinds of synthesized P(S-co-BCB-co-MMA)with different number-average molar mass(Mn)were well controlled and possessed narrow dispersity.When the Mnwas 32300,the surface roughness of PBO@P fibers was increased from 11 nm(PBO fibers)to 39 nm.In addition,PBO@P fibers presented the optimal interfacial compatibility with bisphenol A cyanate(BADCy)resins.And the single fiber pull-out strength of PBO@P fibers/BADCy micro-composites was 4.5 MPa,increasing by 45.2%in comparison with that of PBO fibers/BADCy micro-composites(3.1 MPa).Meantime,PBO@P fibers still retained excellent tensile strength(about 5.1 GPa).Overall,this work illustrates a simple and efficient surface functionalization method,which would provide a strong theoretical basis and technical support for controlling the surface structure&chemistry of inert substrates.
文摘Electroactive shape memory composites were synthesized using polybutadiene epoxy （PBEP） and bisphenol A type cyanate ester （BACE） filled with different contents of carbon black （CB）. Dynamic mechanical analysis （DMA）, scanning electron microscopy （SEM）, electrical performance and electroactive shape memory behavior were systematically investigated. It is found that the volume resistivity decreased due to excellent electrical conductivity of CB, in turn resulting in good electroactive shape memory properties. The content of CB and applied voltage had significant influence on electroactive shape memory effect of developed BACE/PBEP/CB composites. Shape recovery can be observed within a few seconds with the CB content of 5 wt% and voltage of 60 V. Shape recovery time decreased with increasing content of CB and voltage. The infrared thermometer revealed that the temperature rises above the glass transition temperature faster with the increase of voltage and the decrease of resistance.
基金Supported by the National Natural Science Foundation of China(51773048)the Natural Science Foundation of Heilongjiang Province(E2016025)Fundamental Research Funds for the Central Universities(HEUCFP201724,HEUCFP201791)
文摘This present study deals with the reinforcement of thermosetting resin blends composed of cyanate ester(CE) and benzoxazine(BOZ) resins with natural hemp fibers(NHFs). These NHFs were initially treated by using a silane coupling agent(SCA) in order to chiefly enhance their distributions as well as adhesions within the CE/BOZ resin matrix,then incorporated with various weight amounts ranging from 5 wt% to 20 wt% with a regular interval of 5 wt%. The obtained results showed that at the maximum treated fiber loading(20 wt%), distinctive enhancements in the mechanical properties in terms of flexural strength and microhardness were obtained. Besides, the thermal stability and glass transition temperature(Tg) were appreciably enhanced and were higher than those of the pure CE/BOZ resin properties. With respect to the astonishing properties of the NHFs, these enhancements could be possibly due to the good dispersion and adhesion of the treated NHFs inside the CE/BOZ resin achieved upon using the SCA. Therefore,we believe herein that these renewable and cheap NHFs have considerable potential to be used as reinfocer materials for CE/BOZ resin composites to be used in various industrial sectors.
文摘The properties of resin transfer molding(RTM)cyanate ester and its T800 grade carbon fiber composites were studied with the rheometer,differential scanning calorimetry(DSC),FT-IR,dynamic mechanical analyzer(DMA),thermal gravimetric analysis(TGA),mechanical property testing,and scanning electron microscopy(SEM).The results showed that the temperature of cyanate ester suitable for RTM process was 70℃.Curing process of the resin was 130℃/2 h+160℃/2 h+200℃/2 h+220℃/4 h.Glass transition temperature and heat decomposition temperature of the cured resin are 289℃and 415℃,respectively.Mechanical properties of T800/RTM cyanate composites are 13.5%higher than that of T700/RTM cyanate composites and equal to that of T800/Prepreg cyanate composites.Tg of T800/RTM cyanate composites was proved to be 291℃.Fracture pattern of the composites was flat,which proved excellent interface properties between fiber and resin in this composite.
基金supported by the National Research Fund for Fundamental Key Projects(No.2010CB934700)the National Natural Science Foundation of China(No.51003004)the Fundamental Research Funds for the Central Universities
文摘Fumed silica/bisphenol A dicyanate ester （BADCy） nanocomposites were prepared by introducing different contents of nano-sized fumed SiO2 into the BADCy matrix. Two different average primary particle diameters of 12 and 40 nm were chosen. Dibutyltindilaurate （DBTDL） catalyst was chosen to catalyze the cyanate ester group into triazine group via cyclotrimerization reaction. The SEM micrographs indicated that the fumed SiO2 particles were homogeneously dispersed in the poly（bisphenol A dicyanate） matrix by means of ultrasonic treatment and the addition of a coupling agent. The FTIR spectroscopy shows that, not only DBTDL catalyzes the polymerization reaction but also --OH groups of the SiO2 particles surface help the catalyst for the complete polymerization of BADCy monomer. The thermal stability of the cured BADCy can be improved by adequate addition of fumed SiO2. A slight increase in the dielectric constant and dielectric loss values were identified by testing the dielectric properties of the prepared nanocomposite samples. By increasing the SiO2 content, there was a slight increasing in the thermal conductivity values of the tested samples. The obtained results proved that the fumed silica/BADCy nanocomposites had good thermal and dielectrieal properties and can be used in many applications such as in the thermal insulation field.
基金supported by the National Key Researchand Development Programof China(No.2022YFB4600101)the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB 0470303)+2 种基金the National Natural Science Foundation of China(No.21974057)the Western Light Project of Chinese Academy of Sciences(No.xbzg-zdsy-202007)the Oasis Scholar of Shihezi University and the Central Government to Guide Local Technological Development(No.23ZYQA315).
文摘Inkjet 3D printing has potential in the additive manufacturing of electronic circuits and devices.However,inks that can be used for printing layers with T5%>300℃ or hardness>200 MPa have been rarely reported.Cyanate ester(CE)polymers have excellent thermal stability,high strength,and low shrinkage compared to other common dielectric inks for inkjet 3D printing,but cannot be quickly shaped by ultraviolet(UV)irradiation or thermal treatment.Combining CEs with UV-curable monomers may be a possible way to accelerate crosslinking,but there are challenges from the adverse effects of the dilution of both monomers.In this study,dielectric inks with acrylate and cyanate moieties were developed.The low viscosity and surface tension of the CE precursor(Bisphenol E cyanate ester)were combined with photocurable acrylate diluent monomers and cross-linker to realize an ink suitable for inkjet 3D printing.An internal dual three-dimensional cross-linked network structure resin was prepared by a combination of photocuring and thermal curing with T5%up to 326.69℃,hardness up to 431.84 MPa,dielectric constant of 2.70 at 8 GHz,and shrinkage of 1.64%.The developed dielectric inks can be applied to the 3D printing of printed circuit boards and other electronic devices that require dielectric properties.
文摘In the field of highly integrated printed circuit board （PCB）, the heat resistant substrate with low water absorption is very important material. To get the resin composition for the high functional substrate material with low moisture absorption and high glass transition temperature （Tg） simultaneously, a fluorenyl ＂Cardo＂ epoxy was incorporated into novolac cyanate ester resin. As an optimum curing agent for the fiuorenyl epoxy, methyl nadic anhydride （MNA） was selected. Silica powders as fillers were added into the resin composition. The partial replacement of the cyanate ester resin with the fluorenyl epoxy could reduce the moisture absorption with keeping high glass transition temperature over 300 ℃. The laminate, which was fabricated from prepregs made with 40 wt% silica-filled resin composition and glass fabric, showed high Tg of 317 ℃ and low moisture absorption of 0.57%.
文摘A novel benzoxazine(BOZ)monomer is synthesized by a pot method with solvent-free to blend with cyanate ester(CE).A soluble intermediate is obtained after being cured for 20 h at 80℃.The two model compound and the blends are analyzed with the infrared radiation(IR),nuclear magnetic resonance(NMR)spectroscopy,and differential scanning calorimetry(DSC).The results show that an intermediate of the iminocarbonate and BOZ structures is formed by the ring-open BOZ reacting with the cyanate groups and ring-unopened BOZ.Moreover,rearrangement and ring-opening occur in the postcure of the intermediate to form the alkyl isocyanurate structure with polybenzoxazine.
基金the Shanghai Aerospace Science and Technology Innovation Fund of China(No.SAST2019-122)。
文摘The thermal and dimensional stability of epoxy resin(EP)in-situ modified by cyanate ester(CE)and polydimethylsiloxane(PDMS)are investigated by means of experiments and numerical simulation.Thermal gravimetric analysis(TGA)and differential scanning calorimeter(DSC)are used to analyze the heat resistance of the modified EP.The dimensional stability is characterized by the volume shrinkage of the series PDMS/CE/EP obtained by the density method.The chemical structure of the PDMS/CE/EP is analyzed by Fourier transform infrared spectroscopy(FTIR).The results of TGA and DSC indicate that the thermal stability of PDMS/CE/EP decreases firstly and then increases with the increase in the amount of CE.The addition of PDMS shows a slight effect on the thermal stability.The 40%CE makes the blending system exhibit the lowest initial decomposition temperature,which reduces by 15.5%and 40.8%compared with pure EP and CE,respectively.The FTIR results suggested that the influence of CE on the thermal stability of the modified EP is mainly ascribed to the generation of oxazolidinone ring with low thermal stability and the increase in the triazine ring with high thermal stability.The volume shrinkage measurement results show that the introduction of CE and PDMS are both beneficial to the improvement of the dimensional stability of the blending systems.The in-situ addition of 80%CE shows the lowest volume shrinkage of6.11%.The thermal stress distribution of PDMS/CE/EP generated during the solidification process is simulated by the finite element analysis.The results suggested that the introduction of 80%CE into EP results in the lowest thermal stress in the blending system,which indicates that the system has the lowest volume shrinkage,which agrees well with the experimental results.
基金supported by the National Natural Science Foundation of China(grant nos.22179076 and 22225504)the Department of Education of Guangdong Province,China(grant no.2021KCXTD032)+2 种基金the Natural Science Foundation of Guangdong Province,China(grant no.2022A1515011803)the Science and Technology Innovation Fund for College students in Guangdong Province,China(grant no.2020329105600A000003)Guangdong Provincial Key Laboratory of Catalysis,China(grant no.2020B121201002).
文摘The donor–acceptor(D–A)copolymers,which exhibit wide broad absorption and intensified light-harvesting,are highly captivating for applications in solar conversion and optoelectronics.However,designing a polymer structure that can achieve these photophysical properties simultaneously remains a challenge.Herein,we report two novel cyanated units 4-cyanobenzo[1,2-b:6,5-b′:3,4-c″]trithiophene(CBT)and 4,6-dicyanobenzo[1,2-b:6,5-b′:3,4-c″]trithiophene(C2BT)and their corresponding polymers,PCBT and PC2BT.Very interestingly,the PC2BT exhibited a broad absorption band with full width at half maxima(FWHM)of its absorption spectra,almost twice wider than PCBT and benchmark polymers PM6 and D18.Moreover,the PC2BT demonstrated intensified light-harvesting and long-lived exciton.Our in-depth investigation unveiled that the presence of dicyano substitutions induced a strong intramolecular charge transfer(ICT),which,in turn,resulted in the formation of favorable photophysical properties.Therefore,PC2BT-based polymer solar cells(PSCs)exhibited an efficiency of 18.06%,which was a record-setting efficiency for cyanated polymers.This study suggests an efficient strategy for enhancing ICT to design polymers toward favorable photophysical properties and excellent photovoltaic performance.
基金The authors gratefully acknowledge financial support from the National Natural Science Foundation of China(51935012 and 52105223)Major Program of the Lanzhou Institute of Chemical Physics,CAS(No.ZYFZFX-7)Key Research Program of the Chinese Academy of Sciences(Grant No.XDPB24).
文摘High-performance polymer friction materials with tunable tribological behavior to fit varied work conditions remain a challenge of widespread interest for a variety of applications.Shape memory polymer exhibits morphing and modulus changing over temperature changing provides a promising material to adjust the friction process.Herein,we investigated the tribological properties of shape memory cyanate ester(SMCE)under different conditions.The SMCE exhibits the tribological behavior of good friction material with stable high coefficient of friction(COF)and a low wear rate.Besides,the COF increases and wear rate decreases with the temperature increasing show the tunable friction property of the SMCE.We propose a new model of wear-compensation through shape recovery to explain the adjustable friction behavior of thermal-responsive polymer from the aspect of shape recovery and energy conversion.This study provides a high-performance friction material and paves the route for the application of shape memory polymer(SMP)in tribology field with tunable property.
基金the National Natural Science Foundation of China(Nos.22072167,22202218)the Jiangsu Natural Science Funds for Young Scholar(No.BK20211093)is greatly appreciated.
文摘The selective conversion of CO_(2)and NH_(3)into valuable nitriles presents significant potential for CO_(2)utilization.In this study,we exploited the synergistic interplay between silicon and fluoride to augment the nickel-catalyzed reductive cyanation of aryl pseudohalides containing silyl groups,utilizing CO_(2)and NH_(3)as the CN source.Our methodology exhibited exceptional compatibility with diverse functional groups,such as alcohols,ketones,ethers,esters,nitriles,olefins,pyridines,and quinolines,among others,as demonstrated by the successful synthesis of 58 different nitriles.Notably,we achieved high yields in the preparation of bifunctionalized molecules,including intermediates for perampanel,derived from osilylaryl triflates,which are well-known as aryne precursors.Remarkably,no degradation of substrates or formation of aryne intermediates were observed.Mechanistic studies imply that the formation of pentacoordinated silyl isocyanate intermediates is crucial for the key C-C coupling step and the presence of vicinal silyl group in the substrate is beneficial to further make this step kinetically favorable.
基金support of this work by the funding of the National Natural Science Foundation of China(No.22371269)the State Key Laboratory of Elementoorganic Chemistry Nankai University(No.202001)+1 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB0450301)the Open Project of Key Laboratory of Organosilicon Chemistry,and Material Technology of Ministry of Education,Hangzhou Normal University(No.KFJJ2022013)。
文摘Herein,we developed the first example of copper-catalyzed silicon radical-initiated 1,4-silylcyanation of unactivated 1,3-enynes,which provided an efficient method to access CN-bearing tri-and tetrasubstituted homoallenylsilane derivatives in high yields with excellent regioselectivities.This protocol featured good functional group compatibility and broad substrate scopes,enabling the formation of C-Si bond under cheap copper catalyst with a low loading.Furthermore,this means showed potential application value in the late-stage functionalization of natural products.
基金Financial support from National Key R&D Program of China(No.2023YFA1507203)National Natural Science Foundation of China(Nos.22371149,22188101)+2 种基金the Fundamental Research Funds for the Central Universities(No.63224098)Frontiers Science Center for New Organic Matter,Nankai University(No.63181206)the Haihe Laboratory of Sustainable Chemical Transformations for financial support。
文摘Herein,a metal-free electrochemical demethoxyl-cyanation of methoxyarenes via aromatic nucleophilic substitution(S_(N)Ar) using TMSCN as a cheap cyanide source under mild conditions has been presented.This transformation utilizes commercially available reagents,cheap electrodes,and simple equipment.Diverse aryl nitriles were successfully obtained in a direct and efficient way with broad substrate scope,excellent functional group tolerance,and selective C-O bond cleavage.Furthermore,late-stage modification of biorelevant compounds and gram-scale synthesis highlighted the potential application of the strategy.Mechanistic investigations suggest that the arene cation radical was considered as the key intermediate for the transformation,and undergoing the followed S_(N)Ar process.
基金supported by the National Natural Science Foundation of China(21373202,21525315)~~
文摘Covalent triazine-based frameworks（CTFs） are important microporous materials with a wide range of applications.Here,we demonstrate an environmentally benign and economic synthetic pathway to CTFs.The monomers used for CTFs,aromatic nitriles,were obtained by cyanation using nontoxic potassium hexacyanoferrate（Ⅱ） in place of commonly used toxic cyanides.Then,the CTFs were synthesized by trimerization of the corresponding cyano monomers in molten zinc chloride.A series of CTFs was synthesized,and the highest Brunauer-Emmett-Teller surface area measured in this series was 2404 m^2/g.Among the synthesized CTFs,CTF_（DCP） exhibited excellent CO_2 adsorption properties,with a CO_2 uptake of 225 mg/g at 0℃.
基金the National Natural Science Foundation of China(Nos.51603029 and 51773028)China Postdoctoral Science Foundation(No.2017M623001)National Postdoctoral Program for Innovative Talents(No.BX201700044).
文摘Low dielectric in terlayer films have become an important element to ensure the development of the microelectr onics industry.A kind of flexible interlayer dielectrics,polyarylene ether nitrile/bisphenol A cyanate ester(PEN/BADCy)film,with good thermal stability and low frequency dependence,has been developed by solution casting method.Herein,materials were designed to incorporate bisphenol A cyanate ester as a part of blend,contributing to the frequency stability and structural integrity.The morphological study combined with electron microscopy revealed the uniform and flexible microstructure information with controllable morphology through self-polymerization of cyanate esters with different prepolymerization time and curing temperatures.The dielectric films could present high thermal stability with Tg>180℃.Significant improvement in the dielectric properties was achieved for the dielectric constant and loss was much stabler than neat PEN over the frequency range from 100 Hz to 5 MHz.When the prepolymerization time was 3h and final curing temperature reached 230℃,the dielectric constant and dielectric loss of the films were 3.36 and 0.013 at 100 kHz,respectively.The dimensional stability(CTE=53.67×10^-6 K^-1)was confirmed and con sidered beneficial to use as an in terlayer dielectrics.
基金the University of Kurdistan Research Council for the partial support of this work
文摘A fast and efficient method is described for the one-pot synthesis of 2,4（1H,3H）-quinazolinediones by cyclization reaction of anthranilic acid derivatives with potassium cyanate and acetic acid in PEG.Good to high yields of the products obtain in short reaction times with simple work-up.
文摘A new type of the nanometer particles and epoxy/bismaleimide-triazine nanocomposites were prepared using a nanometer silica(nano-SiO(_2)),a 4,5-epoxycyclohexane 1,2-dicarboxylic acid dilycidyl(TDE-85)epoxy resin,a 4,4'-bismaleimidodiphenymethane(BMI)and a bisphenol a dicyanate(BADCy).The properties of nano-SiOJTDE-85/BMI/BADCy composites,such as mechanical and thermal properties,were systemically investigated in detail by mechanical measurement,scanning electron microscope(SEM),dynamic mechanical analysis(DMA)and thermogravimetric analysis(TGA).The experimental results showed that the addition of the appropriate amount of nano-SiO(_2):could improve the impact strength and the flexural strength of the nano-SiO(_2)/TDE-85/BMI/BADCy composites.Simultaneously,the thermal stability of the blends was found to be higher than that of the TDE-85/BMI/BADCy copolymers.
