Cyclic polymers are a class of polymers that feature endless topology,and the synthesis of cyclic polymers has attracted the attention of many researchers.Herein,cyclic polymers were efficiently constructed by self-fo...Cyclic polymers are a class of polymers that feature endless topology,and the synthesis of cyclic polymers has attracted the attention of many researchers.Herein,cyclic polymers were efficiently constructed by self-folding cyclization technique at high concentrations.Linear poly((oligo(ethylene glycol)acrylate)-co-(dodecyl acrylate))(P(OEGA-co-DDA))precursors with different ratios of hydrophilic and hydrophobic moieties were synthesized by reversible addition-fragmentation chain transfer(RAFT)polymerization using a bifunctional chain transfer agent with two anthryl end groups.The amphiphilic linear precursors underwent the self-folding process to generate polymeric nanoparticles in water.By irradiating the aqueous solution of the nanoparticles with 365 nm UV light,cyclic polymers were synthesized successfully via coupling of anthryl groups.The effects of the ratios of hydrophilic and hydrophobic moieties in linear P(OEGA-co-DDA)copolymers and polymer concentration on the purity of the obtained cyclic polymers were explored in detail via ^(1)H nuclear magnetic resonance(^(1)H NMR),dynamic light scattering(DLS),UV‒visible(vis)analysis,three-detection size exclusion chromatography(TD-SEC)and transmission electron microscopy(TEM).It was found that by adjusting the content of the hydrophilic segments in linear precursors,single chain polymeric nanoparticles(SCPNs)can be generated at high polymer concentrations.Therefore,cyclic polymers with high purity can be constructed efficiently.This method overcomes the limitation of traditional ring-closure method,which is typically conducted in highly dilute conditions,providing an efficient method for the scalable preparation of cyclic polymers.展开更多
Cyclic polymers exhibit distinct properties compared with their linear counterparts due to the lack of chain ends.However,the scalable synthesis of cyclic polymers remains a major challenge,especially for ring-closure...Cyclic polymers exhibit distinct properties compared with their linear counterparts due to the lack of chain ends.However,the scalable synthesis of cyclic polymers remains a major challenge,especially for ring-closure method.Herein,we report a novel strategy for large-scale preparation of cyclic polymers,which relies on the prior self-folding of anthracene-telechelic amphiphilic random copolymers(poly((oligo(ethylene glycol)acrylate)-co-(dodecyl acrylate)),P(OEGA-co-DDA))into single-chain polymeric nanoparticles(SCPNs)in water.Subsequent ultraviolet(UV)-induced cyclization occurs in the hydrophobic nano-domain.The formation of SCPNs leads to a shortened distance between the end groups of the linear precursors and spatially separated cyclization loci,and significantly enhances the efficiency of UV-induced cyclization.This self-folding technique permits access to the synthesis of cyclic polymers not only with high molecular weights(M_(n)>10^(5) g/mol),but also in a decent scale(40 g/L),breaking through the limitations of ring-closure method.Furthermore,the dense pendants of the copolymers can magnify the macromolecules by increasing the mass density along the backbones,thus making the polymers more readily detectable by the microscopy.The transmission electron microscopy(TEM)and atomic force microscopy(AFM)images allow us to observe the topological structures directly and provide crucial evidence to confirm the cyclization.展开更多
Environmental-stimulus-triggered self-folding mechanisms have found promising applications in many engineering fields.Recently,a water-activated self-folding procedure has been designed by using the electrospun polyvi...Environmental-stimulus-triggered self-folding mechanisms have found promising applications in many engineering fields.Recently,a water-activated self-folding procedure has been designed by using the electrospun polyvinyl acetate(PVAc)fiber mat which contains high tensile residual stresses in the vitrified fibers during the spinning processes.The water permeation initiates plasticization of PVAc fiber mat and leads to a material shrinkage.When water diffusion starts at the top surface of a PVAc sheet,a shrinkage variation along the diffusion pathway forms a bending hinge on the sheet,which has been demonstrated in 3D origami design.To capture the water-triggered plasticization mechanism and chemomechanical coupling deformation compatibility,a consistent finite deformation viscoplastic model is developed for the PVAc fiber mat under coupled chemomechanical loading conditions.The residual stress and‘fixed’strain are modeled through the unrecoverable plastic strain in the PVAc fiber mat.As water permeates into the PVAc fiber mat,the induced increase in mixing entropy lowers the glass transition temperature of the material,and results in a gradual relaxation of the fixed viscoplastic strain.A non-Fickian diffusion model suitable for glassy material is adopted to capture the water permeation in the PVAc fiber mat.After calibrated and validated by a series of experiments,the proposed model is implemented in ABAQUS software to simulate the water-activated self-folding of PVAc sheet.The numerical example for a typical origami design suggests a promising engineering application prospect.展开更多
The use of non-smart materials in structural components and kinematic pairs allows for flexible assembly in practical applications and is promising for aerospace applications.However,this approach can result in a comp...The use of non-smart materials in structural components and kinematic pairs allows for flexible assembly in practical applications and is promising for aerospace applications.However,this approach can result in a complex structure and excessive kinematic pairs,which limits its potential applications due to the difficulty in controlling and actuating the mechanism.While smart materials have been integrated into certain mechanisms,such integration is generally considered a unique design for specific cases and lacks universality.Therefore,organically combining universal mechanism design with smart materials and 4D printing technology,innovating mechanism types,and systematically exploring the interplay between structural design and morphing control remains an open research area.In this work,a novel form-controlled planar folding mechanism is proposed,which seamlessly integrates the control and actuation system with the structural components and kinematic pairs based on the combination of universal mechanism design with smart materials and 4D printing technology,while achieving self-controlled dimensional ratio adjustment under a predetermined thermal excitation.The design characteristics of the mechanism are analyzed,and the required structural design parameters for the preprogrammed design are derived using a kinematic model.Using smart materials and 4D printing technology,folding programs based on material properties and control programs based on manufacturing parameters are encoded into the form-controlled rod to achieve the preprogrammed design of the mechanism.Finally,two sets of prototype mechanisms are printed to validate the feasibility of the design,the effectiveness of the morphing control programs,and the accuracy of the theoretical analysis.This mechanism not only promotes innovation in mechanism design methods but also shows exceptional promise in satellite calibration devices and spacecraft walking systems.展开更多
基金The financial support from the National Natural Science Foundation of China(Nos.22201276,22131010,52021002)the Fundamental Research Funds for the Central Universities(No.WK2060000012)is gratefully acknowledged.
文摘Cyclic polymers are a class of polymers that feature endless topology,and the synthesis of cyclic polymers has attracted the attention of many researchers.Herein,cyclic polymers were efficiently constructed by self-folding cyclization technique at high concentrations.Linear poly((oligo(ethylene glycol)acrylate)-co-(dodecyl acrylate))(P(OEGA-co-DDA))precursors with different ratios of hydrophilic and hydrophobic moieties were synthesized by reversible addition-fragmentation chain transfer(RAFT)polymerization using a bifunctional chain transfer agent with two anthryl end groups.The amphiphilic linear precursors underwent the self-folding process to generate polymeric nanoparticles in water.By irradiating the aqueous solution of the nanoparticles with 365 nm UV light,cyclic polymers were synthesized successfully via coupling of anthryl groups.The effects of the ratios of hydrophilic and hydrophobic moieties in linear P(OEGA-co-DDA)copolymers and polymer concentration on the purity of the obtained cyclic polymers were explored in detail via ^(1)H nuclear magnetic resonance(^(1)H NMR),dynamic light scattering(DLS),UV‒visible(vis)analysis,three-detection size exclusion chromatography(TD-SEC)and transmission electron microscopy(TEM).It was found that by adjusting the content of the hydrophilic segments in linear precursors,single chain polymeric nanoparticles(SCPNs)can be generated at high polymer concentrations.Therefore,cyclic polymers with high purity can be constructed efficiently.This method overcomes the limitation of traditional ring-closure method,which is typically conducted in highly dilute conditions,providing an efficient method for the scalable preparation of cyclic polymers.
基金supported by the National Natural Science Foundation of China(22201276,22131010,52021002)the Fundamental Research Funds for the Central Universities(WK2060000012).
文摘Cyclic polymers exhibit distinct properties compared with their linear counterparts due to the lack of chain ends.However,the scalable synthesis of cyclic polymers remains a major challenge,especially for ring-closure method.Herein,we report a novel strategy for large-scale preparation of cyclic polymers,which relies on the prior self-folding of anthracene-telechelic amphiphilic random copolymers(poly((oligo(ethylene glycol)acrylate)-co-(dodecyl acrylate)),P(OEGA-co-DDA))into single-chain polymeric nanoparticles(SCPNs)in water.Subsequent ultraviolet(UV)-induced cyclization occurs in the hydrophobic nano-domain.The formation of SCPNs leads to a shortened distance between the end groups of the linear precursors and spatially separated cyclization loci,and significantly enhances the efficiency of UV-induced cyclization.This self-folding technique permits access to the synthesis of cyclic polymers not only with high molecular weights(M_(n)>10^(5) g/mol),but also in a decent scale(40 g/L),breaking through the limitations of ring-closure method.Furthermore,the dense pendants of the copolymers can magnify the macromolecules by increasing the mass density along the backbones,thus making the polymers more readily detectable by the microscopy.The transmission electron microscopy(TEM)and atomic force microscopy(AFM)images allow us to observe the topological structures directly and provide crucial evidence to confirm the cyclization.
基金The authors would like to acknowledge with great gratitude to the supports of the National Natural Science Foundation of China(Grant Nos:11772124 and 11922206)the Science Foundation of Hunan Province(Grant No:2018JJ3027).
文摘Environmental-stimulus-triggered self-folding mechanisms have found promising applications in many engineering fields.Recently,a water-activated self-folding procedure has been designed by using the electrospun polyvinyl acetate(PVAc)fiber mat which contains high tensile residual stresses in the vitrified fibers during the spinning processes.The water permeation initiates plasticization of PVAc fiber mat and leads to a material shrinkage.When water diffusion starts at the top surface of a PVAc sheet,a shrinkage variation along the diffusion pathway forms a bending hinge on the sheet,which has been demonstrated in 3D origami design.To capture the water-triggered plasticization mechanism and chemomechanical coupling deformation compatibility,a consistent finite deformation viscoplastic model is developed for the PVAc fiber mat under coupled chemomechanical loading conditions.The residual stress and‘fixed’strain are modeled through the unrecoverable plastic strain in the PVAc fiber mat.As water permeates into the PVAc fiber mat,the induced increase in mixing entropy lowers the glass transition temperature of the material,and results in a gradual relaxation of the fixed viscoplastic strain.A non-Fickian diffusion model suitable for glassy material is adopted to capture the water permeation in the PVAc fiber mat.After calibrated and validated by a series of experiments,the proposed model is implemented in ABAQUS software to simulate the water-activated self-folding of PVAc sheet.The numerical example for a typical origami design suggests a promising engineering application prospect.
基金Supported by National Natural Science Foundation of China(Grant No.52175019)Beijing Municipal Natural Science Foundations(Grant Nos.3212009 and L222038)Beijing Municipal Key Laboratory of Space-ground Interconnection and Convergence of China.
文摘The use of non-smart materials in structural components and kinematic pairs allows for flexible assembly in practical applications and is promising for aerospace applications.However,this approach can result in a complex structure and excessive kinematic pairs,which limits its potential applications due to the difficulty in controlling and actuating the mechanism.While smart materials have been integrated into certain mechanisms,such integration is generally considered a unique design for specific cases and lacks universality.Therefore,organically combining universal mechanism design with smart materials and 4D printing technology,innovating mechanism types,and systematically exploring the interplay between structural design and morphing control remains an open research area.In this work,a novel form-controlled planar folding mechanism is proposed,which seamlessly integrates the control and actuation system with the structural components and kinematic pairs based on the combination of universal mechanism design with smart materials and 4D printing technology,while achieving self-controlled dimensional ratio adjustment under a predetermined thermal excitation.The design characteristics of the mechanism are analyzed,and the required structural design parameters for the preprogrammed design are derived using a kinematic model.Using smart materials and 4D printing technology,folding programs based on material properties and control programs based on manufacturing parameters are encoded into the form-controlled rod to achieve the preprogrammed design of the mechanism.Finally,two sets of prototype mechanisms are printed to validate the feasibility of the design,the effectiveness of the morphing control programs,and the accuracy of the theoretical analysis.This mechanism not only promotes innovation in mechanism design methods but also shows exceptional promise in satellite calibration devices and spacecraft walking systems.
