An effective strategy for enhancing the heat resistance of polystyrene(PS)with regard to its glass transition temperature(T_(g))involves the anionic solution copolymerization of a-methylstyrene(AMS)with styrene(St),ty...An effective strategy for enhancing the heat resistance of polystyrene(PS)with regard to its glass transition temperature(T_(g))involves the anionic solution copolymerization of a-methylstyrene(AMS)with styrene(St),typically requires much lower temperature(-25℃)and multistep monomer feeding to achieve higher number-average molecular weight(M_(n))block copolymers.However,the anionic copolymerization of AMS and St under the mild temperature remains largely unexplored.This study systematically investigated the anionic copolymerization of AMS and St using n-BuLi in nonpolar solvent(-25℃ to 25℃)through both one-step and two-step approaches.We demonstrated that one-step copolymerization at 25℃ yielded only 1-3 terminal AMS units,with higher feed ratios(5 wt%-20 wt%)increasing AMS incorporation but reducing the exact molecular weight(MW)due to enhanced depolymerization,as evidenced by MALDI-TOF MS.Temperature-controlled AMS conversion at-15℃ achieved 98%AMS conversion(5 wt% feed)by suppressing side reactions and lowering the[M]_(e),while 50℃(near T_(C))almost prevented incorporation.Despite t-BuOK regulation induced broader PDI(1.24)via reactive[(polymer-Li)OR]K intermediates,while other systems showed narrow distributions,t-BuOK outperformed THF in enhancing AMS incorporation via efficient ion pair dissociation.In comparison,the two-step polymerization approach demonstrated superior performance,achieving both higher AMS conversion efficiency and preferential incorporation at the initiation end.At a 20 wt%AMS feed ratio,this method yielded copolymer chains containing up to 6 AMS units on average.Thermal analysis revealed a composition-dependent single T_(g),which exhibited a systematic increase with higher AMS incorporation content.These results collectively demonstrate the precise control over AMS incorporation and heat resistance achievable through the manipulation of polymerization conditions.展开更多
Due to the structure characteristics of huge macromolecular size and the very low motion feature of the polymer chain which is very difficult to arrange regularly their long chain into the three dimensional space,thus...Due to the structure characteristics of huge macromolecular size and the very low motion feature of the polymer chain which is very difficult to arrange regularly their long chain into the three dimensional space,thus the polymer will incompletely crystallize except for the macroscopic single crystal of polydiacetylene polymerized by means of solid state crystalline polymerization.展开更多
Colloidal molecules exhibit unique electronic,optical,and magnetic properties owing to their molecular-like configurations and coupling effects,making them promising building blocks for multifunctional materials.Howev...Colloidal molecules exhibit unique electronic,optical,and magnetic properties owing to their molecular-like configurations and coupling effects,making them promising building blocks for multifunctional materials.However,achieving precise and controllable assembly of isotropic nanoparticles with high yields remains a great challenge.In this study,we present a synergistic strategy that integrates molecular dynamics simulations with interpretable machine learning to develop a programmable assembly system based on block copolymers and DNA-functionalized nanoparticles.Our simulation results reveal that block copolymer modification facilitates stepwise control over surface phase separation and nanoparticle coassembly,thereby enhancing structural stability and efficiently suppressing disordered aggregation of atom-like nanoparticles.Furthermore,we demonstrated that precise,controllable,and programmable assembly of colloidal molecules can be achieved through rational DNA sequence design.SHapley Additive exPlanations(SHAP)analysis identified key structural descriptors that govern assembly outcomes and elucidated their underlying mechanistic roles.This work not only deepens the understanding of colloidal molecule assembly mechanisms but also lays a theoretical foundation for the rational design of functional colloidal architectures in nanomaterial science.展开更多
In 2024,the MOE Key Laboratory of Macromolecular Synthesis and Functionalization at Zhejiang University continued its impactful researches across five core areas.In controllable catalytic polymerization,organoboron ca...In 2024,the MOE Key Laboratory of Macromolecular Synthesis and Functionalization at Zhejiang University continued its impactful researches across five core areas.In controllable catalytic polymerization,organoboron catalysts were developed for CO₂copolymerization and novel photoresist materials.Studies in microstructure and rheology elucidated universal deformation modes in graphene-based 2D membranes and improved graphene fiber properties through shear alignment engineering,defect control,and enhanced interlayer entanglement.For separating functional polymers,Janus membranes and channels were created for multiphase separation,liquid-phase molecular layer-by-layer deposition technique was developed to fabricate aromatic polyamide nanofilms,and the harmonic amide bond density was established as a valuable parameter for polyamide structural analysis.In biomedical functional polymers,a sustainable carboxyl-ester transesterification strategy was proposed for upcycling poly(ethylene terephthalate)(PET)waste into biodegradable plastics.Additionally,immunocompatible biomaterials were designed utilizing zwitterionic polypeptides and albumin-derived coatings,and Cu2+-phenolic nanoflower was designed to combat fungal infections by combining cuproptosis and cell wall digestion.Further,the researchers developed a gelatin-DOPA-knob/fibrinogen hydrogel to achieve rapid and robust hemostatic sealing,utilized a double-network polyelectrolyte-coated hydrogel for enhancing endothelialization of left atrial appendage(LAA)occluders,and the researchers also demonstrated that image-guided high-intensity focused ultrasound enables manipulation of shape-memory polymers.Finally,in the realm of photo-electro-magnetic functional polymers,precise control of through-space conjugation was shown to enhance organic luminescence.Topologically structured hydrogels were revealed to exhibit autonomous actuation.Also,solar-driven photothermal ion pumps were developed for selective lithium extraction from seawater,and high-performance non-solvated C60 single-crystal films were prepared via facile bar coating.Lastly,the researchers demonstrated outstanding dielectric properties of polyethylene(PE)lamellar single crystals.The relevant works are reviewed in this paper.展开更多
Heterogeneous polymerization represents a widely employed method in the polyolefin industry.In recent years,various heterogenization strategies for late transition metal catalysts have been developed,enabling effectiv...Heterogeneous polymerization represents a widely employed method in the polyolefin industry.In recent years,various heterogenization strategies for late transition metal catalysts have been developed,enabling effective control of polymer morphology and optimization of catalytic performance.However,while most studies have focused on designing anchoring groups and advancing support approaches,systematic investigations into how the support influences the catalytic behavior of the late transition metal catalysts.In this work,we fabricated supported α-diimine nickel catalysts by functionalizing the ligand with alkyl alcohol chains of varying lengths and supporting them onto MgCl_(2)supports.The ethylene polymerization behavior of these catalysts was then investigated.By precisely adjusting the alkyl alcohol chain length,the distance between the catalytically active metal center and the support surface was modulated.This approach demonstrates that support-induced steric hindrance effect can be effectively regulated by controlling the separation distance between the metal center and the support surface.展开更多
Charge-transfer complexes(CTCs)have emerged as promising n-type organic thermoelectric(TE)materials due to their inherent high electrical conductivity and tunable transport polarities.In this study,we performed a comp...Charge-transfer complexes(CTCs)have emerged as promising n-type organic thermoelectric(TE)materials due to their inherent high electrical conductivity and tunable transport polarities.In this study,we performed a comprehensive first-principles investigation on the TE properties of nine CTCs comprised of 2,7-dialkyl[1]benzothieno[3,2-b][1]benzothiophenes(CnBTBT,n=4,8,12)as donors and fluorinated derivatives of tetracyanoquinodimethane(F_(m)TCNQ,m=0,2,4)as acceptors,aiming to identify high-performance n-type organic TE materials and elucidate the underlying structure-property relationships.Our calculation results,based on the Boltzmann transport equation and deformation potential theory,reveal that the length of the alkyl side chains and the number of fluorine substitutions significantly impact their electronic structures and TE properties.Notably,the CnBTBT-F_(m)TCNQ CTCs with shorter alkyl chains and more fluorine substitution demonstrate superior n-type characteristics,particularly C4BTBT-F4TCNQ,which achieves an excellent power factor of 671µW cm^(-1) K^(-2) at an optimal charge carrier concentration.Our findings not only clarify the critical role of molecular engineering in CTC-based TE materials but also provide valuable guidance for developing high-efficiency organic TE materials with versatile practical applications.展开更多
Inspired by the self-polymerization and strong adhesion characteristics of dopamine in aqueous conditions, a novel hydrophilic nanofiltration （NF） membrane was fabricated by simply dipping polysulfone （PSf） ultraf...Inspired by the self-polymerization and strong adhesion characteristics of dopamine in aqueous conditions, a novel hydrophilic nanofiltration （NF） membrane was fabricated by simply dipping polysulfone （PSf） ultrafiltration （UF） substrate in dopamine solution. The changes in surface chemical composition and morphology of membranes were determined by Fourier transform infrared spectroscopy （FTIR-ATR）, X-ray photoelectron spectroscopy （XPS）, scanning electron microscopy （SEM） and atomic force microscopy （AFM）. The experimental results indicated that the self-polymerized dopamine formed an ultrathin and defect-free barrier layer on the PSf UF membrane. The surface hydrophilicity of membranes was evaluated through water contact angle measurements. It was found that membrane hydrophilicity was significantly improved after coating a polydopamine （pDA） layer, especially after double coating. The dyes filtration experiments showed that the double-coated membranes were able to reject completely the dyes of brilliant blue, congo red and methyl orange with a pure water flux of 83.7 L/（mE.h） under 0.6 MPa. The zeta potential determination revealed the positively-charged characteristics of PSf/pDA composite membrane in NF process. The salt rejection of the membranes was characterized by 0.01 mmol/L of salts filtration experiment. It was demonstrated that the salts rejections followed the sequence： NaC1 〈 NaaSO4 〈 MgSO4 〈 MgC12 〈 CaCl2, and the rejection to CaC12 reached 68.7%. Moreover, the composite NF membranes showed a good stability in water-phase filtration process.展开更多
A series of stable waterborne polysiloxaneurethane （WPSUR） dispersions were prepared using amino-terminated polydimethylsiloxane （NS）, dimethylolpropionic acid （DMPA）, castor oil, polypropylene glycol and toluen...A series of stable waterborne polysiloxaneurethane （WPSUR） dispersions were prepared using amino-terminated polydimethylsiloxane （NS）, dimethylolpropionic acid （DMPA）, castor oil, polypropylene glycol and toluene diisocyanate. Meanwhile, NS with different molecular weights was synthesized and used as the soft co-segment. Effects of types and contents of soft co-segments as well as chain extenders on the thermal degradation and stability for WPSUR films were examined. Results reveal that WPSUR films exhibit excellent water resistance and mechanical properties as compared with pure polyurethane （PU） films, and the NS soft co-segment possesses a remarkable effect on the second stage （stage Ⅱ）, while the content of the hard segment is propitious to the initial stage （stage Ⅰ）. Moreover, the highest temperature of stage Ⅱ （T2m） for WPSUR films using NS as soft co-segment is 413℃, approximately being 30℃ higher than that of those typical PUs using HDA and APDMS as the chain extenders, respectively.展开更多
Three well-defined diblock copolymers ofpoly（methyl methacrylate-b-methacrylic acid） （P（MMA-b-MAA）） were synthesized using atom transfer radical polymerization method and varying poly（methacrylic acid） （PMAA...Three well-defined diblock copolymers ofpoly（methyl methacrylate-b-methacrylic acid） （P（MMA-b-MAA）） were synthesized using atom transfer radical polymerization method and varying poly（methacrylic acid） （PMAA） chain lengths. These copolymers were blended with PVC to fabricate porous membranes via phase inversion process. Membrane morphologies were observed by scanning electron microscopy （SEM）, and chemical composition changes of the membrane surfaces were measured by X-ray photoelectron spectroscopy （XPS）. Static and dynamic protein adsorption experiments were used to evaluate antifouling properties of the blend membranes. It was found that, the blend membranes containing longer PMAA arm length showed lower static protein adsorption, higher water permeation flux and better protein solution flux recovery.展开更多
Two new chiral ionic liquids, 1 -((-)-menthoxycarbonylmethylene)-3-methylimidazolium hexafluorophosphateand 1-((-)-menthoxycarbonylmethylene)-3-hexadecylimidazolium hexafluorophosphate, were designed an d prepared. Th...Two new chiral ionic liquids, 1 -((-)-menthoxycarbonylmethylene)-3-methylimidazolium hexafluorophosphateand 1-((-)-menthoxycarbonylmethylene)-3-hexadecylimidazolium hexafluorophosphate, were designed an d prepared. Theirchemical structures were characterized by ~1H-NMR. Reverse atom transfer radical polymerization of methyl methacrylate(MMA) in these two ionic liquids was carried out using AIBN/CuCl_2/bipy as the initiating system. The resultant well-definedpolymethyl methacrylate (PMMA) was employed as a macroinitiator to induce the atom transfer radical polymerization ofmenthyl methacrylate (MnMA) in chlorobenzene, which yielded a PMMA-b-PMnMA diblock copolymer with narrow polydispersity.展开更多
Functionalized aliphatic polyesters attract increasing attentions as biocompatible and biodegradable polymers with broad applications in biological science. In this contribution, we propose a facile and controllable s...Functionalized aliphatic polyesters attract increasing attentions as biocompatible and biodegradable polymers with broad applications in biological science. In this contribution, we propose a facile and controllable synthetic technique for functional poly(ε-caprolactone)(PCL) via Janus polymerization, which comprises cationic ring-opening copolymerization (ROP) of ε-caprolactone (CL) with 3,3-bis(chloromethyl)oxacyclobutane (CO) and (coordinated) anionic ROP of CL at a single propagating chain by rare earth metal triflates (RE(OTf)3)and propylene oxide, thus generating block copolymers in one step. The compositions of the copolymers of poly(CLb-(CL-r-CO)) can be modulated by various RE(OTf)3. Scandium triflate catalyzes Janus polymerization to yield the copolymers containing the highest CO contents among all the RE(OTf)3 catalysts used with complete conversion of CL. The chlorine in CO repeating units is ready to be transferred into azide group which affords the modification sites to react with 9-ethynyl-9-fluorenol and mPEG-alkyne, respectively, via copper(I)-catalyzed azide-alkyne cycloaddition reaction with quantitative conversions of azides, as confirmed by FTIR analyses. According to NMR and SEC analyses, copolymers (PCC-g-PEG) bearing a homo-PCL block and a PEG-grafted block of poly(CO-co-CL) demonstrate well-defined chemical structures. The investigations on thermal properties reveal the strong phase separation between PCL and PEG blocks. The amphiphilic PCC-g-PEG is able to sei住assemble into micelles in aqueous solution while cylindrical and lamellar morphologies are observed in bulk. We provide an efficient protocol to synthesize functional PCL combining onestep Janus polymerization and precise post-polymerization click reaction.展开更多
Acryloyl terminated Poly (ethyleneoxide)macromonomers (PEO-A) with different PEO chain lengths have been prepared by deactivation of PEO alkoxide with acryloyl chloride. A new kind of amphiphilic polystyrene-g-poly (e...Acryloyl terminated Poly (ethyleneoxide)macromonomers (PEO-A) with different PEO chain lengths have been prepared by deactivation of PEO alkoxide with acryloyl chloride. A new kind of amphiphilic polystyrene-g-poly (ethylene oxide)graft copolymer containing both microphase separated and PEO side chain structures has been synthesized from radical copolymerization of PEO-A macromonomer with styrene. After careful purification by a newly-developed method called 'selective dissolution', the well-defined structure of the purified copolymers was confirmed by IR, ~1H-NMR and GPC. Various experimental parameters controlling the copolymerization were studied in detail. The results indicated that the feed ratio of styrene to macromonomer(S/M) was the most important determining factor for the composition of the copolymers. A detailed 'comb- model' was proposed to describe the molecular structure of the graft copolymers. Finally, this amphiphilic graft copolymers may readily form microphase separated structures as clearly indicated by transmission electron microscopy.展开更多
We reported an approach to reconstruct the complex phase morphology of impact polypropylene copolymer （IPC） with core-shell dispersed particles and to optimize its toughness in approximate shear condition. The molte...We reported an approach to reconstruct the complex phase morphology of impact polypropylene copolymer （IPC） with core-shell dispersed particles and to optimize its toughness in approximate shear condition. The molten-state annealing results indicate that the phase structure with core-shell dispersed particles is unstable and could be completely destroyed by static annealing, resulting in the degradation of impact strength. By using a co-rotating twin screw extruder, we found that the dispersed particle with core-shell structure could be rebuilt in appropriate condition with the recovery of excellent impact strength due to both the huge interfacial tension during solidification and the great difference in viscosity of components. Results reveal that almost all the extruded IPCs show the impact strength 60%-90% higher than that of annealed IPCs at room temperature. And the twice-extruded IPC shows the highest impact strength, 446% higher than that of IPC annealed for 30 min. As for low temperature tests, the impact strength of extruded IPCs also increases by 33%-58%. According to adjusting the processing conditions including extrusion speed, extrusion frequency and temperature, an optimization of toughness was well established.展开更多
Janus polymerization is featured as a combination of cationic and anionic growing ends in one living polymer chain. In the copolymerization of THF and CL catalyzed by lutetium triflates and initiated by propylene oxid...Janus polymerization is featured as a combination of cationic and anionic growing ends in one living polymer chain. In the copolymerization of THF and CL catalyzed by lutetium triflates and initiated by propylene oxide, three stages are identified by kinetic study including(1) fast cationic polymerization with slow anionic one,(2) fast anionic polymerization with dormant cationic one, and(3)reactivation of cationic polymerization with coupling of anionic and cationic chain ends. In this work, density functional theory(DFT)calculation is employed to investigate the reaction details of ionic polymerization and dormancy. A “tripedal crow” configuration is proposed to illustrate the unique high-coordinated ligand exchange configuration in anionic polymerization in different stages. The trigger of dormancy is determined as chain structures rather than concentration of triflate anion according to both calculation and experimental results.展开更多
Ethylene/propylene-random-copolymer （PPR）/clay nanocomposites were prepared by two-stage melt blending. Four types of compatibilizers, including an ethylene-octene copolymer grafted maleic anhydride （POE-g-MA） and...Ethylene/propylene-random-copolymer （PPR）/clay nanocomposites were prepared by two-stage melt blending. Four types of compatibilizers, including an ethylene-octene copolymer grafted maleic anhydride （POE-g-MA） and three maleic-anhydride-grafted polypropylenes （PP-g-MA） with different melt flow indexes （MFI）, were used to improve the dispersion of organic clay in matrix. On the other hand, the effects of organic montmorillonite （OMMT） content on the nanocomposite structure in terms of clay dispersion in PPR matrix, thermal behavior and tensile properties were also studied. The X-ray diffraction （XRD） and transmission electron microscopy （TEM） results show that the organic clay layers are mainly intercalated and partially exfoliated in the nanocomposites. Moreover, a PP-g-MA compatibilizer （compatibilizer B） having high MFI can greatly increase the interlayer spacing of the clay as compared with other compatibilizers. With the introduction of compatibilizer D （POE-g-MA）, most of the clays are dispersed into the POE phase, and the shape of the dispersed OMMT appears elliptic, which differs from the strip of PP-g-MA. Compared with virgin PPR, the Young＇s modulus of the nanocomposite evidently increases when a compatibilizer C （PP-g-MA） with medium MFI is used. For the nanocomposites with compatibilizer B and C, their crystallinities （Xc） increase as compared with that of the virgin PPR. Furthermore, the increase of OMMT loadings presents little effect on the melt temperature （Tc） of the PPR/OMMT nanocomposites, and slight effect on their crystallization temperature （Tc）. Only compatibilizer B can lead to a marked increases in crystallinity and Tc of the nanocomposite when the OMMT content is 2 wt%.展开更多
The influences of shearing conducted by a Brabender behavior of a commercial impact polypropylene copolymer （IPC） rheometer on phase morphology, thermal and rheological were studied. The crystallization and melting ...The influences of shearing conducted by a Brabender behavior of a commercial impact polypropylene copolymer （IPC） rheometer on phase morphology, thermal and rheological were studied. The crystallization and melting traces show that short-time annealing at 210℃ is unable to completely erase the influence of shearing on the samples. When the samples which were treated at a rotation speed of 80 r/rnin crystallize at a cooling rate of 10 K/min, their Tcs and corresponding Tms obviously rise with the increase of shearing time. Furthermore, the POM results reveal that the shearing can lead to the formation of shish-kebab and the shish-kebab amount is proportional to shearing time. The rheological measurement results show that the treated samples exhibit different G＇-ω dependences. The ＇second plateau＇ appears when the sample is treated at a rotation speed of 60 r/min or 80 r/min for 10 min, and linear G＇-ω dependence is observed at other rotation speeds. In addition, it is found that the appearance of the ＇second plateau＇ depends on the shearing time when the rotation speed is fixed. According to SEM observations, it is proposed that the ＇second plateau＇ of IPC samples should be ascribed to the aggregation of dispersion particles.展开更多
Neodymium-based heterocyclic Schiff base complex was prepared and applied for the coordination polymerization of isoprene. This complex polymerized isoprene to afford products featuring high cis-1,4 stereospecificity ...Neodymium-based heterocyclic Schiff base complex was prepared and applied for the coordination polymerization of isoprene. This complex polymerized isoprene to afford products featuring high cis-1,4 stereospecificity （ca. 95%） and high molecular weight （ca, 10^5） in the presence of the triisobutyl aluminium （AliBu3） as cocatalyst, The microstructure of obtained polyisoprene was investigated by FTIR, 1^H NMR. Two different kinds of active centers in the catalyst system were examined by GPC method.展开更多
A novel graft copolymer consisting of polyisoprene backbone and hydrophilic side chain with carbamic acid ester functional group was prepared via thiol-ene＂click＂reaction and alcohol-isocyanate reactions.Polyisopren...A novel graft copolymer consisting of polyisoprene backbone and hydrophilic side chain with carbamic acid ester functional group was prepared via thiol-ene＂click＂reaction and alcohol-isocyanate reactions.Polyisoprene was synthesized by anionic polymerization using n-butyl lithium as initiator,and the pendant hydroxyl groups were introduced by the thiol-ene reaction of mercaptoethanol with the double bond of 1,2-addition units of PI backbone in the presence of radical initiator azobisisobutyronitrile. Isocyanate end group capped poly（ethylene glycol）（mPEG-NCO） was grafted onto the PI backbone through alcoholisocyanate reaction between the pendant hydroxyl groups and isocyanate group of mPEG-NCO.The structure of the graft copolymer were characterized and confirmed by means of size-exclusion chromatography,~1H NMR and FTIR spectroscopy.展开更多
We report the polymerization of phenyl isocyanides with the chiral palladium（II） initiating system. The resulting polymers with optically active properties were obtained by polymerization of the racemic isocyanide m...We report the polymerization of phenyl isocyanides with the chiral palladium（II） initiating system. The resulting polymers with optically active properties were obtained by polymerization of the racemic isocyanide monomer （rac-1）, and enantiomerically unbalanced polymerization of the monomer was found, providing substantial evidence for the enantiomer-selective polymerization of rac- 1 mediated through chiral catalyst. A comparison between the enantiomerically pure monomers, 4-isocyanobenzoyl-L-alanine decyl ester （1 s） and 4-isocyanobenzoyl-D-alanine decyl ester （1 r）, revealed a drastic discrepancy in the reactivity ratio of their homopolymerizations. It turned out that the monomer reactivity ratio of ls was higher than that of lr with chiral ligands. The results clearly demonstrated the inclination for incorporation of the ls enantiomer during the polymerization process and thus resulted in the enantiomer-selective polymerization in this system. The effects of the catalyst chirality on the optically active properties of polymerization were investigated, and it was concluded that the formation of higher-ordered conformation with a handed helicity might be attributed to the chiral induction of chiral palladium（II） catalyst. Moreover, the polymers obtained through the enantiomer-selective polymerization of the enantiomerically pure monomer were with a significant improvement of the optical activity if the chirality of the monomer and the catalyst matched with each other.展开更多
Poly (lactic acid) (PLA) was synthesized by microwave-assisted ring-opening polymerization of D, L-lactide with stannous octanoate (SnOct(2)) as catalyst. Its weight-average molar mass (M-w) ranged from 39000 to 67000...Poly (lactic acid) (PLA) was synthesized by microwave-assisted ring-opening polymerization of D, L-lactide with stannous octanoate (SnOct(2)) as catalyst. Its weight-average molar mass (M-w) ranged from 39000 to 67000 and the polydispersity index from 1.3 to 1.7. The polymerization rate was much faster than that of the conventional thermal polymerization. A degradation of newly formed PLA in reaction mixture by microwave irradiation was observed.展开更多
基金financially supported by the National Natural Science Foundation of China(No.52373052)Fundamental Research Funds for the Central Universities(No.DUT24MS011)。
文摘An effective strategy for enhancing the heat resistance of polystyrene(PS)with regard to its glass transition temperature(T_(g))involves the anionic solution copolymerization of a-methylstyrene(AMS)with styrene(St),typically requires much lower temperature(-25℃)and multistep monomer feeding to achieve higher number-average molecular weight(M_(n))block copolymers.However,the anionic copolymerization of AMS and St under the mild temperature remains largely unexplored.This study systematically investigated the anionic copolymerization of AMS and St using n-BuLi in nonpolar solvent(-25℃ to 25℃)through both one-step and two-step approaches.We demonstrated that one-step copolymerization at 25℃ yielded only 1-3 terminal AMS units,with higher feed ratios(5 wt%-20 wt%)increasing AMS incorporation but reducing the exact molecular weight(MW)due to enhanced depolymerization,as evidenced by MALDI-TOF MS.Temperature-controlled AMS conversion at-15℃ achieved 98%AMS conversion(5 wt% feed)by suppressing side reactions and lowering the[M]_(e),while 50℃(near T_(C))almost prevented incorporation.Despite t-BuOK regulation induced broader PDI(1.24)via reactive[(polymer-Li)OR]K intermediates,while other systems showed narrow distributions,t-BuOK outperformed THF in enhancing AMS incorporation via efficient ion pair dissociation.In comparison,the two-step polymerization approach demonstrated superior performance,achieving both higher AMS conversion efficiency and preferential incorporation at the initiation end.At a 20 wt%AMS feed ratio,this method yielded copolymer chains containing up to 6 AMS units on average.Thermal analysis revealed a composition-dependent single T_(g),which exhibited a systematic increase with higher AMS incorporation content.These results collectively demonstrate the precise control over AMS incorporation and heat resistance achievable through the manipulation of polymerization conditions.
文摘Due to the structure characteristics of huge macromolecular size and the very low motion feature of the polymer chain which is very difficult to arrange regularly their long chain into the three dimensional space,thus the polymer will incompletely crystallize except for the macroscopic single crystal of polydiacetylene polymerized by means of solid state crystalline polymerization.
基金financially supported by the National Natural Science Foundation of China(Nos.92477118 and 22173045)the Postgraduate Research and Practice Innovation Program of Jiangsu Province(No.KYCX25_0188)。
文摘Colloidal molecules exhibit unique electronic,optical,and magnetic properties owing to their molecular-like configurations and coupling effects,making them promising building blocks for multifunctional materials.However,achieving precise and controllable assembly of isotropic nanoparticles with high yields remains a great challenge.In this study,we present a synergistic strategy that integrates molecular dynamics simulations with interpretable machine learning to develop a programmable assembly system based on block copolymers and DNA-functionalized nanoparticles.Our simulation results reveal that block copolymer modification facilitates stepwise control over surface phase separation and nanoparticle coassembly,thereby enhancing structural stability and efficiently suppressing disordered aggregation of atom-like nanoparticles.Furthermore,we demonstrated that precise,controllable,and programmable assembly of colloidal molecules can be achieved through rational DNA sequence design.SHapley Additive exPlanations(SHAP)analysis identified key structural descriptors that govern assembly outcomes and elucidated their underlying mechanistic roles.This work not only deepens the understanding of colloidal molecule assembly mechanisms but also lays a theoretical foundation for the rational design of functional colloidal architectures in nanomaterial science.
基金supported by the Fundamental Research Funds for the Central Universities(No.226-2025-00031).
文摘In 2024,the MOE Key Laboratory of Macromolecular Synthesis and Functionalization at Zhejiang University continued its impactful researches across five core areas.In controllable catalytic polymerization,organoboron catalysts were developed for CO₂copolymerization and novel photoresist materials.Studies in microstructure and rheology elucidated universal deformation modes in graphene-based 2D membranes and improved graphene fiber properties through shear alignment engineering,defect control,and enhanced interlayer entanglement.For separating functional polymers,Janus membranes and channels were created for multiphase separation,liquid-phase molecular layer-by-layer deposition technique was developed to fabricate aromatic polyamide nanofilms,and the harmonic amide bond density was established as a valuable parameter for polyamide structural analysis.In biomedical functional polymers,a sustainable carboxyl-ester transesterification strategy was proposed for upcycling poly(ethylene terephthalate)(PET)waste into biodegradable plastics.Additionally,immunocompatible biomaterials were designed utilizing zwitterionic polypeptides and albumin-derived coatings,and Cu2+-phenolic nanoflower was designed to combat fungal infections by combining cuproptosis and cell wall digestion.Further,the researchers developed a gelatin-DOPA-knob/fibrinogen hydrogel to achieve rapid and robust hemostatic sealing,utilized a double-network polyelectrolyte-coated hydrogel for enhancing endothelialization of left atrial appendage(LAA)occluders,and the researchers also demonstrated that image-guided high-intensity focused ultrasound enables manipulation of shape-memory polymers.Finally,in the realm of photo-electro-magnetic functional polymers,precise control of through-space conjugation was shown to enhance organic luminescence.Topologically structured hydrogels were revealed to exhibit autonomous actuation.Also,solar-driven photothermal ion pumps were developed for selective lithium extraction from seawater,and high-performance non-solvated C60 single-crystal films were prepared via facile bar coating.Lastly,the researchers demonstrated outstanding dielectric properties of polyethylene(PE)lamellar single crystals.The relevant works are reviewed in this paper.
基金financially supported by the National Natural Science Foundation of China(No.52473338)the National Natural Science Foundation of China(Nos.52173004 and 51873055)+3 种基金Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDA0540000)Advanced Materials-National Science and Technology Major Project(No.2025ZD0614000)Hebei Natural Science Foundation(No.E2022202015)Anhui Province Science and Technology Innovation Tackling Key Project(No.202423i08050025)。
文摘Heterogeneous polymerization represents a widely employed method in the polyolefin industry.In recent years,various heterogenization strategies for late transition metal catalysts have been developed,enabling effective control of polymer morphology and optimization of catalytic performance.However,while most studies have focused on designing anchoring groups and advancing support approaches,systematic investigations into how the support influences the catalytic behavior of the late transition metal catalysts.In this work,we fabricated supported α-diimine nickel catalysts by functionalizing the ligand with alkyl alcohol chains of varying lengths and supporting them onto MgCl_(2)supports.The ethylene polymerization behavior of these catalysts was then investigated.By precisely adjusting the alkyl alcohol chain length,the distance between the catalytically active metal center and the support surface was modulated.This approach demonstrates that support-induced steric hindrance effect can be effectively regulated by controlling the separation distance between the metal center and the support surface.
基金supported by the Strategic Priority Research Program of the Chinese Academy of Science(No.XDB0520000)the National Natural Science Foundation of China(Nos.52273170 and 52394271)the National Key R&D Program of China(No.2022YFA1203200).
文摘Charge-transfer complexes(CTCs)have emerged as promising n-type organic thermoelectric(TE)materials due to their inherent high electrical conductivity and tunable transport polarities.In this study,we performed a comprehensive first-principles investigation on the TE properties of nine CTCs comprised of 2,7-dialkyl[1]benzothieno[3,2-b][1]benzothiophenes(CnBTBT,n=4,8,12)as donors and fluorinated derivatives of tetracyanoquinodimethane(F_(m)TCNQ,m=0,2,4)as acceptors,aiming to identify high-performance n-type organic TE materials and elucidate the underlying structure-property relationships.Our calculation results,based on the Boltzmann transport equation and deformation potential theory,reveal that the length of the alkyl side chains and the number of fluorine substitutions significantly impact their electronic structures and TE properties.Notably,the CnBTBT-F_(m)TCNQ CTCs with shorter alkyl chains and more fluorine substitution demonstrate superior n-type characteristics,particularly C4BTBT-F4TCNQ,which achieves an excellent power factor of 671µW cm^(-1) K^(-2) at an optimal charge carrier concentration.Our findings not only clarify the critical role of molecular engineering in CTC-based TE materials but also provide valuable guidance for developing high-efficiency organic TE materials with versatile practical applications.
基金financially supported by the National Natural Science Foundation of China(No.50803054)Zhejiang Provincial Nature Science Foundation of China(No.Y4100204)
文摘Inspired by the self-polymerization and strong adhesion characteristics of dopamine in aqueous conditions, a novel hydrophilic nanofiltration （NF） membrane was fabricated by simply dipping polysulfone （PSf） ultrafiltration （UF） substrate in dopamine solution. The changes in surface chemical composition and morphology of membranes were determined by Fourier transform infrared spectroscopy （FTIR-ATR）, X-ray photoelectron spectroscopy （XPS）, scanning electron microscopy （SEM） and atomic force microscopy （AFM）. The experimental results indicated that the self-polymerized dopamine formed an ultrathin and defect-free barrier layer on the PSf UF membrane. The surface hydrophilicity of membranes was evaluated through water contact angle measurements. It was found that membrane hydrophilicity was significantly improved after coating a polydopamine （pDA） layer, especially after double coating. The dyes filtration experiments showed that the double-coated membranes were able to reject completely the dyes of brilliant blue, congo red and methyl orange with a pure water flux of 83.7 L/（mE.h） under 0.6 MPa. The zeta potential determination revealed the positively-charged characteristics of PSf/pDA composite membrane in NF process. The salt rejection of the membranes was characterized by 0.01 mmol/L of salts filtration experiment. It was demonstrated that the salts rejections followed the sequence： NaC1 〈 NaaSO4 〈 MgSO4 〈 MgC12 〈 CaCl2, and the rejection to CaC12 reached 68.7%. Moreover, the composite NF membranes showed a good stability in water-phase filtration process.
基金supported by the Science and Technology Department of Zhejiang Province(No.2006C11050)
文摘A series of stable waterborne polysiloxaneurethane （WPSUR） dispersions were prepared using amino-terminated polydimethylsiloxane （NS）, dimethylolpropionic acid （DMPA）, castor oil, polypropylene glycol and toluene diisocyanate. Meanwhile, NS with different molecular weights was synthesized and used as the soft co-segment. Effects of types and contents of soft co-segments as well as chain extenders on the thermal degradation and stability for WPSUR films were examined. Results reveal that WPSUR films exhibit excellent water resistance and mechanical properties as compared with pure polyurethane （PU） films, and the NS soft co-segment possesses a remarkable effect on the second stage （stage Ⅱ）, while the content of the hard segment is propitious to the initial stage （stage Ⅰ）. Moreover, the highest temperature of stage Ⅱ （T2m） for WPSUR films using NS as soft co-segment is 413℃, approximately being 30℃ higher than that of those typical PUs using HDA and APDMS as the chain extenders, respectively.
基金supported by the National 973 Program(No.2009CB623402)the National Natural Science Foundation of China(No.20974094)
文摘Three well-defined diblock copolymers ofpoly（methyl methacrylate-b-methacrylic acid） （P（MMA-b-MAA）） were synthesized using atom transfer radical polymerization method and varying poly（methacrylic acid） （PMAA） chain lengths. These copolymers were blended with PVC to fabricate porous membranes via phase inversion process. Membrane morphologies were observed by scanning electron microscopy （SEM）, and chemical composition changes of the membrane surfaces were measured by X-ray photoelectron spectroscopy （XPS）. Static and dynamic protein adsorption experiments were used to evaluate antifouling properties of the blend membranes. It was found that, the blend membranes containing longer PMAA arm length showed lower static protein adsorption, higher water permeation flux and better protein solution flux recovery.
基金This work was supported by the National Natural Science Foundation of China (Grants 20174001, 29992590-4) and the Ministry of Education of China for the teaching and research award fund for outstanding young teacher in higher education institutions.
文摘Two new chiral ionic liquids, 1 -((-)-menthoxycarbonylmethylene)-3-methylimidazolium hexafluorophosphateand 1-((-)-menthoxycarbonylmethylene)-3-hexadecylimidazolium hexafluorophosphate, were designed an d prepared. Theirchemical structures were characterized by ~1H-NMR. Reverse atom transfer radical polymerization of methyl methacrylate(MMA) in these two ionic liquids was carried out using AIBN/CuCl_2/bipy as the initiating system. The resultant well-definedpolymethyl methacrylate (PMMA) was employed as a macroinitiator to induce the atom transfer radical polymerization ofmenthyl methacrylate (MnMA) in chlorobenzene, which yielded a PMMA-b-PMnMA diblock copolymer with narrow polydispersity.
基金financially supported by the National Natural Science Foundation of China (No. 21871232)Zhejiang Provincial Natural Science Foundation of China (No. LR15B040001)
文摘Functionalized aliphatic polyesters attract increasing attentions as biocompatible and biodegradable polymers with broad applications in biological science. In this contribution, we propose a facile and controllable synthetic technique for functional poly(ε-caprolactone)(PCL) via Janus polymerization, which comprises cationic ring-opening copolymerization (ROP) of ε-caprolactone (CL) with 3,3-bis(chloromethyl)oxacyclobutane (CO) and (coordinated) anionic ROP of CL at a single propagating chain by rare earth metal triflates (RE(OTf)3)and propylene oxide, thus generating block copolymers in one step. The compositions of the copolymers of poly(CLb-(CL-r-CO)) can be modulated by various RE(OTf)3. Scandium triflate catalyzes Janus polymerization to yield the copolymers containing the highest CO contents among all the RE(OTf)3 catalysts used with complete conversion of CL. The chlorine in CO repeating units is ready to be transferred into azide group which affords the modification sites to react with 9-ethynyl-9-fluorenol and mPEG-alkyne, respectively, via copper(I)-catalyzed azide-alkyne cycloaddition reaction with quantitative conversions of azides, as confirmed by FTIR analyses. According to NMR and SEC analyses, copolymers (PCC-g-PEG) bearing a homo-PCL block and a PEG-grafted block of poly(CO-co-CL) demonstrate well-defined chemical structures. The investigations on thermal properties reveal the strong phase separation between PCL and PEG blocks. The amphiphilic PCC-g-PEG is able to sei住assemble into micelles in aqueous solution while cylindrical and lamellar morphologies are observed in bulk. We provide an efficient protocol to synthesize functional PCL combining onestep Janus polymerization and precise post-polymerization click reaction.
基金Supported by the National Natural Science Foundation of China and the State Education Committee of China
文摘Acryloyl terminated Poly (ethyleneoxide)macromonomers (PEO-A) with different PEO chain lengths have been prepared by deactivation of PEO alkoxide with acryloyl chloride. A new kind of amphiphilic polystyrene-g-poly (ethylene oxide)graft copolymer containing both microphase separated and PEO side chain structures has been synthesized from radical copolymerization of PEO-A macromonomer with styrene. After careful purification by a newly-developed method called 'selective dissolution', the well-defined structure of the purified copolymers was confirmed by IR, ~1H-NMR and GPC. Various experimental parameters controlling the copolymerization were studied in detail. The results indicated that the feed ratio of styrene to macromonomer(S/M) was the most important determining factor for the composition of the copolymers. A detailed 'comb- model' was proposed to describe the molecular structure of the graft copolymers. Finally, this amphiphilic graft copolymers may readily form microphase separated structures as clearly indicated by transmission electron microscopy.
基金financially supported by the National Natural Science Foundation of China(Nos.51173157 and 51173165)the Fundamental Research Funds for the Central Universities(No.2013QNA4048)
文摘We reported an approach to reconstruct the complex phase morphology of impact polypropylene copolymer （IPC） with core-shell dispersed particles and to optimize its toughness in approximate shear condition. The molten-state annealing results indicate that the phase structure with core-shell dispersed particles is unstable and could be completely destroyed by static annealing, resulting in the degradation of impact strength. By using a co-rotating twin screw extruder, we found that the dispersed particle with core-shell structure could be rebuilt in appropriate condition with the recovery of excellent impact strength due to both the huge interfacial tension during solidification and the great difference in viscosity of components. Results reveal that almost all the extruded IPCs show the impact strength 60%-90% higher than that of annealed IPCs at room temperature. And the twice-extruded IPC shows the highest impact strength, 446% higher than that of IPC annealed for 30 min. As for low temperature tests, the impact strength of extruded IPCs also increases by 33%-58%. According to adjusting the processing conditions including extrusion speed, extrusion frequency and temperature, an optimization of toughness was well established.
基金financially supported by the National Natural Science Foundation of China (No. 21871232)the Zhejiang Provincial Natural Science Foundation of China (No. LR15B040001)
文摘Janus polymerization is featured as a combination of cationic and anionic growing ends in one living polymer chain. In the copolymerization of THF and CL catalyzed by lutetium triflates and initiated by propylene oxide, three stages are identified by kinetic study including(1) fast cationic polymerization with slow anionic one,(2) fast anionic polymerization with dormant cationic one, and(3)reactivation of cationic polymerization with coupling of anionic and cationic chain ends. In this work, density functional theory(DFT)calculation is employed to investigate the reaction details of ionic polymerization and dormancy. A “tripedal crow” configuration is proposed to illustrate the unique high-coordinated ligand exchange configuration in anionic polymerization in different stages. The trigger of dormancy is determined as chain structures rather than concentration of triflate anion according to both calculation and experimental results.
基金supported by the National Basic Research Program of China(No.2005CB623800)Joint Research Fund for Overseas Chinese Young Scholars(No.50728302)the Program for Zhejiang Provincial Innovative Research Team (No.2009R50004)
文摘Ethylene/propylene-random-copolymer （PPR）/clay nanocomposites were prepared by two-stage melt blending. Four types of compatibilizers, including an ethylene-octene copolymer grafted maleic anhydride （POE-g-MA） and three maleic-anhydride-grafted polypropylenes （PP-g-MA） with different melt flow indexes （MFI）, were used to improve the dispersion of organic clay in matrix. On the other hand, the effects of organic montmorillonite （OMMT） content on the nanocomposite structure in terms of clay dispersion in PPR matrix, thermal behavior and tensile properties were also studied. The X-ray diffraction （XRD） and transmission electron microscopy （TEM） results show that the organic clay layers are mainly intercalated and partially exfoliated in the nanocomposites. Moreover, a PP-g-MA compatibilizer （compatibilizer B） having high MFI can greatly increase the interlayer spacing of the clay as compared with other compatibilizers. With the introduction of compatibilizer D （POE-g-MA）, most of the clays are dispersed into the POE phase, and the shape of the dispersed OMMT appears elliptic, which differs from the strip of PP-g-MA. Compared with virgin PPR, the Young＇s modulus of the nanocomposite evidently increases when a compatibilizer C （PP-g-MA） with medium MFI is used. For the nanocomposites with compatibilizer B and C, their crystallinities （Xc） increase as compared with that of the virgin PPR. Furthermore, the increase of OMMT loadings presents little effect on the melt temperature （Tc） of the PPR/OMMT nanocomposites, and slight effect on their crystallization temperature （Tc）. Only compatibilizer B can lead to a marked increases in crystallinity and Tc of the nanocomposite when the OMMT content is 2 wt%.
基金financially supported by the National Natural Science Foundation of China(No.51173157),National Basic Research Program of China(No.2005CB623800) and Natural Science Foundation of Zhejiang Province(No.Y4100314).
文摘The influences of shearing conducted by a Brabender behavior of a commercial impact polypropylene copolymer （IPC） rheometer on phase morphology, thermal and rheological were studied. The crystallization and melting traces show that short-time annealing at 210℃ is unable to completely erase the influence of shearing on the samples. When the samples which were treated at a rotation speed of 80 r/rnin crystallize at a cooling rate of 10 K/min, their Tcs and corresponding Tms obviously rise with the increase of shearing time. Furthermore, the POM results reveal that the shearing can lead to the formation of shish-kebab and the shish-kebab amount is proportional to shearing time. The rheological measurement results show that the treated samples exhibit different G＇-ω dependences. The ＇second plateau＇ appears when the sample is treated at a rotation speed of 60 r/min or 80 r/min for 10 min, and linear G＇-ω dependence is observed at other rotation speeds. In addition, it is found that the appearance of the ＇second plateau＇ depends on the shearing time when the rotation speed is fixed. According to SEM observations, it is proposed that the ＇second plateau＇ of IPC samples should be ascribed to the aggregation of dispersion particles.
基金The authors are indebted to the financial supports of the National Natural Science Foundation of China （No.20774078 and the Key Program No.20434020）；the Special Funds for Major Basic Research Projects （G2005CB623802）.
文摘Neodymium-based heterocyclic Schiff base complex was prepared and applied for the coordination polymerization of isoprene. This complex polymerized isoprene to afford products featuring high cis-1,4 stereospecificity （ca. 95%） and high molecular weight （ca, 10^5） in the presence of the triisobutyl aluminium （AliBu3） as cocatalyst, The microstructure of obtained polyisoprene was investigated by FTIR, 1^H NMR. Two different kinds of active centers in the catalyst system were examined by GPC method.
基金supports of the Special Funds for Major Basic Research Projects (NoG2011CB606001)Zhejiang Provincial Top Key Discipline of New Materials and Process Engineering(No 20110926)
文摘A novel graft copolymer consisting of polyisoprene backbone and hydrophilic side chain with carbamic acid ester functional group was prepared via thiol-ene＂click＂reaction and alcohol-isocyanate reactions.Polyisoprene was synthesized by anionic polymerization using n-butyl lithium as initiator,and the pendant hydroxyl groups were introduced by the thiol-ene reaction of mercaptoethanol with the double bond of 1,2-addition units of PI backbone in the presence of radical initiator azobisisobutyronitrile. Isocyanate end group capped poly（ethylene glycol）（mPEG-NCO） was grafted onto the PI backbone through alcoholisocyanate reaction between the pendant hydroxyl groups and isocyanate group of mPEG-NCO.The structure of the graft copolymer were characterized and confirmed by means of size-exclusion chromatography,~1H NMR and FTIR spectroscopy.
基金financially supported by the National Natural Science Foundation of China (Nos. 51673057, 21622402, and 21574036)N. Liu thanks Anhui Provincial Natural Science Foundation (No. 1608085MB41)
文摘We report the polymerization of phenyl isocyanides with the chiral palladium（II） initiating system. The resulting polymers with optically active properties were obtained by polymerization of the racemic isocyanide monomer （rac-1）, and enantiomerically unbalanced polymerization of the monomer was found, providing substantial evidence for the enantiomer-selective polymerization of rac- 1 mediated through chiral catalyst. A comparison between the enantiomerically pure monomers, 4-isocyanobenzoyl-L-alanine decyl ester （1 s） and 4-isocyanobenzoyl-D-alanine decyl ester （1 r）, revealed a drastic discrepancy in the reactivity ratio of their homopolymerizations. It turned out that the monomer reactivity ratio of ls was higher than that of lr with chiral ligands. The results clearly demonstrated the inclination for incorporation of the ls enantiomer during the polymerization process and thus resulted in the enantiomer-selective polymerization in this system. The effects of the catalyst chirality on the optically active properties of polymerization were investigated, and it was concluded that the formation of higher-ordered conformation with a handed helicity might be attributed to the chiral induction of chiral palladium（II） catalyst. Moreover, the polymers obtained through the enantiomer-selective polymerization of the enantiomerically pure monomer were with a significant improvement of the optical activity if the chirality of the monomer and the catalyst matched with each other.
文摘Poly (lactic acid) (PLA) was synthesized by microwave-assisted ring-opening polymerization of D, L-lactide with stannous octanoate (SnOct(2)) as catalyst. Its weight-average molar mass (M-w) ranged from 39000 to 67000 and the polydispersity index from 1.3 to 1.7. The polymerization rate was much faster than that of the conventional thermal polymerization. A degradation of newly formed PLA in reaction mixture by microwave irradiation was observed.
