Heterogeneous TiCl4/MgCl_(2) type Ziegler-Natta(Z-N)catalysts with unique advantages like low cost,high activity,high stereoregularity and pretty particle morphology,contribute to more than 130 Mt polyolefin large-sca...Heterogeneous TiCl4/MgCl_(2) type Ziegler-Natta(Z-N)catalysts with unique advantages like low cost,high activity,high stereoregularity and pretty particle morphology,contribute to more than 130 Mt polyolefin large-scale production.However,most researches related with heterogeneous Z-N catalysts focused onα-olefin polymerizations like ethylene,propylene,etc.展开更多
Graphene oxide(GO)with excellent dispersion ability can assist the dispersion of single-walled carbon nanotube(SWCNT)and promote the formation of uniform and stable GO/SWCNT coating liquid.The highly conductive polyet...Graphene oxide(GO)with excellent dispersion ability can assist the dispersion of single-walled carbon nanotube(SWCNT)and promote the formation of uniform and stable GO/SWCNT coating liquid.The highly conductive polyethylene terephthalate/reduced graphene oxide/SWCNT(PET/rGO/SWCNT)electromagnetic shielding composite fabric was successfully prepared by anchoring rGO/SWCNT on PET fabric via dip-coating piror to low-temperature thermal reduction.The results showed that the carboxyl groups and hydroxyl groups formed of hydrophilic-treated PET were conducive to the formation of hydrogen bonds with that of GO,which enhanced the interaction between PET fabric and GO/SWCNT coating;the loading of GO/SWCNT increased with the number of dip-coating,the unit area loading of rGO/SWCNT in the final composite fabric was 2.7 mg/cm^(2) after 10 dip-coating cycles and thermal reduction;the PET/rGO/SWCNT composite fabric had a continuous and dense conductive network,with a conductivity of up to 41.6 S/m and the average electromagnetic interference shielding effectiveness in X-band was 22 dB;the flexible PET/rGO/SWCNT composite fabric was not only easy to process,but also exhibited excellent conductivity and shielding efficiency,showing great potential in the application of electromagnetic shielding fabrics.展开更多
Neodymium(Nd)-based catalyst in butadiene(Bd)polymerization has drawn interests due to its availability in affording higher cis-1,4-unit selectivity than transition metal(Ti,Co,Ni,etc.)-based catalysts[1-2].Such outst...Neodymium(Nd)-based catalyst in butadiene(Bd)polymerization has drawn interests due to its availability in affording higher cis-1,4-unit selectivity than transition metal(Ti,Co,Ni,etc.)-based catalysts[1-2].Such outstanding high cis-1,4-unit selecti-vity is hypothetically originated from the presence of 4 f orbitals,that can participate in monomer coordination and thereby govern subsequent enchainment manners.This unique characteristic also renders the active species highly susceptible to Lewis bases,and may impact the overall selectivity as well as polyme-rization behavior after coordination.Nevertheless,it is still a virgin area in such a field,and the influence of Lewis bases on Nd-based diene polymerizations is still a black box.Based on this consideration,how nitrogen-containing donors(D)impacts the overall behaviors of Nd-mediated Bd polymerizations is disclosed.展开更多
End-functionalization of polydiene rubbers can not only improve its compatibility with inorganic fillers,but also enhance the overall mechanical properties.Nevertheless,for traditional neodymium(Nd)diene polymerizatio...End-functionalization of polydiene rubbers can not only improve its compatibility with inorganic fillers,but also enhance the overall mechanical properties.Nevertheless,for traditional neodymium(Nd)diene polymerization systems,it is highly challenging to achieve such end-functionalizations,because most of polydienyl chains are capped withη3-allyl-Nd moiety during the end of polymerization,which shows very poor reactivity with nucleophile compounds.We launched a new diene polymerization strategy calling coordinative chain transfer polymerization(CCTP)[1].In such a system,all the polydienyl chains are capped withη1-allyl-Al moieties,which reveal greater reactivity with cyclic esters and epoxide compounds,providing an effective manner to prepare polydiene-polyester amphiphilic block copolymers.Inspired by such findings,we now show herein how such types of chain-ends react with isot-hiocyanate to demonstrate an efficient in-situ manner to access end-functionalized polydienes by using CCTP.展开更多
The gas-liquid phase equilibrium is used in controlling the nitrosation reaction process. Decomposition of nitrous acid and oxidation side reaction.are suppressed in a closed reaction system. The system pressure is us...The gas-liquid phase equilibrium is used in controlling the nitrosation reaction process. Decomposition of nitrous acid and oxidation side reaction.are suppressed in a closed reaction system. The system pressure is used as the criterion of the end of reaction, avoiding excessive feeding and reducing＇the decomposition＇of nitrous acid. The head space of the reactor is used as the gas buffer, stabilizing the feeding fluctuations and inhibiting the side reaction, decomposition of nitrous acid. Nitrogen oxide concentration is controlled at the minimum level.Thus the zero release ofnitrogen ox!de waste gas can be achieved without using any absorption process.展开更多
Hydrogenated nitrile rubber(HNBR)was prepared by selective hydrogenation of nitrile-butadiene rubber latex using hydrazine hydrate/hydrogen peroxide catalytic system,which effectively resolved the problems with enviro...Hydrogenated nitrile rubber(HNBR)was prepared by selective hydrogenation of nitrile-butadiene rubber latex using hydrazine hydrate/hydrogen peroxide catalytic system,which effectively resolved the problems with environment pollution and high cost caused by noble metal catalyst via solution hydrogenation method.Because of the saturation of carbon-carbon double bonds after hydrogenation,HNBR presented excellent thermal-oxidative aging resistance.The thermaloxidative activation of HNBR prepared in situ was investigated by thermogravimetric analysis(TGA)and Flynn-Wall-Ozawa method.Meanwhile,the microstructure and mechanical properties of HNBR was studied during the thermal-oxidative aging process.The relationship between lifetime and aging temperature was evaluated as well as the thermal-oxidative aging coefficient of HNBR,which provided theoretical basis for the application of HNBR under the high temperature and in harsh environment.展开更多
In this study,a novel iron-based catalyst system,Fe(acac)3/(isocyanoimino)triptenylphosphorane(IITP)/AlR3,was employed for the synthesis of syndiotactic 1,2-polybutadiene in hexane.This catalyst system exhibits remark...In this study,a novel iron-based catalyst system,Fe(acac)3/(isocyanoimino)triptenylphosphorane(IITP)/AlR3,was employed for the synthesis of syndiotactic 1,2-polybutadiene in hexane.This catalyst system exhibits remarkably high catalytic activity,achieving a polymerization activity of 762 kgpolymer·molcatalyst^(-1)·h^(-1)at 50℃with a[BD]/[Fe]molar ratio of 20000.Furthermore,living polymerization characteristic were observed during the investigation of the polymerization kinetics of 1,3-butadiene polymerization.These characteristics were well demonstrated by a narrow molecular weight distribution(PDI≈2.0)of the resulting polybutadiene and a linear relationship between-ln(1-c)and polymerization time as well as number average molecular weight and polymer yield.The resultant polymer showed a 1,2-selectivity of approximately 76%and stereoregularity ranging from 62%to 73%(rrrr).Additionally,through kinetic studies on polymerization reaction,an apparent activation energy Ea value of this catalytic system was calculated to be 84.98 kJ·mol^(-1),which suggests that high polymerization temperature favors efficient polymerization.展开更多
Well-defined polycarbonate diol was successfully synthesized through a strategy using a combination of organocatalyst and water.Such strategy was less developed in organocatalyzed polymerization and frequently regarde...Well-defined polycarbonate diol was successfully synthesized through a strategy using a combination of organocatalyst and water.Such strategy was less developed in organocatalyzed polymerization and frequently regarded as side reactions.Herein,one-component phosphonium borane Lewis pairs PB1-PB8 were successfully applied in the copolymerization of CO_(2) and cyclohexene oxide(CHO)to generate poly(CHO-alt-CO_(2))carbonate(PCHC).Parameters of linker length and counter anion effects on the catalyst activity were investigated.It was found that Lewis pair PB3 served as a dual initiator and catalyst in the copolymerization of CHO and CO_(2) with or without the presence of water.In contrast,Lewis pair PB8 can serve as a true catalyst for the preparation of well-definedα,ω-hydroxyl PCHC diols.This was achieved by introducing a labile CF3COO group as counter anion through anion exchange reaction while water molecules acted as chain transfer agents.The function of trifluoroacetate group in the polymerization process was investigated in detail and possible mechanism was proposed.Upon changing the amount of water and catalyst loading,PCHC diols with varied molecular weight(1.5 kg/mol to 7.5 kg/mol),low dispersities(D<1.2)and carbonate content(>99%)could be easily obtained.The low molecular weight PCHC diol was used as a bifunctional macroinitiator for the ring-opening polymerization of L-lactide(LLA)to afford ABA triblock copolymer in one-pot synthesis.展开更多
Identification and visualization of phase structures inside polymer blends are of critical importance in the understanding of their intrinsic structure and dynamics.However,the direct optical observation of the indivi...Identification and visualization of phase structures inside polymer blends are of critical importance in the understanding of their intrinsic structure and dynamics.However,the direct optical observation of the individual component phase in a dense bulk material poses a significant challenge.Herein,three-dimensional fluorescence imaging of phase separation and realtime visualization of phase transformation in immiscible polymer blends of polypropylene and polystyrene is realized through multiphoton laser scanning microscopy.Owing to the specific fluorescence behavior of the cyanostyrene derivative 2-(4-bromophenyl)-3-(4-(4-(diphenylamino)styryl)phenyl)fumaronitrile,the high-contrast imaging of the macrophase of the component polymer in two and three dimensions with a maximum depth of 140μm and a high signal-to-noise ratio of 300 can be achieved.Detailed spectroscopic and structural studies reveal that the distinctive fluorescence features of each phase domain should originate from the formation of a completely different aggregate between probes and component polymer.Furthermore,visualizations of the internal morphology deformation and macrophase transformation were realized by employing a stretched dumbbell sample under constant tension.展开更多
Solid electrolytes play a vital role in solid-state Li secondary batteries,which are promising high-energy storage devices for new-generation electric vehicles.Nevertheless,obtaining a suitable solid electrolyte by a ...Solid electrolytes play a vital role in solid-state Li secondary batteries,which are promising high-energy storage devices for new-generation electric vehicles.Nevertheless,obtaining a suitable solid electrolyte by a simple and residue-free preparation process,resulting in a stable interface between electrolyte and electrode,is still a great challenge for practical applications.Herein,we report a self-crosslinked polymer electrolyte(SCPE)for high-performance lithium batteries,prepared by a one-step method based on 3-methoxysilyl-terminated polypropylene glycol(SPPG,a liquid oligomer).It is worth noting that lithium bis(oxalate)borate(Li BOB)can react with SPPG to form a crosslinked structure via a curing reaction.This self-formed polymer electrolyte exhibits excellent properties,including high roomtemperature ionic conductivity(2.6×10^(-4) S cm^(-1)),wide electrochemical window(4.7 V),and high Li ion transference number(0.65).The excellent cycling stability(500 cycles,83%)further highlights the improved interfacial stability after the in situ formation of SCPE on the electrode surface.Moreover,this self-formation strategy enhances the safety of the battery under mechanical deformation.Therefore,the present self-crosslinked polymer electrolyte shows great potential for applications in high-performance lithium batteries.展开更多
Linear and non-linear rheological properties were examined for in-reactor alloy samples composed of isotactic polypropylene(iPP),ethylene-propylene rubber(EPR),and polyethylene(PE).The samples were prepared through tw...Linear and non-linear rheological properties were examined for in-reactor alloy samples composed of isotactic polypropylene(iPP),ethylene-propylene rubber(EPR),and polyethylene(PE).The samples were prepared through two-or three-stage sequential polymerization,where iPP,as the majority,was synthesized in the first stage,and either EPR or PE,as the minority,was synthesized in the second or third stage.Above Tm of both PE and iPP,the linear viscoelasticity shows two relaxation processes,where the fast and slow processes are attributable to the relaxation of the iPP component and that of the EPR/PE domains,respectively.Both the damping behavior upon applying the step-strain measurements and the shear-thinning behavior under the shear-rate sweep measurements are strongly related to the different degrees of nonlinearity of the two relaxation processes.展开更多
Abstract Two series of trans-1,4-poly（butadiene-co-isoprene） copolymers （TBIR） were prepared using the catalyst system TiCl4/MgCl2-Al（i-Bu）3 at different reaction temperatures. All dyad and triads sequence distr...Abstract Two series of trans-1,4-poly（butadiene-co-isoprene） copolymers （TBIR） were prepared using the catalyst system TiCl4/MgCl2-Al（i-Bu）3 at different reaction temperatures. All dyad and triads sequence distributions, the number-average sequence length and the sequence concentration of the copolymers were calculated according to 13C-NMR spectra. The influences of temperature and initial molar ratio of butadiene to isoprene （Bd to Ip） on the distribution of the chain segments in the TBIR copolymers were discussed. The correlation of copolymer compositions and thermal properties were also evaluated, which facilitated the understanding of controlling the degree of crystallinity and the transition tempera^re by changing Bd content and temperature.展开更多
A series of trans-1,4-butadiene/isoprene copolymers were prepared using the catalyst system TiCl4/MgCl2-Al（i- Bu）3 with bulk precipitation technology at different temperatures. Monomers reactivity ratios were calcul...A series of trans-1,4-butadiene/isoprene copolymers were prepared using the catalyst system TiCl4/MgCl2-Al（i- Bu）3 with bulk precipitation technology at different temperatures. Monomers reactivity ratios were calculated based on the Kelen-Tiid6s （K-T） method and the Mao-Huglin （M-H） method. The influence of temperature on copolymer composition and polymerization rate was discussed in detail. The increase of reaction temperature brought the decrease of butadiene reactivity ratio rBd and supplied an effective adjustment on copolymers＇ composition distribution.展开更多
The catalytic activity and stereospecificity of olefin polymerization by using heterogeneous TiCl_(4)/MgCl_(2) Ziegler-Natta(Z-N) catalysts are determined by the structure and nature of active centers, which are myste...The catalytic activity and stereospecificity of olefin polymerization by using heterogeneous TiCl_(4)/MgCl_(2) Ziegler-Natta(Z-N) catalysts are determined by the structure and nature of active centers, which are mysterious and fairly controversial. In this work, the propylene polymerization kinetics under different polymerization temperatures by using Z-N catalysts were investigated through monitoring the concentration of active centers [C*] with different tacticity. SEM was applied to characterize the catalyst morphologies and growing polypropylene(PP) particles. The lamellar thickness and crystallizability of PP obtained under different polymerization conditions were analyzed by DSC and SAXS. The PP fractions and active centers with different tacticity were obtained with solvent extraction fractionation method. The catalytic activity, active centers with different tacticity and propagation rate constant kp, fragmentation of the catalyst, crystalline structure of PP are correlated with temperature and time for propylene polymerizations. The polymerization temperature and time show complex influences on the propylene polymerization. The higher polymerization temperature(60 ℃) resulted higher activity, kp and lower [C*], and the isotactic active centers Ci* as the majority ones producing the highest isotactic polypropylene(iPP) components showed much higher kp when compared with the active centers with lower stereoselectivity. Appropriate polymerization time provided full fragmentation of the catalyst and minimum diffusion limitation. This work aims to elucidate the formation and evolution of active centers with different tacticity under different polymerization temperature and time and its relations with the fragmentation of the PP/catalyst particles, and provide the solutions to the improvement of catalyst activity and isotacticity of PP.展开更多
Two types of bifunctional bis（salicylaldimine） ligands（syn-L and anti-L） were designed and synthesized to support bimetallic aluminum complexes. Owing to the rigid anthracene skeleton, syn-L and anti-L successfull...Two types of bifunctional bis（salicylaldimine） ligands（syn-L and anti-L） were designed and synthesized to support bimetallic aluminum complexes. Owing to the rigid anthracene skeleton, syn-L and anti-L successfully locked two Al centers in close proximity（syn-Al2） and far apart（anti-Al2）, respectively. The distance between two Al centers in syn-Al2 was defined by X-ray diffraction as 6.665 ？, which is far shorter than that in anti-Al2. In the presence of stoichiometrical Bn OH, syn-Al2 and anti-Al2 were both efficient for ring-opening polymerization（ROP） of rac-LA with the former being more active. In the presence of excess Bn OH, syn-Al2 showed an efficient and immortal feature, consistent with high conversions, matched Mns, narrow molecular weight distributions and end group fidelity, while anti-Al2 had a much lower activity or even became entirely inactive due to rapid decomposition, indicated by in situ ～1H-NMR experiments of Al complexes with Bn OH.展开更多
Traditional donor-acceptor type organic luminescent materials usually suffer from unfavorable spectral broadening and fluorescence quenching problems arising from strong inter/intra-chromophore interactions in aggrega...Traditional donor-acceptor type organic luminescent materials usually suffer from unfavorable spectral broadening and fluorescence quenching problems arising from strong inter/intra-chromophore interactions in aggregation state.Here,two ultraviolet carbazole-pyrimidine isomers(named o-DCz-Pm and m-DCz-Pm)with novel aggregation-induced narrowband phenomenon are constructed and systematic investigated by experiments and theoretical simulations.Benefitting from strengthened steric hindrance and multiple noncovalent interactions,the nonradiative decay,vibrational motion,and structural relaxation of singlet state can be effectively suppressed in aggregation state.Consequently,the electroluminescence peak of 397 nm,full width at half maximum of 21 nm and external quantum efficiency of 3.4%are achieved simultaneously in nondoped o-DCz-Pm-based device.This work paves an avenue toward the development of high-performance narrowband nondoped ultraviolet materials and organic light-emitting diodes.展开更多
We use a Monte Carlo method to study the phase and interracial behaviors of A-b-B diblocks in a blend of homopolymers, A and B, which are confined between two asymmetric hard and impenetrable walls. Our results show t...We use a Monte Carlo method to study the phase and interracial behaviors of A-b-B diblocks in a blend of homopolymers, A and B, which are confined between two asymmetric hard and impenetrable walls. Our results show that, when the interaction strength is weak, the block copolymers are uniformly distributed in the ternary mixtures under considered concentrations. Under strong interaction strength, distribution region of the block copolymers changes from a single smooth interface to a curved interface or multi-layer interface in the ternary mixtures. Furthermore, our findings show that with increasing volume fraction of A-b-B diblock copolymer （φc）, copolymer profiles broaden while φc ≥ 0.4, a lamellar phase is formed and by further increasing φc, more thinner layers are observed. Moreover, the results show that, with the increase of φc, the phase interface first gradually transforms from plane to a curved surface rather than micelle or lamellar phase while with the increase of the interaction between A and B segments （CAB）, the copolymer chains not only get stretched in the direction perpendicular to the interface, but also are oriented. The simulations also reveal that the difference between symmetric and asymmetric copolymers is negligible in statistics if the lengths of two blocks are comparable.展开更多
L-glutamic acid(LA)is a bio-based,non-toxic,environmentally friendly material derived from biomass.The present study reports the application of Passerini three-component polymerization(P-3CP)for the straightforward pr...L-glutamic acid(LA)is a bio-based,non-toxic,environmentally friendly material derived from biomass.The present study reports the application of Passerini three-component polymerization(P-3CP)for the straightforward preparation of LA-based light-responsive polyesters(PLTDs)under mild conditions.PLTDs with molar masses up to 8500 g/mol and high yields exceeding 90%are obtained.The chemical structures and light-responsive self-immolative behavior of PLTDs are comprehensively characterized by employing ultraviolet-visible(UV-Vis)spectroscopy,size exclusion chromatography(SEC),nuclear magnetic resonance(NMR)spectroscopy,and liquid chromatography mass spectrometry(LC-MS).Meanwhile,monodisperse PLTD-based doxorubicin-loaded nanoparticles(PLTD-DOX-NP)(size=193 nm,PDI=0.018)are formulated by nanoprecipitation method.Upon light-induced depolymerization,the PLTD-DOX-NP undergoes rapid decomposition,resulting in a burst release of 80%cargo within 13 s.Furthermore,according to biological toxicity tests,the PLTD-NP possesses adequate biosafety,both before and after irradiation.Overall,the incorporation of P-3CP with biorenewable LA-based monomer adheres to the principles of green chemistry,significantly simplifying the synthetic pathway of light-responsive polymers.展开更多
Hollow semiconductor nanostructures with direct Z-scheme heterojunction have significant advantages for photocatalytic reactions,and optimizing the interfacial charge transmission of Z-scheme heterojunction is the hin...Hollow semiconductor nanostructures with direct Z-scheme heterojunction have significant advantages for photocatalytic reactions,and optimizing the interfacial charge transmission of Z-scheme heterojunction is the hinge to achieve excellent solar conversion efficiency.In this work,tubular Ni_(1−x)Co_(x)S_(2)-CdS heterostructures with reinforced Z-scheme charge transmission were constructed through an In-metal-organic framework(MOF)templated strategy.The Z-scheme charge transfer mechanism was sufficiently confirmed by combining density functional theory(DFT)calculation,X-ray photoelectron spectroscopy(XPS),surface photovoltage spectroscopy(SPV),and radical testing results.Crucially,the use of sodium citrate complexant contributes to the formation of intimate heterointerface,and the Fermi level gap between CdS and NiS_(2)is enlarged through Co doping into NiS_(2),which enhances the built-in electric field and photo-carriers transmission driving force for Ni_(1−x)Co_(x)S_(2)-CdS heterojunction,resulting in an evidently promoted activity toward H2 evolution reaction(HER).Under visible-light(λ>400 nm)irradiation,the Ni_(1−x)Co_(x)S_(2)-CdS composite with 10 mol%Co doping and 80 wt.%CdS(NC_(0.10)S-80%CdS)achieved an outstanding HER rate up to 35.94 mmol·g^(−1)·h^(−1)(corresponding to the apparent quantum efficiency of 34.7%at 420 nm),approximately 76.4 times that of 3 wt.%Pt-loaded CdS and it is much superior to that of most CdS-based photocatalysts ever reported.Moreover,the good photocatalytic durability of Ni_(1−x)Co_(x)S_(2)-CdS heterostructures was validated by cycling and long-term HER tests.This work could inspire the development of high-performance Z-scheme heterojunction via optimizing the morphology and interfacial charge transmission.展开更多
基金Supported by National Key Research and Development Program of China(2022 YFB 3704700(2022 YFB 3704702))Major Scientific and Technological Innovation Project of Shandong Province(2021 CXGC 010901)Taishan Scholar Program。
文摘Heterogeneous TiCl4/MgCl_(2) type Ziegler-Natta(Z-N)catalysts with unique advantages like low cost,high activity,high stereoregularity and pretty particle morphology,contribute to more than 130 Mt polyolefin large-scale production.However,most researches related with heterogeneous Z-N catalysts focused onα-olefin polymerizations like ethylene,propylene,etc.
文摘Graphene oxide(GO)with excellent dispersion ability can assist the dispersion of single-walled carbon nanotube(SWCNT)and promote the formation of uniform and stable GO/SWCNT coating liquid.The highly conductive polyethylene terephthalate/reduced graphene oxide/SWCNT(PET/rGO/SWCNT)electromagnetic shielding composite fabric was successfully prepared by anchoring rGO/SWCNT on PET fabric via dip-coating piror to low-temperature thermal reduction.The results showed that the carboxyl groups and hydroxyl groups formed of hydrophilic-treated PET were conducive to the formation of hydrogen bonds with that of GO,which enhanced the interaction between PET fabric and GO/SWCNT coating;the loading of GO/SWCNT increased with the number of dip-coating,the unit area loading of rGO/SWCNT in the final composite fabric was 2.7 mg/cm^(2) after 10 dip-coating cycles and thermal reduction;the PET/rGO/SWCNT composite fabric had a continuous and dense conductive network,with a conductivity of up to 41.6 S/m and the average electromagnetic interference shielding effectiveness in X-band was 22 dB;the flexible PET/rGO/SWCNT composite fabric was not only easy to process,but also exhibited excellent conductivity and shielding efficiency,showing great potential in the application of electromagnetic shielding fabrics.
基金Supported by PetroChina Company Limited Project (2020 B-2711)。
文摘Neodymium(Nd)-based catalyst in butadiene(Bd)polymerization has drawn interests due to its availability in affording higher cis-1,4-unit selectivity than transition metal(Ti,Co,Ni,etc.)-based catalysts[1-2].Such outstanding high cis-1,4-unit selecti-vity is hypothetically originated from the presence of 4 f orbitals,that can participate in monomer coordination and thereby govern subsequent enchainment manners.This unique characteristic also renders the active species highly susceptible to Lewis bases,and may impact the overall selectivity as well as polyme-rization behavior after coordination.Nevertheless,it is still a virgin area in such a field,and the influence of Lewis bases on Nd-based diene polymerizations is still a black box.Based on this consideration,how nitrogen-containing donors(D)impacts the overall behaviors of Nd-mediated Bd polymerizations is disclosed.
基金Supported by PetroChina Company Limited(2020 B-2711)。
文摘End-functionalization of polydiene rubbers can not only improve its compatibility with inorganic fillers,but also enhance the overall mechanical properties.Nevertheless,for traditional neodymium(Nd)diene polymerization systems,it is highly challenging to achieve such end-functionalizations,because most of polydienyl chains are capped withη3-allyl-Nd moiety during the end of polymerization,which shows very poor reactivity with nucleophile compounds.We launched a new diene polymerization strategy calling coordinative chain transfer polymerization(CCTP)[1].In such a system,all the polydienyl chains are capped withη1-allyl-Al moieties,which reveal greater reactivity with cyclic esters and epoxide compounds,providing an effective manner to prepare polydiene-polyester amphiphilic block copolymers.Inspired by such findings,we now show herein how such types of chain-ends react with isot-hiocyanate to demonstrate an efficient in-situ manner to access end-functionalized polydienes by using CCTP.
文摘The gas-liquid phase equilibrium is used in controlling the nitrosation reaction process. Decomposition of nitrous acid and oxidation side reaction.are suppressed in a closed reaction system. The system pressure is used as the criterion of the end of reaction, avoiding excessive feeding and reducing＇the decomposition＇of nitrous acid. The head space of the reactor is used as the gas buffer, stabilizing the feeding fluctuations and inhibiting the side reaction, decomposition of nitrous acid. Nitrogen oxide concentration is controlled at the minimum level.Thus the zero release ofnitrogen ox!de waste gas can be achieved without using any absorption process.
基金Supported by Shandong Key Research and Development Plan(Military and Civilian Technology Integration)(2018JMRH0205).
文摘Hydrogenated nitrile rubber(HNBR)was prepared by selective hydrogenation of nitrile-butadiene rubber latex using hydrazine hydrate/hydrogen peroxide catalytic system,which effectively resolved the problems with environment pollution and high cost caused by noble metal catalyst via solution hydrogenation method.Because of the saturation of carbon-carbon double bonds after hydrogenation,HNBR presented excellent thermal-oxidative aging resistance.The thermaloxidative activation of HNBR prepared in situ was investigated by thermogravimetric analysis(TGA)and Flynn-Wall-Ozawa method.Meanwhile,the microstructure and mechanical properties of HNBR was studied during the thermal-oxidative aging process.The relationship between lifetime and aging temperature was evaluated as well as the thermal-oxidative aging coefficient of HNBR,which provided theoretical basis for the application of HNBR under the high temperature and in harsh environment.
基金This work was financially supported by the National Key R&D Program of China(No.2022YFB3704700).
文摘In this study,a novel iron-based catalyst system,Fe(acac)3/(isocyanoimino)triptenylphosphorane(IITP)/AlR3,was employed for the synthesis of syndiotactic 1,2-polybutadiene in hexane.This catalyst system exhibits remarkably high catalytic activity,achieving a polymerization activity of 762 kgpolymer·molcatalyst^(-1)·h^(-1)at 50℃with a[BD]/[Fe]molar ratio of 20000.Furthermore,living polymerization characteristic were observed during the investigation of the polymerization kinetics of 1,3-butadiene polymerization.These characteristics were well demonstrated by a narrow molecular weight distribution(PDI≈2.0)of the resulting polybutadiene and a linear relationship between-ln(1-c)and polymerization time as well as number average molecular weight and polymer yield.The resultant polymer showed a 1,2-selectivity of approximately 76%and stereoregularity ranging from 62%to 73%(rrrr).Additionally,through kinetic studies on polymerization reaction,an apparent activation energy Ea value of this catalytic system was calculated to be 84.98 kJ·mol^(-1),which suggests that high polymerization temperature favors efficient polymerization.
基金financially supported by the National Key R&D Program of China(No.2021YFA1501600)the National Natural Science Foundation of China(Nos.22175105 and 22031005)。
文摘Well-defined polycarbonate diol was successfully synthesized through a strategy using a combination of organocatalyst and water.Such strategy was less developed in organocatalyzed polymerization and frequently regarded as side reactions.Herein,one-component phosphonium borane Lewis pairs PB1-PB8 were successfully applied in the copolymerization of CO_(2) and cyclohexene oxide(CHO)to generate poly(CHO-alt-CO_(2))carbonate(PCHC).Parameters of linker length and counter anion effects on the catalyst activity were investigated.It was found that Lewis pair PB3 served as a dual initiator and catalyst in the copolymerization of CHO and CO_(2) with or without the presence of water.In contrast,Lewis pair PB8 can serve as a true catalyst for the preparation of well-definedα,ω-hydroxyl PCHC diols.This was achieved by introducing a labile CF3COO group as counter anion through anion exchange reaction while water molecules acted as chain transfer agents.The function of trifluoroacetate group in the polymerization process was investigated in detail and possible mechanism was proposed.Upon changing the amount of water and catalyst loading,PCHC diols with varied molecular weight(1.5 kg/mol to 7.5 kg/mol),low dispersities(D<1.2)and carbonate content(>99%)could be easily obtained.The low molecular weight PCHC diol was used as a bifunctional macroinitiator for the ring-opening polymerization of L-lactide(LLA)to afford ABA triblock copolymer in one-pot synthesis.
基金This work was financially supported by the National Natural Science Foundation of China(grant nos.21835001,52073116,and 51773080)the JLU Science and Technology Innovative Research Team(grant no.2021TD-03).
文摘Identification and visualization of phase structures inside polymer blends are of critical importance in the understanding of their intrinsic structure and dynamics.However,the direct optical observation of the individual component phase in a dense bulk material poses a significant challenge.Herein,three-dimensional fluorescence imaging of phase separation and realtime visualization of phase transformation in immiscible polymer blends of polypropylene and polystyrene is realized through multiphoton laser scanning microscopy.Owing to the specific fluorescence behavior of the cyanostyrene derivative 2-(4-bromophenyl)-3-(4-(4-(diphenylamino)styryl)phenyl)fumaronitrile,the high-contrast imaging of the macrophase of the component polymer in two and three dimensions with a maximum depth of 140μm and a high signal-to-noise ratio of 300 can be achieved.Detailed spectroscopic and structural studies reveal that the distinctive fluorescence features of each phase domain should originate from the formation of a completely different aggregate between probes and component polymer.Furthermore,visualizations of the internal morphology deformation and macrophase transformation were realized by employing a stretched dumbbell sample under constant tension.
基金supported by funding from the Shandong Natural Science Excellent Youth Fund(ZR2019YQ22)the Research Initiation Fund of Qingdao University of Science and Technology。
文摘Solid electrolytes play a vital role in solid-state Li secondary batteries,which are promising high-energy storage devices for new-generation electric vehicles.Nevertheless,obtaining a suitable solid electrolyte by a simple and residue-free preparation process,resulting in a stable interface between electrolyte and electrode,is still a great challenge for practical applications.Herein,we report a self-crosslinked polymer electrolyte(SCPE)for high-performance lithium batteries,prepared by a one-step method based on 3-methoxysilyl-terminated polypropylene glycol(SPPG,a liquid oligomer).It is worth noting that lithium bis(oxalate)borate(Li BOB)can react with SPPG to form a crosslinked structure via a curing reaction.This self-formed polymer electrolyte exhibits excellent properties,including high roomtemperature ionic conductivity(2.6×10^(-4) S cm^(-1)),wide electrochemical window(4.7 V),and high Li ion transference number(0.65).The excellent cycling stability(500 cycles,83%)further highlights the improved interfacial stability after the in situ formation of SCPE on the electrode surface.Moreover,this self-formation strategy enhances the safety of the battery under mechanical deformation.Therefore,the present self-crosslinked polymer electrolyte shows great potential for applications in high-performance lithium batteries.
基金the National Natural Science Foundation of China (No. 21790343)
文摘Linear and non-linear rheological properties were examined for in-reactor alloy samples composed of isotactic polypropylene(iPP),ethylene-propylene rubber(EPR),and polyethylene(PE).The samples were prepared through two-or three-stage sequential polymerization,where iPP,as the majority,was synthesized in the first stage,and either EPR or PE,as the minority,was synthesized in the second or third stage.Above Tm of both PE and iPP,the linear viscoelasticity shows two relaxation processes,where the fast and slow processes are attributable to the relaxation of the iPP component and that of the EPR/PE domains,respectively.Both the damping behavior upon applying the step-strain measurements and the shear-thinning behavior under the shear-rate sweep measurements are strongly related to the different degrees of nonlinearity of the two relaxation processes.
基金financially supported by the National Basic Research Program of China(No.2015CB654700(2015CB654706))Shandong Province Natural Science Fund for Distinguished Young Scholars(No.JQ201213)the National Natural Science Foundation of China(No.51473083)
文摘Abstract Two series of trans-1,4-poly（butadiene-co-isoprene） copolymers （TBIR） were prepared using the catalyst system TiCl4/MgCl2-Al（i-Bu）3 at different reaction temperatures. All dyad and triads sequence distributions, the number-average sequence length and the sequence concentration of the copolymers were calculated according to 13C-NMR spectra. The influences of temperature and initial molar ratio of butadiene to isoprene （Bd to Ip） on the distribution of the chain segments in the TBIR copolymers were discussed. The correlation of copolymer compositions and thermal properties were also evaluated, which facilitated the understanding of controlling the degree of crystallinity and the transition tempera^re by changing Bd content and temperature.
基金financially supported by the National Key Technology R&D Program of China(No.2011BAE26B05)the Shandong Province Natural Science Fund for Distinguished Young Scholars(No.JQ201213)+2 种基金National Natural Science Foundation of China(No.21174074)Shandong Province Science and Technology Development Plan(No.2012GGA05042)the Major Projects of Independent Innovation Achievements Transformation in Shandong Province(No.2013ZHZX1A0207)
文摘A series of trans-1,4-butadiene/isoprene copolymers were prepared using the catalyst system TiCl4/MgCl2-Al（i- Bu）3 with bulk precipitation technology at different temperatures. Monomers reactivity ratios were calculated based on the Kelen-Tiid6s （K-T） method and the Mao-Huglin （M-H） method. The influence of temperature on copolymer composition and polymerization rate was discussed in detail. The increase of reaction temperature brought the decrease of butadiene reactivity ratio rBd and supplied an effective adjustment on copolymers＇ composition distribution.
基金financially supported by the Major Scientific and Technological Innovation Project of Shandong Province(No.2019JZZY010352)Natural Science Foundation of Shandong Province(No.ZR2019MB072)Taishan Scholar Program。
文摘The catalytic activity and stereospecificity of olefin polymerization by using heterogeneous TiCl_(4)/MgCl_(2) Ziegler-Natta(Z-N) catalysts are determined by the structure and nature of active centers, which are mysterious and fairly controversial. In this work, the propylene polymerization kinetics under different polymerization temperatures by using Z-N catalysts were investigated through monitoring the concentration of active centers [C*] with different tacticity. SEM was applied to characterize the catalyst morphologies and growing polypropylene(PP) particles. The lamellar thickness and crystallizability of PP obtained under different polymerization conditions were analyzed by DSC and SAXS. The PP fractions and active centers with different tacticity were obtained with solvent extraction fractionation method. The catalytic activity, active centers with different tacticity and propagation rate constant kp, fragmentation of the catalyst, crystalline structure of PP are correlated with temperature and time for propylene polymerizations. The polymerization temperature and time show complex influences on the propylene polymerization. The higher polymerization temperature(60 ℃) resulted higher activity, kp and lower [C*], and the isotactic active centers Ci* as the majority ones producing the highest isotactic polypropylene(iPP) components showed much higher kp when compared with the active centers with lower stereoselectivity. Appropriate polymerization time provided full fragmentation of the catalyst and minimum diffusion limitation. This work aims to elucidate the formation and evolution of active centers with different tacticity under different polymerization temperature and time and its relations with the fragmentation of the PP/catalyst particles, and provide the solutions to the improvement of catalyst activity and isotacticity of PP.
基金financially supported by the National Natural Science Foundation of China (No. B040102)State Key Laboratory for Modification of Chemical Fibers and Polymer Materials (Donghua University) (No. LK1501)Department of Science and Technology of Qingdao and Shandong Province (Nos. 159181jch and 2015GGX107015)
文摘Two types of bifunctional bis（salicylaldimine） ligands（syn-L and anti-L） were designed and synthesized to support bimetallic aluminum complexes. Owing to the rigid anthracene skeleton, syn-L and anti-L successfully locked two Al centers in close proximity（syn-Al2） and far apart（anti-Al2）, respectively. The distance between two Al centers in syn-Al2 was defined by X-ray diffraction as 6.665 ？, which is far shorter than that in anti-Al2. In the presence of stoichiometrical Bn OH, syn-Al2 and anti-Al2 were both efficient for ring-opening polymerization（ROP） of rac-LA with the former being more active. In the presence of excess Bn OH, syn-Al2 showed an efficient and immortal feature, consistent with high conversions, matched Mns, narrow molecular weight distributions and end group fidelity, while anti-Al2 had a much lower activity or even became entirely inactive due to rapid decomposition, indicated by in situ ～1H-NMR experiments of Al complexes with Bn OH.
基金National Natural Science Foundation of China,Grant/Award Numbers:52002804,52103220,52103017,22022501Shandong Provincial Natural Science Foundation,Grant/Award Numbers:ZR2023QE078,ZR2022ZD37,ZR2019ZD50Natural Science Foundation of Qingdao Municipality,Grant/Award Number:23-2-1-75-zyyd-jch。
文摘Traditional donor-acceptor type organic luminescent materials usually suffer from unfavorable spectral broadening and fluorescence quenching problems arising from strong inter/intra-chromophore interactions in aggregation state.Here,two ultraviolet carbazole-pyrimidine isomers(named o-DCz-Pm and m-DCz-Pm)with novel aggregation-induced narrowband phenomenon are constructed and systematic investigated by experiments and theoretical simulations.Benefitting from strengthened steric hindrance and multiple noncovalent interactions,the nonradiative decay,vibrational motion,and structural relaxation of singlet state can be effectively suppressed in aggregation state.Consequently,the electroluminescence peak of 397 nm,full width at half maximum of 21 nm and external quantum efficiency of 3.4%are achieved simultaneously in nondoped o-DCz-Pm-based device.This work paves an avenue toward the development of high-performance narrowband nondoped ultraviolet materials and organic light-emitting diodes.
基金supported by the National Natural Science Foundation of China(Nos.21304097,21334007and 21674113)
文摘We use a Monte Carlo method to study the phase and interracial behaviors of A-b-B diblocks in a blend of homopolymers, A and B, which are confined between two asymmetric hard and impenetrable walls. Our results show that, when the interaction strength is weak, the block copolymers are uniformly distributed in the ternary mixtures under considered concentrations. Under strong interaction strength, distribution region of the block copolymers changes from a single smooth interface to a curved interface or multi-layer interface in the ternary mixtures. Furthermore, our findings show that with increasing volume fraction of A-b-B diblock copolymer （φc）, copolymer profiles broaden while φc ≥ 0.4, a lamellar phase is formed and by further increasing φc, more thinner layers are observed. Moreover, the results show that, with the increase of φc, the phase interface first gradually transforms from plane to a curved surface rather than micelle or lamellar phase while with the increase of the interaction between A and B segments （CAB）, the copolymer chains not only get stretched in the direction perpendicular to the interface, but also are oriented. The simulations also reveal that the difference between symmetric and asymmetric copolymers is negligible in statistics if the lengths of two blocks are comparable.
基金This work was financially supported by the International Science and Technology Assistance Program of the Ministry of Science and Technology(No.KY202001016)Shandong Provincial Natural Science Foundation Magnitude Fundamental Research,China(No.ZR2022ZD11)Qingdao New Energy Shandong Laboratory Open Project(No.QNESL OP202312).
文摘L-glutamic acid(LA)is a bio-based,non-toxic,environmentally friendly material derived from biomass.The present study reports the application of Passerini three-component polymerization(P-3CP)for the straightforward preparation of LA-based light-responsive polyesters(PLTDs)under mild conditions.PLTDs with molar masses up to 8500 g/mol and high yields exceeding 90%are obtained.The chemical structures and light-responsive self-immolative behavior of PLTDs are comprehensively characterized by employing ultraviolet-visible(UV-Vis)spectroscopy,size exclusion chromatography(SEC),nuclear magnetic resonance(NMR)spectroscopy,and liquid chromatography mass spectrometry(LC-MS).Meanwhile,monodisperse PLTD-based doxorubicin-loaded nanoparticles(PLTD-DOX-NP)(size=193 nm,PDI=0.018)are formulated by nanoprecipitation method.Upon light-induced depolymerization,the PLTD-DOX-NP undergoes rapid decomposition,resulting in a burst release of 80%cargo within 13 s.Furthermore,according to biological toxicity tests,the PLTD-NP possesses adequate biosafety,both before and after irradiation.Overall,the incorporation of P-3CP with biorenewable LA-based monomer adheres to the principles of green chemistry,significantly simplifying the synthetic pathway of light-responsive polymers.
基金supported by the National Natural Science Foundation of China(Nos.22179068,52272222,52072197,and 52171140)the 111 Project of China(No.D20017)+5 种基金the Natural Science Foundation of Shandong Province(No.ZR2019JQ14)the Major Scientific and Technological Innovation Project of Shandong Province(No.2019JZZY020405)the Key Research and Development Program of Jiangsu Province(No.BE2021070)the Scientific and Technological Innovation Promotion Project for Small-medium Enterprises of Shandong Province(No.2022TSGC1257)the Shandong Province“Double-Hundred Talent Plan”(Nos.WST2019011,WST2020003,and WST2021021)the Major Research Program of Jining City(No.2020ZDZP024).
文摘Hollow semiconductor nanostructures with direct Z-scheme heterojunction have significant advantages for photocatalytic reactions,and optimizing the interfacial charge transmission of Z-scheme heterojunction is the hinge to achieve excellent solar conversion efficiency.In this work,tubular Ni_(1−x)Co_(x)S_(2)-CdS heterostructures with reinforced Z-scheme charge transmission were constructed through an In-metal-organic framework(MOF)templated strategy.The Z-scheme charge transfer mechanism was sufficiently confirmed by combining density functional theory(DFT)calculation,X-ray photoelectron spectroscopy(XPS),surface photovoltage spectroscopy(SPV),and radical testing results.Crucially,the use of sodium citrate complexant contributes to the formation of intimate heterointerface,and the Fermi level gap between CdS and NiS_(2)is enlarged through Co doping into NiS_(2),which enhances the built-in electric field and photo-carriers transmission driving force for Ni_(1−x)Co_(x)S_(2)-CdS heterojunction,resulting in an evidently promoted activity toward H2 evolution reaction(HER).Under visible-light(λ>400 nm)irradiation,the Ni_(1−x)Co_(x)S_(2)-CdS composite with 10 mol%Co doping and 80 wt.%CdS(NC_(0.10)S-80%CdS)achieved an outstanding HER rate up to 35.94 mmol·g^(−1)·h^(−1)(corresponding to the apparent quantum efficiency of 34.7%at 420 nm),approximately 76.4 times that of 3 wt.%Pt-loaded CdS and it is much superior to that of most CdS-based photocatalysts ever reported.Moreover,the good photocatalytic durability of Ni_(1−x)Co_(x)S_(2)-CdS heterostructures was validated by cycling and long-term HER tests.This work could inspire the development of high-performance Z-scheme heterojunction via optimizing the morphology and interfacial charge transmission.
