The density functional theory on the level of B3LYP/6-31G was empolyed to study the chain growth mechanism in polymerization process of α-linear olefin in TiCl3/AlEt2Cl catalytic system to synthesize drag reduction a...The density functional theory on the level of B3LYP/6-31G was empolyed to study the chain growth mechanism in polymerization process of α-linear olefin in TiCl3/AlEt2Cl catalytic system to synthesize drag reduction agent. Full parameter optimization without symmetry restrictions for reactants, products, the possible transition states, and intermediates was calculated. Vibration frequency was analyzed for all of stagnation points on the potential energy surface at the same theoretical level. The internal reaction coordinate was calculated from the transition states to reactants and products respectively. The results showed as flloes： （i） Coordination compounds were formed on the optimum configuration of TiCl3/AlEt2Cl.（ii） The transition states were formed. The energy di？erence between transition states and the coordination compounds was 40.687 kJ/mol. （iii） Double bond opened and Ti-C（4） bond fractured, and the polymerization was completed. The calculation results also showed that the chain growth mechanism did not essentially change with the increase of carbon atom number of α-linear olefin. From the relationship between polymerization activation energy and carbon atom number of the α-linear olefin, it can be seen that the α-linear olefin monomers with 6-10 carbon atoms had low activation energy and wide range. It was optimum to synthesize drag reduction agent by polymerization.展开更多
A new monomer, 3,9-diallyl-3, 9-dibenzyl-1, 5,7,11 - tetraoxa- spiro [5,5] undecane (6) was prepared by the reaction of 2- allyl- 2' - benzyl- propanediol - 1.3 with dibutyltin oxide, and then treated with CS_2. M...A new monomer, 3,9-diallyl-3, 9-dibenzyl-1, 5,7,11 - tetraoxa- spiro [5,5] undecane (6) was prepared by the reaction of 2- allyl- 2' - benzyl- propanediol - 1.3 with dibutyltin oxide, and then treated with CS_2. Monomer 4 could be initiated by cationic initiators to give a viscous polymer (white powder in the case of polymerization at 0℃). Upon the NMR and IR spectra of the obtained polymer, the components and their relative amount were estimated. The polymerization mechanism was discussed.展开更多
(η^-C_H_5)_2CeCl_5Mg_2(tmed)_2 was used as a catalyst to polymerize isoprene,Terminal ends of polyisoprene were identified as -CH_2-CH=CH_,which indicates that the insertion reaction of the monomer occurred between ...(η^-C_H_5)_2CeCl_5Mg_2(tmed)_2 was used as a catalyst to polymerize isoprene,Terminal ends of polyisoprene were identified as -CH_2-CH=CH_,which indicates that the insertion reaction of the monomer occurred between η^-allyl and cerium ion and gives a direct evidence for the η^-allyl mechanism of conjugated diene polymerzation with rare earth coordination catalysts.展开更多
The deformation mechanism of glycerol plasticized poly(vinyl alcohol)(PVA)with different hydrolyses(88%,92%,98%)at elevated temperatures(60-100℃)was elucidated by in situ synchrotron radiation X-ray scattering.The vi...The deformation mechanism of glycerol plasticized poly(vinyl alcohol)(PVA)with different hydrolyses(88%,92%,98%)at elevated temperatures(60-100℃)was elucidated by in situ synchrotron radiation X-ray scattering.The vinyl acetate(VAc)in PVA acts as a non-crystalline chain defect,which significantly influences the plastic deformation and stretching-induced crystallization behavior of PVA.The key microstructural parameters of PVA during deformation,such as crystallinity(χ_(c)),lateral crystallite size(L),and long period(l),in combination with the stress-strain curves,were obtained.The experimental results show that the deformation process of the plasticized PVA film present a three-stage evolution:(i)a plastic deformation zone.The plastic deformation of the crystallite occurs as evidenced by the apparent decrease in crystallinity and lamellar reorientation induced by stretching;(ii)the stress softening zone.The decreasing trend of crystallinity becomes slow,and the long period becomes smaller,which indicates that PVA crystallization is induced by stretching;and(iii)the strain-hardening zone.There is a synergistic effect between the crystallite destruction and formation.Further research reveals that a high temperature and low degree of alcoholysis favor the stretching-induced crystallization of PVA,while the system with a high degree of alcoholysis shows significant characteristics of preferred crystal growth.展开更多
The CO_2 quenching method has been used for the first time to determine the active complex concen- tration in Nd(naph)_3-Al(i-Bu)_3 catalyst system for polymerization of phenylacetylene into polyphenylacetylene(PPA)fi...The CO_2 quenching method has been used for the first time to determine the active complex concen- tration in Nd(naph)_3-Al(i-Bu)_3 catalyst system for polymerization of phenylacetylene into polyphenylacetylene(PPA)films.The kinetics and mechanism of this polymerization have been investigated by CO_2 quenching and IR,UV analytical methods.The kinetic equation can be expressed as Rp=k[M][Cp],and the apparent activation energy is about 13.6 kJ/mol.There is self-termination of chain propagating.Models for formation of the active complex and polymerization mechanism are proposed.展开更多
It is found that acetoacetanilide possesses very high promoting reactivity towards ceric ion in initiating polymerization of vinyl monomer. The kinetics of acrylamide polymerization and the activation energies were st...It is found that acetoacetanilide possesses very high promoting reactivity towards ceric ion in initiating polymerization of vinyl monomer. The kinetics of acrylamide polymerization and the activation energies were studied. The initiation mechanism of ceric/acetoacetanilide is proposed on the basis of experimental results of FT-IR and ESR.展开更多
A novel benzoxazine(BOZ)monomer is synthesized by a pot method with solvent-free to blend with cyanate ester(CE).A soluble intermediate is obtained after being cured for 20 h at 80℃.The two model compound and the ble...A novel benzoxazine(BOZ)monomer is synthesized by a pot method with solvent-free to blend with cyanate ester(CE).A soluble intermediate is obtained after being cured for 20 h at 80℃.The two model compound and the blends are analyzed with the infrared radiation(IR),nuclear magnetic resonance(NMR)spectroscopy,and differential scanning calorimetry(DSC).The results show that an intermediate of the iminocarbonate and BOZ structures is formed by the ring-open BOZ reacting with the cyanate groups and ring-unopened BOZ.Moreover,rearrangement and ring-opening occur in the postcure of the intermediate to form the alkyl isocyanurate structure with polybenzoxazine.展开更多
Polymer solid-state lithium batteries(SSLB)are regarded as a promising energy storage technology to meet growing demand due to their high energy density and safety.Ion conductivity,interface stability and battery asse...Polymer solid-state lithium batteries(SSLB)are regarded as a promising energy storage technology to meet growing demand due to their high energy density and safety.Ion conductivity,interface stability and battery assembly process are still the main challenges to hurdle the commercialization of SSLB.As the main component of SSLB,poly(1,3-dioxolane)(PDOL)-based solid polymer electrolytes polymerized in-situ are becoming a promising candidate solid elec-trolyte,for their high ion conductivity at room temperature,good battery elec-trochemical performances,and simple assembly process.This review analyzes opportunities and challenges of PDOL electrolytes toward practical application for polymer SSLB.The focuses include exploring the polymerization mechanism of DOL,the performance of PDOL composite electrolytes,and the application of PDOL.Furthermore,we provide a perspective on future research directions that need to be emphasized for commercialization of PDOL-based electrolytes in SSLB.The exploration of these schemes facilitates a comprehensive and profound understanding of PDOL-based polymer electrolyte and provides new research ideas to boost them toward practical application in solid-state batteries.展开更多
Water existing in water-absorbing plasma polymerized N-vinyl-2-pyrrolidone(PPNVP) include pure bulk water, freezable water and non-freezing, or bound, water. The C-N bond of N, N-disubstituted amides in PPNVP was cons...Water existing in water-absorbing plasma polymerized N-vinyl-2-pyrrolidone(PPNVP) include pure bulk water, freezable water and non-freezing, or bound, water. The C-N bond of N, N-disubstituted amides in PPNVP was considered as an active binding site for bound water.展开更多
The development of living radical polymerization(LRP)methods has served as one of the most remarkable milestones for polymer chemistry.Independent LRP method requires specific conditions,catalysts,and monomers,which f...The development of living radical polymerization(LRP)methods has served as one of the most remarkable milestones for polymer chemistry.Independent LRP method requires specific conditions,catalysts,and monomers,which fits certain scenes,while it is unfit for others.While the combination of different methods integrates the advantages of various LRP methods,not all methods could be combined directly due to the complexity of the mutual influence between them.To overcome this,we established a criterion that could tell whether a combination of LRP methods was effective or not.With the help of this criterion,the dual concurrent ATRP-RAFT was constructed by the combination of ICAR-ATRP and RAFT.The binary LRP method allowed for(1)the expansion of monomer range for RAFT;(2)the reduction of CuII loading for ICAR-ATRP;(3)the enhanced control of dispersity.We believe that this research provides a different route for the development of the LRP methods.展开更多
The general development of Rheo-NMR during the last four decades as well as selective hyphenated apparatuses is presented.Based on different magnet types,the current review is divided into two categories,namely low-fi...The general development of Rheo-NMR during the last four decades as well as selective hyphenated apparatuses is presented.Based on different magnet types,the current review is divided into two categories,namely low-field and high-field NMR,while the timedomain NMR is normally applied in the former case and the frequency-domain NMR is adopted in the latter one.Depending on different rheometer cells,it can be further divided into tensile and shear mode Rheo-NMR.The combination of various rheometer cells and NMR facility guarantees our acquisition of molecular level structure and dynamics information under flow conditions,which is crucial for our understanding of the molecular origin of complex fluids.A personal perspective is also presented at last to highlight possible development in this direction.展开更多
In this paper, the content of water glass before and after adding modifying agent was measured by Trimethylsilyl-gas-chromatography. The experimental results showed that different modulus of water glass could generate...In this paper, the content of water glass before and after adding modifying agent was measured by Trimethylsilyl-gas-chromatography. The experimental results showed that different modulus of water glass could generate different content of mono-silicate acid and oligomeric silicate acid in water glass. After a period of storage, different modulus of water glass led to decrease of silicate content at different levels. Because higher content of Na<sub>2</sub>O in water glass tended to incur the alkaline polymerization, the occurrence of depolymerization of silicate species would lead to an increase of oligomeric silicate species, resulting in a drawback of silicate species content after a period of storage. And contrary to that, lower content of Na<sub>2</sub>O in water glass tended to incur the acidic polymerization. When the modifying agent was added to the newly made water glass, the amount of mono-silicate acid and oligomeric silicate acid also decreased. In modified water glass, the change of each silicate acid species was less than that in unmodified water glass. These results showed that the modifying agent retarded the aging of water glass. It had remarkable significance on the theory and practical application of water glass chemistry.展开更多
A calcium sulfate whisker （CSW） coated with glutaraldehyde crosslinked chitosan （GACS） was prepared to reinforce polyvinyl chloride （PVC） in this study. The results show that the optimum concentration of both ch...A calcium sulfate whisker （CSW） coated with glutaraldehyde crosslinked chitosan （GACS） was prepared to reinforce polyvinyl chloride （PVC） in this study. The results show that the optimum concentration of both chitosan （CS） and glutaraldehyde （GA） is 0.05 wt%. The tensile strength, impact strength, flexural modulus and vicat softening temperature of the PVC composite with 12 wt% of modified CSW are in- creased by 1 Z5%, 40.4%, 0.8% and 3.8% compared with those of the PVC composite with 12 wt~ of unmodified CSW, and by 2.9%, 42.4%, 2Z1% and 6.8% compared with those of pure PVC, respectively. The dynamic mechanical analysis results indicate that the modified CSW/PVC composite exhibits much higher storage modulus and glass transition temperature than those of unmodified CSW/PVC composite and pure PVC. In addition, the modified CSW/PVC composite also demonstrates good thermal properties with a high rapidest decomposition temperature （Trvd） and char residue. The scanning electron microscopy images of tensile-fractured surfaces show that the modified CSW has a strong interfacial adhesion with PVC matrix.展开更多
The strain and temperature sensing performance of fiber-optic Bragg gratings （FBGs） with soft polymeric coating, which can be used to sense internal strain in superconducting coils, are evaluated under variable cryo...The strain and temperature sensing performance of fiber-optic Bragg gratings （FBGs） with soft polymeric coating, which can be used to sense internal strain in superconducting coils, are evaluated under variable cryogenic field and magnetic field. The response to a temperature and strain change of coated-soft polymeric FBGs is tested by comparing with those of coated-metal FBGs. The results indicate that the coated-soft polymeric FBGs can freely detect temperature and thermal strain, their At variable magnetic field, the tested results indicate accuracy and repeatability are also discussed in detail. that the cross-coupling effects of FBGs with different matrixes are not negligible to measure electromagnetic strain during fast excitation. The present results are expected to be able to provide basis measurements on the strain of pulsed superconducting magnet/cable （cable- around-conduit conductors, cable-in-conduit conductors）, independently or utilized together with other strain measurement methods.展开更多
By using redispersible polymer powder（RPP） and carbon fiber（CF） to adjust the flexibility and electrical properties of the smart aggregate, a new kind of smart aggregate with Z type structure was proposed. The stu...By using redispersible polymer powder（RPP） and carbon fiber（CF） to adjust the flexibility and electrical properties of the smart aggregate, a new kind of smart aggregate with Z type structure was proposed. The study shows that Z type aggregate is more sensitive to the feedback of external force than the prism aggregate in the same loading environment, and it indicates that Z type aggregate is more suitable for the research and application of concrete health monitoring. Although the incorporation of RPP would cause the compressive strength of the aggregates and the elastic modulus of hardened cement mortar to reduce slightly within the dosage of RPP by 2.25% because of the polymer film formed in the internal system, this would improve the deformability of the aggregates. In the early loading stage（in the first 60 seconds）, the intelligent concrete specimens implanted with Z type smart aggregate do not show higher sensitivity as expected, although the resistance change rate changes a little bit more, the overall of it is still in balance. Adding RPP could improve the flexibility of smart aggregates exactly, and it plays an active role in prolonging the life of the smart aggregates. By implanting Z type aggregates the damage and failure of the concrete structure could be predicted accurately in this study. The results of this paper will help to promote further research and application of intelligent concrete.展开更多
PMMA/reactive nanoclay nanocomposites were prepared by emulsion polymerization using two different reactive nanoclays. X-ray diffraction（XRD） and thermogravimetric analysis（TGA） results confirmed that the reactive...PMMA/reactive nanoclay nanocomposites were prepared by emulsion polymerization using two different reactive nanoclays. X-ray diffraction（XRD） and thermogravimetric analysis（TGA） results confirmed that the reactive nanoclays, kaolinite and montmorillonite, were obtained by the silylation reaction and the double bonds were grafted onto the edges and surfaces of the nanoclays. The presence of reactive nanoclays could increase the average molecular weights, the glass transition temperatures（Tg） and improve the thermal properties of nanocomposite. The tensile properties, Young＇s modulus, and the aging properties of the nanocomposite films were also enhanced while the light transmittance decreased. Furthermore, the nanocomposites with the reactive kaolinite presented better performances than that with the reactive montmorillonite. Finally, the action mechanism of the reactive nanoclays to the performances of PMMA/reactive nanoclay nanocomposites was proposed.展开更多
The copolymerization of ethylene and styrene can be efficiently carried out by using Cp＊TiCl2（N=CtBu2）/ MAO （Cp＊=η5-C5Me5） system, yielding the poly（ethylene-co-styrene）s with isolated styrene units. In order...The copolymerization of ethylene and styrene can be efficiently carried out by using Cp＊TiCl2（N=CtBu2）/ MAO （Cp＊=η5-C5Me5） system, yielding the poly（ethylene-co-styrene）s with isolated styrene units. In order to in- vestigate the reasons for formation of the structure, the mechanism of copolymerization, especially the selective in- sertion of ethylene and styrene, is studied in detail by density functional theory （DFT） method. At the initiation stage, insertion of ethylene is kinetically more favorable than insertion of styrene, and insertion of styrene kinet- ically and thermodynamically prefers 2,1-insertion. That is different from the conventional half-titanocene system, in which the 1,2-insertion is favorable. At chain propagation stage, the computational results suggest that the con- tinuous insertion of styrene is hard to occur at room temperature due to the high free energy barriers （28.90 and 35.04 kcal/mol for 1,2-insertion, and 29.15 and 34.00 kcal/mol for 2,1-insertion） and thermodynamically unfavora- ble factors in two different conditions. That is mainly attributed to the steric hindrance between the coming styrene and chain-end styrene or ketimide ligand. The computational results are in good agreement with the experimental data.展开更多
The electrochemical oxidation of diphenylamine in acetonitrile produces an adherent uniform polymer film which exhibits mutiple colour variation(yellow-green-blue) in a wide range of potential scan. The polymerization...The electrochemical oxidation of diphenylamine in acetonitrile produces an adherent uniform polymer film which exhibits mutiple colour variation(yellow-green-blue) in a wide range of potential scan. The polymerization mechanism and the structure of the polymer were studied by cyclic voltammetry, FT-IR and in situ ESR. The results indicate that the electrochemical polymerization of diphenylamine belongs to a cationic radical polymerization process. During electrolysis, only oligomers were initialy produced, then polymer film was formed on the electrode surface. The electropolymerization performs via the 4,4' C-C phenyl-phenyl coupling mechanism.展开更多
Our present study demonstrated and explored the solvent effects on the association mechanism of the supramolecular nanomaterials in a series of cyclo-tetrasiloxane-appended alkynylplatinum(II)terpyri-dine complexes.Th...Our present study demonstrated and explored the solvent effects on the association mechanism of the supramolecular nanomaterials in a series of cyclo-tetrasiloxane-appended alkynylplatinum(II)terpyri-dine complexes.Through the delicate balance of molecular interactions,some of these complexes were found to exhibit molecular association prop-erties,with possible morphological transformation in response to solvent polarities.展开更多
文摘The density functional theory on the level of B3LYP/6-31G was empolyed to study the chain growth mechanism in polymerization process of α-linear olefin in TiCl3/AlEt2Cl catalytic system to synthesize drag reduction agent. Full parameter optimization without symmetry restrictions for reactants, products, the possible transition states, and intermediates was calculated. Vibration frequency was analyzed for all of stagnation points on the potential energy surface at the same theoretical level. The internal reaction coordinate was calculated from the transition states to reactants and products respectively. The results showed as flloes： （i） Coordination compounds were formed on the optimum configuration of TiCl3/AlEt2Cl.（ii） The transition states were formed. The energy di？erence between transition states and the coordination compounds was 40.687 kJ/mol. （iii） Double bond opened and Ti-C（4） bond fractured, and the polymerization was completed. The calculation results also showed that the chain growth mechanism did not essentially change with the increase of carbon atom number of α-linear olefin. From the relationship between polymerization activation energy and carbon atom number of the α-linear olefin, it can be seen that the α-linear olefin monomers with 6-10 carbon atoms had low activation energy and wide range. It was optimum to synthesize drag reduction agent by polymerization.
基金This project is supported by the National Natural Science Foundation of China
文摘A new monomer, 3,9-diallyl-3, 9-dibenzyl-1, 5,7,11 - tetraoxa- spiro [5,5] undecane (6) was prepared by the reaction of 2- allyl- 2' - benzyl- propanediol - 1.3 with dibutyltin oxide, and then treated with CS_2. Monomer 4 could be initiated by cationic initiators to give a viscous polymer (white powder in the case of polymerization at 0℃). Upon the NMR and IR spectra of the obtained polymer, the components and their relative amount were estimated. The polymerization mechanism was discussed.
文摘(η^-C_H_5)_2CeCl_5Mg_2(tmed)_2 was used as a catalyst to polymerize isoprene,Terminal ends of polyisoprene were identified as -CH_2-CH=CH_,which indicates that the insertion reaction of the monomer occurred between η^-allyl and cerium ion and gives a direct evidence for the η^-allyl mechanism of conjugated diene polymerzation with rare earth coordination catalysts.
基金supported by the National Natural Science Foundation of China(No.52422302)Anhui Provincial Natural Science Foundation(Nos.2308085UM02,2408055UM001,and 2308085UM04)the Major Science and Technology Project“Unveiling and Commanding”of Hefei City,Anhui Province(No.2022-SZD-005).
文摘The deformation mechanism of glycerol plasticized poly(vinyl alcohol)(PVA)with different hydrolyses(88%,92%,98%)at elevated temperatures(60-100℃)was elucidated by in situ synchrotron radiation X-ray scattering.The vinyl acetate(VAc)in PVA acts as a non-crystalline chain defect,which significantly influences the plastic deformation and stretching-induced crystallization behavior of PVA.The key microstructural parameters of PVA during deformation,such as crystallinity(χ_(c)),lateral crystallite size(L),and long period(l),in combination with the stress-strain curves,were obtained.The experimental results show that the deformation process of the plasticized PVA film present a three-stage evolution:(i)a plastic deformation zone.The plastic deformation of the crystallite occurs as evidenced by the apparent decrease in crystallinity and lamellar reorientation induced by stretching;(ii)the stress softening zone.The decreasing trend of crystallinity becomes slow,and the long period becomes smaller,which indicates that PVA crystallization is induced by stretching;and(iii)the strain-hardening zone.There is a synergistic effect between the crystallite destruction and formation.Further research reveals that a high temperature and low degree of alcoholysis favor the stretching-induced crystallization of PVA,while the system with a high degree of alcoholysis shows significant characteristics of preferred crystal growth.
文摘The CO_2 quenching method has been used for the first time to determine the active complex concen- tration in Nd(naph)_3-Al(i-Bu)_3 catalyst system for polymerization of phenylacetylene into polyphenylacetylene(PPA)films.The kinetics and mechanism of this polymerization have been investigated by CO_2 quenching and IR,UV analytical methods.The kinetic equation can be expressed as Rp=k[M][Cp],and the apparent activation energy is about 13.6 kJ/mol.There is self-termination of chain propagating.Models for formation of the active complex and polymerization mechanism are proposed.
文摘It is found that acetoacetanilide possesses very high promoting reactivity towards ceric ion in initiating polymerization of vinyl monomer. The kinetics of acrylamide polymerization and the activation energies were studied. The initiation mechanism of ceric/acetoacetanilide is proposed on the basis of experimental results of FT-IR and ESR.
文摘A novel benzoxazine(BOZ)monomer is synthesized by a pot method with solvent-free to blend with cyanate ester(CE).A soluble intermediate is obtained after being cured for 20 h at 80℃.The two model compound and the blends are analyzed with the infrared radiation(IR),nuclear magnetic resonance(NMR)spectroscopy,and differential scanning calorimetry(DSC).The results show that an intermediate of the iminocarbonate and BOZ structures is formed by the ring-open BOZ reacting with the cyanate groups and ring-unopened BOZ.Moreover,rearrangement and ring-opening occur in the postcure of the intermediate to form the alkyl isocyanurate structure with polybenzoxazine.
基金We express our sincere appreciation to the National Natural Science Foundation of China(No.51474113(M.Jing),22279070[L.Wang]and U21A20170[X.He])the Ministry of Science and Technology of China(No.2019YFA0705703[L.Wang]).And we would like to thank the“Explorer 100”cluster system of Tsinghua National Laboratory for Information Science and Technology for facility support.
文摘Polymer solid-state lithium batteries(SSLB)are regarded as a promising energy storage technology to meet growing demand due to their high energy density and safety.Ion conductivity,interface stability and battery assembly process are still the main challenges to hurdle the commercialization of SSLB.As the main component of SSLB,poly(1,3-dioxolane)(PDOL)-based solid polymer electrolytes polymerized in-situ are becoming a promising candidate solid elec-trolyte,for their high ion conductivity at room temperature,good battery elec-trochemical performances,and simple assembly process.This review analyzes opportunities and challenges of PDOL electrolytes toward practical application for polymer SSLB.The focuses include exploring the polymerization mechanism of DOL,the performance of PDOL composite electrolytes,and the application of PDOL.Furthermore,we provide a perspective on future research directions that need to be emphasized for commercialization of PDOL-based electrolytes in SSLB.The exploration of these schemes facilitates a comprehensive and profound understanding of PDOL-based polymer electrolyte and provides new research ideas to boost them toward practical application in solid-state batteries.
文摘Water existing in water-absorbing plasma polymerized N-vinyl-2-pyrrolidone(PPNVP) include pure bulk water, freezable water and non-freezing, or bound, water. The C-N bond of N, N-disubstituted amides in PPNVP was considered as an active binding site for bound water.
基金supported by the National Key R&D Program of China(2023YFF0724100)Yangtze River Scholar Program(WF221411002)+2 种基金National Natural Science Foundation of China(52421006,22001166)State Key Laboratory of Polyolefins and CatalysisShanghai Key Laboratory of Catalysis Technology for Polyolefins.
文摘The development of living radical polymerization(LRP)methods has served as one of the most remarkable milestones for polymer chemistry.Independent LRP method requires specific conditions,catalysts,and monomers,which fits certain scenes,while it is unfit for others.While the combination of different methods integrates the advantages of various LRP methods,not all methods could be combined directly due to the complexity of the mutual influence between them.To overcome this,we established a criterion that could tell whether a combination of LRP methods was effective or not.With the help of this criterion,the dual concurrent ATRP-RAFT was constructed by the combination of ICAR-ATRP and RAFT.The binary LRP method allowed for(1)the expansion of monomer range for RAFT;(2)the reduction of CuII loading for ICAR-ATRP;(3)the enhanced control of dispersity.We believe that this research provides a different route for the development of the LRP methods.
基金This work was financially supported by the National Natural Science Foundation of China(U20A20256,51973207)the NSAF Joint Fund(U2030203).
文摘The general development of Rheo-NMR during the last four decades as well as selective hyphenated apparatuses is presented.Based on different magnet types,the current review is divided into two categories,namely low-field and high-field NMR,while the timedomain NMR is normally applied in the former case and the frequency-domain NMR is adopted in the latter one.Depending on different rheometer cells,it can be further divided into tensile and shear mode Rheo-NMR.The combination of various rheometer cells and NMR facility guarantees our acquisition of molecular level structure and dynamics information under flow conditions,which is crucial for our understanding of the molecular origin of complex fluids.A personal perspective is also presented at last to highlight possible development in this direction.
文摘In this paper, the content of water glass before and after adding modifying agent was measured by Trimethylsilyl-gas-chromatography. The experimental results showed that different modulus of water glass could generate different content of mono-silicate acid and oligomeric silicate acid in water glass. After a period of storage, different modulus of water glass led to decrease of silicate content at different levels. Because higher content of Na<sub>2</sub>O in water glass tended to incur the alkaline polymerization, the occurrence of depolymerization of silicate species would lead to an increase of oligomeric silicate species, resulting in a drawback of silicate species content after a period of storage. And contrary to that, lower content of Na<sub>2</sub>O in water glass tended to incur the acidic polymerization. When the modifying agent was added to the newly made water glass, the amount of mono-silicate acid and oligomeric silicate acid also decreased. In modified water glass, the change of each silicate acid species was less than that in unmodified water glass. These results showed that the modifying agent retarded the aging of water glass. It had remarkable significance on the theory and practical application of water glass chemistry.
基金supported by the National Natural Science Foundation of China (No. U 1507123)the Foundation from Qinghai Science and Technology Department (No. 2014-HZ-817)
文摘A calcium sulfate whisker （CSW） coated with glutaraldehyde crosslinked chitosan （GACS） was prepared to reinforce polyvinyl chloride （PVC） in this study. The results show that the optimum concentration of both chitosan （CS） and glutaraldehyde （GA） is 0.05 wt%. The tensile strength, impact strength, flexural modulus and vicat softening temperature of the PVC composite with 12 wt% of modified CSW are in- creased by 1 Z5%, 40.4%, 0.8% and 3.8% compared with those of the PVC composite with 12 wt~ of unmodified CSW, and by 2.9%, 42.4%, 2Z1% and 6.8% compared with those of pure PVC, respectively. The dynamic mechanical analysis results indicate that the modified CSW/PVC composite exhibits much higher storage modulus and glass transition temperature than those of unmodified CSW/PVC composite and pure PVC. In addition, the modified CSW/PVC composite also demonstrates good thermal properties with a high rapidest decomposition temperature （Trvd） and char residue. The scanning electron microscopy images of tensile-fractured surfaces show that the modified CSW has a strong interfacial adhesion with PVC matrix.
基金Supported by the National Natural Science Foundation of China under Grant Nos 11302225,11121202 and 11327802the National Key Project of Magneto-Constrained Fusion Energy Development Program under Grant No 2013GB110002the Postdoctoral Science Foundation of China under Grant No 2014M560820
文摘The strain and temperature sensing performance of fiber-optic Bragg gratings （FBGs） with soft polymeric coating, which can be used to sense internal strain in superconducting coils, are evaluated under variable cryogenic field and magnetic field. The response to a temperature and strain change of coated-soft polymeric FBGs is tested by comparing with those of coated-metal FBGs. The results indicate that the coated-soft polymeric FBGs can freely detect temperature and thermal strain, their At variable magnetic field, the tested results indicate accuracy and repeatability are also discussed in detail. that the cross-coupling effects of FBGs with different matrixes are not negligible to measure electromagnetic strain during fast excitation. The present results are expected to be able to provide basis measurements on the strain of pulsed superconducting magnet/cable （cable- around-conduit conductors, cable-in-conduit conductors）, independently or utilized together with other strain measurement methods.
基金Funded by the Natural Science Foundation of Fujian Province(No.2016J01241)the National Natural Science Foundation of China(No.51608212)the Science&Technology Pillar Program of Fujian Provincial Education Department(No.JA14024)
文摘By using redispersible polymer powder（RPP） and carbon fiber（CF） to adjust the flexibility and electrical properties of the smart aggregate, a new kind of smart aggregate with Z type structure was proposed. The study shows that Z type aggregate is more sensitive to the feedback of external force than the prism aggregate in the same loading environment, and it indicates that Z type aggregate is more suitable for the research and application of concrete health monitoring. Although the incorporation of RPP would cause the compressive strength of the aggregates and the elastic modulus of hardened cement mortar to reduce slightly within the dosage of RPP by 2.25% because of the polymer film formed in the internal system, this would improve the deformability of the aggregates. In the early loading stage（in the first 60 seconds）, the intelligent concrete specimens implanted with Z type smart aggregate do not show higher sensitivity as expected, although the resistance change rate changes a little bit more, the overall of it is still in balance. Adding RPP could improve the flexibility of smart aggregates exactly, and it plays an active role in prolonging the life of the smart aggregates. By implanting Z type aggregates the damage and failure of the concrete structure could be predicted accurately in this study. The results of this paper will help to promote further research and application of intelligent concrete.
基金Funded by the National Youth Natural Science Foundation of China(No.21406247)
文摘PMMA/reactive nanoclay nanocomposites were prepared by emulsion polymerization using two different reactive nanoclays. X-ray diffraction（XRD） and thermogravimetric analysis（TGA） results confirmed that the reactive nanoclays, kaolinite and montmorillonite, were obtained by the silylation reaction and the double bonds were grafted onto the edges and surfaces of the nanoclays. The presence of reactive nanoclays could increase the average molecular weights, the glass transition temperatures（Tg） and improve the thermal properties of nanocomposite. The tensile properties, Young＇s modulus, and the aging properties of the nanocomposite films were also enhanced while the light transmittance decreased. Furthermore, the nanocomposites with the reactive kaolinite presented better performances than that with the reactive montmorillonite. Finally, the action mechanism of the reactive nanoclays to the performances of PMMA/reactive nanoclay nanocomposites was proposed.
基金This work was supported by the National Natural Science Foundation of China （Nos. 21404018, 21503030） and the Fundamental Research Funds for the Central Universities （No. DUT16RC（4）79）. Gaohong He gratefully acknowledges Education Department of the Liaoning Province of China （No. LT2015007）, the Fundamental Research Funds for the Central Universi- ties （No. DUT16TD19） and the Chang Jiang Scholar Program （No. T2012049）.
文摘The copolymerization of ethylene and styrene can be efficiently carried out by using Cp＊TiCl2（N=CtBu2）/ MAO （Cp＊=η5-C5Me5） system, yielding the poly（ethylene-co-styrene）s with isolated styrene units. In order to in- vestigate the reasons for formation of the structure, the mechanism of copolymerization, especially the selective in- sertion of ethylene and styrene, is studied in detail by density functional theory （DFT） method. At the initiation stage, insertion of ethylene is kinetically more favorable than insertion of styrene, and insertion of styrene kinet- ically and thermodynamically prefers 2,1-insertion. That is different from the conventional half-titanocene system, in which the 1,2-insertion is favorable. At chain propagation stage, the computational results suggest that the con- tinuous insertion of styrene is hard to occur at room temperature due to the high free energy barriers （28.90 and 35.04 kcal/mol for 1,2-insertion, and 29.15 and 34.00 kcal/mol for 2,1-insertion） and thermodynamically unfavora- ble factors in two different conditions. That is mainly attributed to the steric hindrance between the coming styrene and chain-end styrene or ketimide ligand. The computational results are in good agreement with the experimental data.
基金Project supported by the National Natural Science Foundation of China.
文摘The electrochemical oxidation of diphenylamine in acetonitrile produces an adherent uniform polymer film which exhibits mutiple colour variation(yellow-green-blue) in a wide range of potential scan. The polymerization mechanism and the structure of the polymer were studied by cyclic voltammetry, FT-IR and in situ ESR. The results indicate that the electrochemical polymerization of diphenylamine belongs to a cationic radical polymerization process. During electrolysis, only oligomers were initialy produced, then polymer film was formed on the electrode surface. The electropolymerization performs via the 4,4' C-C phenyl-phenyl coupling mechanism.
基金This work was also sup-ported by the University Grants Committee Areas of Excellence(AoE)Scheme(AoE/P-03/08)a General Research Fund(GRF)grant from the Research Grants Council of Hong Kong Special Administrative Region,P.R.China(HKU 17304715).
文摘Our present study demonstrated and explored the solvent effects on the association mechanism of the supramolecular nanomaterials in a series of cyclo-tetrasiloxane-appended alkynylplatinum(II)terpyri-dine complexes.Through the delicate balance of molecular interactions,some of these complexes were found to exhibit molecular association prop-erties,with possible morphological transformation in response to solvent polarities.
