It is shown theoretically that the viscoelasticity of polymer melts is determined by three combining factorst they are the primary molecular weight and its distribution, the number of entanglement sites on polymer cha...It is shown theoretically that the viscoelasticity of polymer melts is determined by three combining factorst they are the primary molecular weight and its distribution, the number of entanglement sites on polymer chain and the sequence distribution of constituent chains in entanglement spacings. A unified quantity for the three combing factors is the average constrained dimensional number of constituent chains in the long entanglement spacings (v). A new relation of v to the primary molecular weight and the number of testing polymers were derived from the multiple entanglement and reptation model, and a new method for determining v was proposed. The dependences of linear viscoelastic functions on the primary molecular weight and its distribution were derived by the statistical method. When Mn=6Me to 18 Me, the values of (v) can range from 3.33 to 3.70. Their values are in a good agreement with the experiment data, and it can slightjy vary with the different species of polymers and the different ranges of molecular weight of polymers展开更多
By the reaction of poly(acryloyl chloride) with N-(3-aminopropyl)imidazole, poly(N-(3-(1H-imidazol-1-yl)propyl)acrylamide) was synthesized. The new polymer contains an imidazole ring removed from the main chain by a s...By the reaction of poly(acryloyl chloride) with N-(3-aminopropyl)imidazole, poly(N-(3-(1H-imidazol-1-yl)propyl)acrylamide) was synthesized. The new polymer contains an imidazole ring removed from the main chain by a spacer of five bonds. The structure and purity, molecular weight, hydrodynamic and thermosensitive properties of the obtained sample were studied by1H-and13C-NMR, FTIR spectroscopy, acid-base titration, light scattering, turbidimetry and viscometry. The observed ability of the imidazole-containing polymer to form and destroy associates in water-salt solutions at pH 6.6-7.4 and temperatures of 29-48℃ indicates that these are promising candidates for designing complex biomedical systems. The new polymer is able to form complexes with oligo-DNA more actively than poly(1-vinylimidazole), which is of interest for gene delivery applications. The polymer cross-linked with epichlorohydrin gives micro-relief coatings on the plastic surface, and the modified surface is able to attach negatively charged objects. This thermo-and pH-sensitive polymer modification can be applied to create finely controlled surfaces for cell culturing.展开更多
Positively charged composite nanofiltration （NF） membranes were prepared through interfacial polymerization of poly[2-（N,N-dimethyl amino）ethyl methacrylate]（PDMAEMA） on porous polysulfone （PSF） substrate memb...Positively charged composite nanofiltration （NF） membranes were prepared through interfacial polymerization of poly[2-（N,N-dimethyl amino）ethyl methacrylate]（PDMAEMA） on porous polysulfone （PSF） substrate membranes. The effects of pH on swelling ratio （SR） of the pure crosslinked PDMAEMA membrane and on separation performances of the composite NF membrane were investigated. The results show that the quaternized amino groups produced through interfacial polymerization technique are soluble in both phases, which accelerate the crosslinking reaction as self-catalysts. The swelling/contracting behavior of the pure crosslinked PDMAEMA exhibited a well reversible pH sensitive property. Importantly, the rejection and flux of the composite NF membrane show pH-sensitive behavior in NF process. Furthermore, with the help of a relatively novel method to measure membrane conduction, the true zeta potentials calculated on the basis of the streaming potential measurements proved the pH-sensitive behavior of the NF membrane.展开更多
At this article studies of nonlinear viscoelastic fluid with one internal tensor parameter flow between parallel planes under a constant pressure gradient, taking into account the slipping phenomenon on the boundary. ...At this article studies of nonlinear viscoelastic fluid with one internal tensor parameter flow between parallel planes under a constant pressure gradient, taking into account the slipping phenomenon on the boundary. Numerically depending found on the components of the stress tensor and the flow velocity of the pressure gradient and the distance to the wall, enabled us to explain the emergence of non-parabolic profile of the flow velocity of the polymeric melt.展开更多
Constitutive equations for melts and concentrated solutions of linear polymers are derived as consequences of dynamics of a separate macromolecule. The model is investigated for viscometric flows. It was shown that th...Constitutive equations for melts and concentrated solutions of linear polymers are derived as consequences of dynamics of a separate macromolecule. The model is investigated for viscometric flows. It was shown that the model gives a good description of non-linear effects of simple shear polymer flows: viscosity anomalies, first and second normal stresses, non-steady shear stresses.展开更多
Three major types of protective coating of wood and wood-based materials have been considered. These three types include the coatings based on carboxyl-containing water-soluble polymers which are easily cross-linked b...Three major types of protective coating of wood and wood-based materials have been considered. These three types include the coatings based on carboxyl-containing water-soluble polymers which are easily cross-linked by inorganic salts or OH-containing compounds, pH-sensitive coatings and polymer multi-layer structures. First of three mentioned approaches allows affecting permeability and enhancing the prevention the loss of water from the surface of wood to its surrounding. The advantage of the second approach is its ability to vary and purposely adjust the polymer composition and the number and distribution of -COOH groups in the chain which make the originally water-soluble polymers completely insoluble. The strong feature of the third approach which includes broad use of hydrogen-bonded films produced by layer-by-layer self-assembly is the possibility of manipulation of coatings stability after construction.展开更多
The polymer-bound Schiff base ternary manganese complexes [PS-SalPhe-Mn-L(L=Phen, Bipy and 8HQ)] have been prepared from the polymer-bound Schiff base ligand, a manganese salt and the second ligand, such as 1,10-phena...The polymer-bound Schiff base ternary manganese complexes [PS-SalPhe-Mn-L(L=Phen, Bipy and 8HQ)] have been prepared from the polymer-bound Schiff base ligand, a manganese salt and the second ligand, such as 1,10-phenanthroline(phen), 2,2′-bipyridyl(bipy) and 8-quinolinol(8HQ). The polymer-bound Schiff base ternary manganese complexes were characterized by means of infrared spectrometry and ICP-AES. The catalytic activities of the complexes have been studied in the aerobic epoxidation of long-chain linear aliphatic olefins. It is shown that 1-octene or 1-decene can be directly oxidized by molecular oxygen when catalyzed by PS-SalPhe-Mn-L(L=Phen, Bipy and 8HQ), and 1,2-epoxy alkane can be afforded in these reactions.展开更多
Dissipative particle dynamics(DPD)with bond uncrossability shows a great potential in studying entangled polymers,however relatively little is known of applicability range of entangled DPD model to be use as a model f...Dissipative particle dynamics(DPD)with bond uncrossability shows a great potential in studying entangled polymers,however relatively little is known of applicability range of entangled DPD model to be use as a model for ideal chains and properly describe the full dynamics of entangled melts.Therefore,we perform a comprehensive study on structure,dynamics and linear viscoelasticity of a typical DPD entangled model system,semiflexible linear polymer melt.These polymers obey Flory's ideality hypothesis in chain dimensions,but their local structure exhibits nonideal behavior due to weak correlated hole effect.Both monomer motion and viscoelasticity relaxation reproduce the full pictures as predicted by reptation theory.The stronger chain length dependent diffusion coefficient and relaxation time as well as dynamic moduli are in close agreement with predictions of modern tube model that accounts for additional relaxation mechanisms besides chain reptation.However,an anomalous sub-diffusive center of mass motion is observed both before and after the intermediate reptation regime and the cross-correlation between chains is not negligible even these polymers obey stress-optical law,indicating limitations of the reptation theory.Hence semiflexible linear entangled DPD model can correctly describe statics and dynamics of entangled polymer melts.展开更多
Here we use nor-seco-cucurbit[10]uril(ns-CB[10]) based ternary complexation to construct [5]rotaxane,linear supramolecular dynamic rotaxane polymers and cubic 3D supramolecular organic framework.A [5]rotaxane is const...Here we use nor-seco-cucurbit[10]uril(ns-CB[10]) based ternary complexation to construct [5]rotaxane,linear supramolecular dynamic rotaxane polymers and cubic 3D supramolecular organic framework.A [5]rotaxane is constructed by ns-CB[10], TMe CB[6] and short linear derivatives of 4,4'-bipyridinium(M2). ns-CB[10], CB[7] and long linear derivatives of 4,4'-bipyridinium(M3) self-assemble into a linear supramolecular dynamic rotaxane polymer. ns-CB[10] and tetracationic tetrahedral monomer selfassemble and form a three-dimensional supramolecular organic framework. The above results demonstrate that ns-CB[10]-based ternary complexation is a versatile platform to build various supramolecular systems.展开更多
A novel tripyridylporphyrin monomer,5-[4-[2-（acryloyloxy）ethoxy]phenyl]-10,15,20-tris（4-pyridyl）porphyrin （TrPyP）,was synthesized and polymerized with acrylamide（AM） to prepare the hydrophobically associating ...A novel tripyridylporphyrin monomer,5-[4-[2-（acryloyloxy）ethoxy]phenyl]-10,15,20-tris（4-pyridyl）porphyrin （TrPyP）,was synthesized and polymerized with acrylamide（AM） to prepare the hydrophobically associating water-soluble polymer PAM-TrPyP.The aggregation behavior of porphyrin pendants was investigated by UV-Visible and fluorescence spectra.The polymer displays a strong tendency of hydrophobic association even in dilute solutions.With increasing the concentration,the maximum absorption wavelength of Soret band changes from 416 nm to 407 nm,and the fluorescence corrected for the inner filter effect exhibits moderate concentration quenching.All the results indicate thatπ-πinteraction of porphyrin pendants plays a key role in association of PAM-TrPyP,and H-aggregates of porphyrins are mainly formed in the concentrated solution.On the other hand,dynamic light scattering（DLS） and transmission electron microscopy（TEM） were used to follow the changes in size and structure of the macromolecular assemblies with the concentration increase.The polymer aggregation conformation changes from loose ＂vesicle-like＂ morphology to solid globule accordingly.When pH value of solution decreases to 4.3,pyridine moieties on porphyrin pendants could be protonated and the H-aggregates formed in macromolecular matrix are destroyed by electrostatic repulsion interactions.展开更多
In order to better understand linear polymer aqueous solutions in soft lubrication from boundary to mixed lubrication,poly(ethylene glycol) and sodium hyaluronateare used as model polymers were investigated by using U...In order to better understand linear polymer aqueous solutions in soft lubrication from boundary to mixed lubrication,poly(ethylene glycol) and sodium hyaluronateare used as model polymers were investigated by using UMT-2 tribometer with the ball-on-disk mode. The relationship between the master Stribeck curves of the polymer aqueous solutions and the influence factors were investigated. Experimental results indicated that soft lubrication is determined by lubricant rheological properties and surface-lubricant interactions, e.g., wetting behavior of polymer aqueous solution on tribological surfaces.展开更多
A novel light-emitting alternating copolymer, known as hyperbranched conjugated polymer (HPV), has been designed and synthesized by Wittig reaction, and so have its linear counterparts, including MPV and PPV. FTIR, 1H...A novel light-emitting alternating copolymer, known as hyperbranched conjugated polymer (HPV), has been designed and synthesized by Wittig reaction, and so have its linear counterparts, including MPV and PPV. FTIR, 1H NMR, 13C NMR and GPC were combined to characterize these polymers. Their photophysical properties were investigated both in solution and in solid film. Interestingly, almost the same maxima of absorption and emission wavelengths were observed for the solution of HPV and MPV in CH2Cl2 respectively, located at the shorter wavelength region related to PPV. In addition, the absorption peak of HPV film blue shifted while its emission peak red shifted as MPV compared with the case of its CH2Cl2 solution. However, both the absorption and emission spectra of the PPV film showed red shift, which resulted from a special electronic structure.展开更多
文摘It is shown theoretically that the viscoelasticity of polymer melts is determined by three combining factorst they are the primary molecular weight and its distribution, the number of entanglement sites on polymer chain and the sequence distribution of constituent chains in entanglement spacings. A unified quantity for the three combing factors is the average constrained dimensional number of constituent chains in the long entanglement spacings (v). A new relation of v to the primary molecular weight and the number of testing polymers were derived from the multiple entanglement and reptation model, and a new method for determining v was proposed. The dependences of linear viscoelastic functions on the primary molecular weight and its distribution were derived by the statistical method. When Mn=6Me to 18 Me, the values of (v) can range from 3.33 to 3.70. Their values are in a good agreement with the experiment data, and it can slightjy vary with the different species of polymers and the different ranges of molecular weight of polymers
基金supported by the Russian Science Foundation(No.22-24-00474).
文摘By the reaction of poly(acryloyl chloride) with N-(3-aminopropyl)imidazole, poly(N-(3-(1H-imidazol-1-yl)propyl)acrylamide) was synthesized. The new polymer contains an imidazole ring removed from the main chain by a spacer of five bonds. The structure and purity, molecular weight, hydrodynamic and thermosensitive properties of the obtained sample were studied by1H-and13C-NMR, FTIR spectroscopy, acid-base titration, light scattering, turbidimetry and viscometry. The observed ability of the imidazole-containing polymer to form and destroy associates in water-salt solutions at pH 6.6-7.4 and temperatures of 29-48℃ indicates that these are promising candidates for designing complex biomedical systems. The new polymer is able to form complexes with oligo-DNA more actively than poly(1-vinylimidazole), which is of interest for gene delivery applications. The polymer cross-linked with epichlorohydrin gives micro-relief coatings on the plastic surface, and the modified surface is able to attach negatively charged objects. This thermo-and pH-sensitive polymer modification can be applied to create finely controlled surfaces for cell culturing.
基金Funded by the National Natural Science Foundation of China (No.50673077)National Basic Research Program of China (No.2006CB708602)
文摘Positively charged composite nanofiltration （NF） membranes were prepared through interfacial polymerization of poly[2-（N,N-dimethyl amino）ethyl methacrylate]（PDMAEMA） on porous polysulfone （PSF） substrate membranes. The effects of pH on swelling ratio （SR） of the pure crosslinked PDMAEMA membrane and on separation performances of the composite NF membrane were investigated. The results show that the quaternized amino groups produced through interfacial polymerization technique are soluble in both phases, which accelerate the crosslinking reaction as self-catalysts. The swelling/contracting behavior of the pure crosslinked PDMAEMA exhibited a well reversible pH sensitive property. Importantly, the rejection and flux of the composite NF membrane show pH-sensitive behavior in NF process. Furthermore, with the help of a relatively novel method to measure membrane conduction, the true zeta potentials calculated on the basis of the streaming potential measurements proved the pH-sensitive behavior of the NF membrane.
文摘At this article studies of nonlinear viscoelastic fluid with one internal tensor parameter flow between parallel planes under a constant pressure gradient, taking into account the slipping phenomenon on the boundary. Numerically depending found on the components of the stress tensor and the flow velocity of the pressure gradient and the distance to the wall, enabled us to explain the emergence of non-parabolic profile of the flow velocity of the polymeric melt.
文摘Constitutive equations for melts and concentrated solutions of linear polymers are derived as consequences of dynamics of a separate macromolecule. The model is investigated for viscometric flows. It was shown that the model gives a good description of non-linear effects of simple shear polymer flows: viscosity anomalies, first and second normal stresses, non-steady shear stresses.
文摘Three major types of protective coating of wood and wood-based materials have been considered. These three types include the coatings based on carboxyl-containing water-soluble polymers which are easily cross-linked by inorganic salts or OH-containing compounds, pH-sensitive coatings and polymer multi-layer structures. First of three mentioned approaches allows affecting permeability and enhancing the prevention the loss of water from the surface of wood to its surrounding. The advantage of the second approach is its ability to vary and purposely adjust the polymer composition and the number and distribution of -COOH groups in the chain which make the originally water-soluble polymers completely insoluble. The strong feature of the third approach which includes broad use of hydrogen-bonded films produced by layer-by-layer self-assembly is the possibility of manipulation of coatings stability after construction.
基金Supported by the National Natural Science Foundation of China(No.2 99330 5 0,2 95 74 176 ,2 0 2 74 0 34)
文摘The polymer-bound Schiff base ternary manganese complexes [PS-SalPhe-Mn-L(L=Phen, Bipy and 8HQ)] have been prepared from the polymer-bound Schiff base ligand, a manganese salt and the second ligand, such as 1,10-phenanthroline(phen), 2,2′-bipyridyl(bipy) and 8-quinolinol(8HQ). The polymer-bound Schiff base ternary manganese complexes were characterized by means of infrared spectrometry and ICP-AES. The catalytic activities of the complexes have been studied in the aerobic epoxidation of long-chain linear aliphatic olefins. It is shown that 1-octene or 1-decene can be directly oxidized by molecular oxygen when catalyzed by PS-SalPhe-Mn-L(L=Phen, Bipy and 8HQ), and 1,2-epoxy alkane can be afforded in these reactions.
基金financially supported by the National Natural Science Foundation of China(Nos.21790343,21574142 and 21174154)the National Key Research and Development Program of China(No.2016YFB1100800)。
文摘Dissipative particle dynamics(DPD)with bond uncrossability shows a great potential in studying entangled polymers,however relatively little is known of applicability range of entangled DPD model to be use as a model for ideal chains and properly describe the full dynamics of entangled melts.Therefore,we perform a comprehensive study on structure,dynamics and linear viscoelasticity of a typical DPD entangled model system,semiflexible linear polymer melt.These polymers obey Flory's ideality hypothesis in chain dimensions,but their local structure exhibits nonideal behavior due to weak correlated hole effect.Both monomer motion and viscoelasticity relaxation reproduce the full pictures as predicted by reptation theory.The stronger chain length dependent diffusion coefficient and relaxation time as well as dynamic moduli are in close agreement with predictions of modern tube model that accounts for additional relaxation mechanisms besides chain reptation.However,an anomalous sub-diffusive center of mass motion is observed both before and after the intermediate reptation regime and the cross-correlation between chains is not negligible even these polymers obey stress-optical law,indicating limitations of the reptation theory.Hence semiflexible linear entangled DPD model can correctly describe statics and dynamics of entangled polymer melts.
基金supports from the National Natural Science Foundation of China(Nos.21890732,21890730 and 21921003)。
文摘Here we use nor-seco-cucurbit[10]uril(ns-CB[10]) based ternary complexation to construct [5]rotaxane,linear supramolecular dynamic rotaxane polymers and cubic 3D supramolecular organic framework.A [5]rotaxane is constructed by ns-CB[10], TMe CB[6] and short linear derivatives of 4,4'-bipyridinium(M2). ns-CB[10], CB[7] and long linear derivatives of 4,4'-bipyridinium(M3) self-assemble into a linear supramolecular dynamic rotaxane polymer. ns-CB[10] and tetracationic tetrahedral monomer selfassemble and form a three-dimensional supramolecular organic framework. The above results demonstrate that ns-CB[10]-based ternary complexation is a versatile platform to build various supramolecular systems.
文摘A novel tripyridylporphyrin monomer,5-[4-[2-（acryloyloxy）ethoxy]phenyl]-10,15,20-tris（4-pyridyl）porphyrin （TrPyP）,was synthesized and polymerized with acrylamide（AM） to prepare the hydrophobically associating water-soluble polymer PAM-TrPyP.The aggregation behavior of porphyrin pendants was investigated by UV-Visible and fluorescence spectra.The polymer displays a strong tendency of hydrophobic association even in dilute solutions.With increasing the concentration,the maximum absorption wavelength of Soret band changes from 416 nm to 407 nm,and the fluorescence corrected for the inner filter effect exhibits moderate concentration quenching.All the results indicate thatπ-πinteraction of porphyrin pendants plays a key role in association of PAM-TrPyP,and H-aggregates of porphyrins are mainly formed in the concentrated solution.On the other hand,dynamic light scattering（DLS） and transmission electron microscopy（TEM） were used to follow the changes in size and structure of the macromolecular assemblies with the concentration increase.The polymer aggregation conformation changes from loose ＂vesicle-like＂ morphology to solid globule accordingly.When pH value of solution decreases to 4.3,pyridine moieties on porphyrin pendants could be protonated and the H-aggregates formed in macromolecular matrix are destroyed by electrostatic repulsion interactions.
基金supported by the National Natural Science Foundation of China(Grant No.51175514)the Ph.D.Programs Foundation of Ministry of Education of China(Grant No.20100007120010)+1 种基金the Tribology Science Fund of State Key Laboratory of Tribology(Grant No.SKLTKF11A05)the Science Foundation of China University of Petroleum,Beijing(Grant No.KYJJ2012-04-17)
文摘In order to better understand linear polymer aqueous solutions in soft lubrication from boundary to mixed lubrication,poly(ethylene glycol) and sodium hyaluronateare used as model polymers were investigated by using UMT-2 tribometer with the ball-on-disk mode. The relationship between the master Stribeck curves of the polymer aqueous solutions and the influence factors were investigated. Experimental results indicated that soft lubrication is determined by lubricant rheological properties and surface-lubricant interactions, e.g., wetting behavior of polymer aqueous solution on tribological surfaces.
基金the National NaturalScience Foundation of China (Grant Nos. 29992530 and 29873060) and the CAS.
文摘A novel light-emitting alternating copolymer, known as hyperbranched conjugated polymer (HPV), has been designed and synthesized by Wittig reaction, and so have its linear counterparts, including MPV and PPV. FTIR, 1H NMR, 13C NMR and GPC were combined to characterize these polymers. Their photophysical properties were investigated both in solution and in solid film. Interestingly, almost the same maxima of absorption and emission wavelengths were observed for the solution of HPV and MPV in CH2Cl2 respectively, located at the shorter wavelength region related to PPV. In addition, the absorption peak of HPV film blue shifted while its emission peak red shifted as MPV compared with the case of its CH2Cl2 solution. However, both the absorption and emission spectra of the PPV film showed red shift, which resulted from a special electronic structure.
