Block copolymer polystyrene-b-poly(acrylic acid)(PS-b-PAA) was used as structural template for the synthesis of CaCO3 microparticles. Through this procedure, acid resistant hybrid CaCO3 micro- spheres were obtaine...Block copolymer polystyrene-b-poly(acrylic acid)(PS-b-PAA) was used as structural template for the synthesis of CaCO3 microparticles. Through this procedure, acid resistant hybrid CaCO3 micro- spheres were obtained. Acid resistant properties of this type of hybrid CaCO3 were studied. Size measurement shows that the acid resistant properties of the hybrid particles are different in different solutions, such as HCl, EDTA, and H2SO4 solutions.展开更多
Amphiphilic block copolymers of poly(5-benzyloxy trimethylene carbonate) (PBTMC) and poly(ethylene glycol) (PEG) were synthesized through enzymatic polymerization using immobilized porcine pancreas lipase (I...Amphiphilic block copolymers of poly(5-benzyloxy trimethylene carbonate) (PBTMC) and poly(ethylene glycol) (PEG) were synthesized through enzymatic polymerization using immobilized porcine pancreas lipase (IPPL). The obtained copolymers with different compositions were characterized by GPC and IH NMR. The copolymer composition was in agreement with the feed ratio. The molecular weight of the copolymers showed an increasing trend with the decrease of PEG contents. MiceUes of the copolymers were formed by dialysis procedure, and characterized by transmission electron microscopy (TEM).展开更多
Isothermal-isobaric molecular dynamics simu- lation was used to study the diffusion mechanism of water in polyurethane-block-poly(N-isopropyl acrylamide) (PU- block-PNIPAm) with a hydrophobic PU/hydrophilic PNIPAm...Isothermal-isobaric molecular dynamics simu- lation was used to study the diffusion mechanism of water in polyurethane-block-poly(N-isopropyl acrylamide) (PU- block-PNIPAm) with a hydrophobic PU/hydrophilic PNIPAm mass ratio of 1.4 to 1 at 298 K and 450 K. Here, the experimental glass transition temperature (Tg) of PU is 243 K while that of PNIPAm is 383 K. Different amounts of water up to 15 wt-% were added to PU-block- PNIPAm. We were able to reproduce the specific volumes and glass transition temperatures (250 K and 390 K) of PU- block-PNIPAm. The computed self-diffusion coefficient of water increased exponentially with increasing water concentration at both temperatures (i.e., following the free volume model of Fujita). It suggested that water diffusion in PU-block-PNIPAm depends only on its fractional free volume despite the free volume inhomo- geneity. It is noted that at 298 K, PU is rubbery while PNIPAm is glassy. Regardless of temperature, radial distribution functions showed that water formed clusters with sizes in the range of 0.2-0.4 nm in PU-block- PNIPAm. At low water concentrations, more clusters were found in the PU domain but at high water concentrations, more in the PNIPAm domain. It is believed that water molecules diffuse as clusters rather than as individual molecules.展开更多
Herein, the ability to optimize the morphology and photovoltaic performance of poly(3-hexylthiophene) (P3HT)/ZnO hybrid bulk-heterojunction solar cells via introducing all-conjugated amphiphilic P3HT-based block c...Herein, the ability to optimize the morphology and photovoltaic performance of poly(3-hexylthiophene) (P3HT)/ZnO hybrid bulk-heterojunction solar cells via introducing all-conjugated amphiphilic P3HT-based block copolymer (BCP), poly(3- hexylthiophene)-block-poly(3-triethylene glycol-thiophene) (P3HT-b-P3TEGT), as polymeric additives is demonstrated. The results show that the addition of P3HT-b-P3TEGT additives can effectively improve the compatibility between P3HT and ZnO nanocrystals, increase the crystalline and ordered packing of P3HT chains, and form optimized hybrid nanomorphology with stable and intimate hybrid interface. The improvement is ascribed to the P3HT-b-P3TEGT at the P3HT/ZnO interface that has strong coordination interactions between the TEG side chains and the polar surface of ZnO nanoparticles. All of these are favor of the efficient exciton dissociation, charge separation and transport, thereby, contributing to the improvement of the efficiency and thermal stability of solar cells. These observations indicate that introducing all-conjugated amphiphilic BCP additives can be a promising and effective protocol for high-performance hybrid solar cells.展开更多
Poly(vinylidene fluoride) (PVDF) has become one of the most popular materials for membrane preparation via nonsolvent induced phase separation (NIPS) process. In this study, an amphiphilic block copolymer, Pluro...Poly(vinylidene fluoride) (PVDF) has become one of the most popular materials for membrane preparation via nonsolvent induced phase separation (NIPS) process. In this study, an amphiphilic block copolymer, Pluronic F127, has been used as both a pore-former and a surface-modifier in the fabrication of PVDF hollow fibermembranes to enhance the membrane permeability and hydrophilicity. The effects of 2nd additive and coagulant temperature on the formation of PVDF/Pluronic F 127 membranes have also been investigated. The as-spun hollow fibers were characterized in terms of cross-sectional morphology, pure water permeation (PWP), relative molecular mass cut-off (MWCO), membrane chemistry, and hydrolphilicity. It was obsered that the addition of Pluronic F 127 significantly increased the PWP of as-spun fibers, while the membrane contact angle was reduced. However, the size of macrovoids in the membranes was undesirably large. The addition of a 2nd additive, including lithium chloride (LiC1) and water, or an increase in coagulant temperature was found to effectively suppress the macrovoid for- mation in the Pluronic-containing membranes. In addition, the use of LiC1 as a 2nd additive also further enhanced the PWP and hydrophilicity of the membranes, while the surface pore size became smaller. PVDF hollow fiber with a PWP as high as 2330 L·m-2·h-1·MPa-1, a MWCO of 53000 and'a contact angle of 71 o was successfully fabricated with 3% (by mass) of Pluronic F127 and 3% (by mass) of LiC1 at a coagulant temperature of 25 ℃, which shows better performance as compared with most of PVDF hollow fiber membranes made by NIPS method.展开更多
Functional amphiphilic block copolymer poly(ethylene glycol)-block-poly[(3-(triethoxysilyl)propyl methacrylate)- co-(1-pyrene-methyl) methacrylate], PEG113-b-P(TEPM26-co-PyMMA4), was synthesized via atom tra...Functional amphiphilic block copolymer poly(ethylene glycol)-block-poly[(3-(triethoxysilyl)propyl methacrylate)- co-(1-pyrene-methyl) methacrylate], PEG113-b-P(TEPM26-co-PyMMA4), was synthesized via atom transfer radical polymerization (ATRP) initiated by monomethoxy capped poly(ethylene glycol) bromoisobutyrate. This polymer exhibited strong ability to disperse and exfoliate single-walled carbon nanotubes (SWNTs) in different solvents due to the adhesion of pyrene units to surface of SWNTs. In aqueous solution, the PTEPM segments that were located on the nanotube surfaces with the pyrene units could be gelated and, as a result, the silica oxide networks with PEG coronas were formed on the surface of nanotubes, which ensured the composites with a good dispersibility and stability. Furthermore, functional silane coupling agents, 3-mereaptopropyltrimethoxysilane and 3-aminopropyltriethoxysilane, were introduced during dispersion of SWNTs using the block copolymers. They were co-gelated with PTEPM segments, and the --SH and --NH2 functionalities were introduced into the silica oxide coats respectively.展开更多
A series of cis-5-norbornene-endo-2,3-dicarboxylic anhydride (NDCA, M1) derivatives (M2-M4) with different types of nonpolar substituted groups were synthesized and characterized by 1H/13C-NMR and mass spectromet...A series of cis-5-norbornene-endo-2,3-dicarboxylic anhydride (NDCA, M1) derivatives (M2-M4) with different types of nonpolar substituted groups were synthesized and characterized by 1H/13C-NMR and mass spectrometry (MS). Ring- opening metathesis polymerization (ROMP) of these monomers using the Grubbs third generation catalyst (G3) generated high molecular weight polymers with much improved solubility compared with the NDCA's homopolymer. It was found that the solubility of these polymers increased with increased substituent's steric hindrance. The living polymerization of NDCA derivative containing the bulkiest substituent (M4) catalyzed by G3 in tetrahydrofuran was confirmed by the kinetic studies with low polydispersity indices (PDI) (〈 1.30). By using sequential ROMP, well-defined diblock copolymers containing anhydride groups were synthesized.展开更多
基金Supported by the National Natural Science Foundation of China(Nos.50803055, 30872902).
文摘Block copolymer polystyrene-b-poly(acrylic acid)(PS-b-PAA) was used as structural template for the synthesis of CaCO3 microparticles. Through this procedure, acid resistant hybrid CaCO3 micro- spheres were obtained. Acid resistant properties of this type of hybrid CaCO3 were studied. Size measurement shows that the acid resistant properties of the hybrid particles are different in different solutions, such as HCl, EDTA, and H2SO4 solutions.
文摘Amphiphilic block copolymers of poly(5-benzyloxy trimethylene carbonate) (PBTMC) and poly(ethylene glycol) (PEG) were synthesized through enzymatic polymerization using immobilized porcine pancreas lipase (IPPL). The obtained copolymers with different compositions were characterized by GPC and IH NMR. The copolymer composition was in agreement with the feed ratio. The molecular weight of the copolymers showed an increasing trend with the decrease of PEG contents. MiceUes of the copolymers were formed by dialysis procedure, and characterized by transmission electron microscopy (TEM).
文摘Isothermal-isobaric molecular dynamics simu- lation was used to study the diffusion mechanism of water in polyurethane-block-poly(N-isopropyl acrylamide) (PU- block-PNIPAm) with a hydrophobic PU/hydrophilic PNIPAm mass ratio of 1.4 to 1 at 298 K and 450 K. Here, the experimental glass transition temperature (Tg) of PU is 243 K while that of PNIPAm is 383 K. Different amounts of water up to 15 wt-% were added to PU-block- PNIPAm. We were able to reproduce the specific volumes and glass transition temperatures (250 K and 390 K) of PU- block-PNIPAm. The computed self-diffusion coefficient of water increased exponentially with increasing water concentration at both temperatures (i.e., following the free volume model of Fujita). It suggested that water diffusion in PU-block-PNIPAm depends only on its fractional free volume despite the free volume inhomo- geneity. It is noted that at 298 K, PU is rubbery while PNIPAm is glassy. Regardless of temperature, radial distribution functions showed that water formed clusters with sizes in the range of 0.2-0.4 nm in PU-block- PNIPAm. At low water concentrations, more clusters were found in the PU domain but at high water concentrations, more in the PNIPAm domain. It is believed that water molecules diffuse as clusters rather than as individual molecules.
文摘Herein, the ability to optimize the morphology and photovoltaic performance of poly(3-hexylthiophene) (P3HT)/ZnO hybrid bulk-heterojunction solar cells via introducing all-conjugated amphiphilic P3HT-based block copolymer (BCP), poly(3- hexylthiophene)-block-poly(3-triethylene glycol-thiophene) (P3HT-b-P3TEGT), as polymeric additives is demonstrated. The results show that the addition of P3HT-b-P3TEGT additives can effectively improve the compatibility between P3HT and ZnO nanocrystals, increase the crystalline and ordered packing of P3HT chains, and form optimized hybrid nanomorphology with stable and intimate hybrid interface. The improvement is ascribed to the P3HT-b-P3TEGT at the P3HT/ZnO interface that has strong coordination interactions between the TEG side chains and the polar surface of ZnO nanoparticles. All of these are favor of the efficient exciton dissociation, charge separation and transport, thereby, contributing to the improvement of the efficiency and thermal stability of solar cells. These observations indicate that introducing all-conjugated amphiphilic BCP additives can be a promising and effective protocol for high-performance hybrid solar cells.
文摘Poly(vinylidene fluoride) (PVDF) has become one of the most popular materials for membrane preparation via nonsolvent induced phase separation (NIPS) process. In this study, an amphiphilic block copolymer, Pluronic F127, has been used as both a pore-former and a surface-modifier in the fabrication of PVDF hollow fibermembranes to enhance the membrane permeability and hydrophilicity. The effects of 2nd additive and coagulant temperature on the formation of PVDF/Pluronic F 127 membranes have also been investigated. The as-spun hollow fibers were characterized in terms of cross-sectional morphology, pure water permeation (PWP), relative molecular mass cut-off (MWCO), membrane chemistry, and hydrolphilicity. It was obsered that the addition of Pluronic F 127 significantly increased the PWP of as-spun fibers, while the membrane contact angle was reduced. However, the size of macrovoids in the membranes was undesirably large. The addition of a 2nd additive, including lithium chloride (LiC1) and water, or an increase in coagulant temperature was found to effectively suppress the macrovoid for- mation in the Pluronic-containing membranes. In addition, the use of LiC1 as a 2nd additive also further enhanced the PWP and hydrophilicity of the membranes, while the surface pore size became smaller. PVDF hollow fiber with a PWP as high as 2330 L·m-2·h-1·MPa-1, a MWCO of 53000 and'a contact angle of 71 o was successfully fabricated with 3% (by mass) of Pluronic F127 and 3% (by mass) of LiC1 at a coagulant temperature of 25 ℃, which shows better performance as compared with most of PVDF hollow fiber membranes made by NIPS method.
基金financially supported by the National Natural Science Foundation of China(Nos.21090350,21090353, 50973119 and 20625412)SKLSSM(201015)
文摘Functional amphiphilic block copolymer poly(ethylene glycol)-block-poly[(3-(triethoxysilyl)propyl methacrylate)- co-(1-pyrene-methyl) methacrylate], PEG113-b-P(TEPM26-co-PyMMA4), was synthesized via atom transfer radical polymerization (ATRP) initiated by monomethoxy capped poly(ethylene glycol) bromoisobutyrate. This polymer exhibited strong ability to disperse and exfoliate single-walled carbon nanotubes (SWNTs) in different solvents due to the adhesion of pyrene units to surface of SWNTs. In aqueous solution, the PTEPM segments that were located on the nanotube surfaces with the pyrene units could be gelated and, as a result, the silica oxide networks with PEG coronas were formed on the surface of nanotubes, which ensured the composites with a good dispersibility and stability. Furthermore, functional silane coupling agents, 3-mereaptopropyltrimethoxysilane and 3-aminopropyltriethoxysilane, were introduced during dispersion of SWNTs using the block copolymers. They were co-gelated with PTEPM segments, and the --SH and --NH2 functionalities were introduced into the silica oxide coats respectively.
基金financially supported by the National Natural Science Foundation of China(Nos.21234006 and 21574098)
文摘A series of cis-5-norbornene-endo-2,3-dicarboxylic anhydride (NDCA, M1) derivatives (M2-M4) with different types of nonpolar substituted groups were synthesized and characterized by 1H/13C-NMR and mass spectrometry (MS). Ring- opening metathesis polymerization (ROMP) of these monomers using the Grubbs third generation catalyst (G3) generated high molecular weight polymers with much improved solubility compared with the NDCA's homopolymer. It was found that the solubility of these polymers increased with increased substituent's steric hindrance. The living polymerization of NDCA derivative containing the bulkiest substituent (M4) catalyzed by G3 in tetrahydrofuran was confirmed by the kinetic studies with low polydispersity indices (PDI) (〈 1.30). By using sequential ROMP, well-defined diblock copolymers containing anhydride groups were synthesized.