Grafting of polystyrene with narrowly dispersed polymer microspheres through surface-initiated atom transferradical polymerization(ATRP)was investigated.Polydivinylbenzene(PDVB)microspheres were prepared by dispersion...Grafting of polystyrene with narrowly dispersed polymer microspheres through surface-initiated atom transferradical polymerization(ATRP)was investigated.Polydivinylbenzene(PDVB)microspheres were prepared by dispersionpolymerization with poly(N-vinyl pyrrolidone)(PVP)as stabilizer.The surfaces of PDVB microspheres werechloromethylated by chloromethyl methyl ether in the presence of zinc chloride as catalyst to form chloromethylbenzeneinitiating core sites for subsequent ATRP grafting of styrene using CuCl/bpy as catalytic system.Polystyrene was found to begrafted not only from the particle surfaces but also from within a thin shell layer,resulting in the formation of particles sizeincreased from 2.38-2.58 μm,which can further grow to 2.93 μm during secondary grafting polymerization of styrene.Thisdemonstrates that grafting polymerization proceeds through a typical ATRP procedure with living nature.All of the preparedmicrospheres have narrow particle size distribution with coefficient of variation around 10%.展开更多
Photo-grafting of hydrophilic monomer was used to enhance the hydrophilicity of poly（ether ether ketone） （PEEK） with the aim of extending its applications to biological fields. PEEK sheets were surface modified by...Photo-grafting of hydrophilic monomer was used to enhance the hydrophilicity of poly（ether ether ketone） （PEEK） with the aim of extending its applications to biological fields. PEEK sheets were surface modified by grafting of acrylamide（AAm） with ultraviolet（UV） irradiation in the presence or absence of benzophenone（BP）. The effects of BP, irradiation time and monomer concentration on the surface wettability of PEEK were investigated. Characteriza tion of modified PEEK using scanning electron microscopy（SEM）, energy-disperse spectrometer（EDS） and water contact angle measurements shows that AAm was successfully grafted on PEEK surface both in presence and absence of BP. With the increase in irradiation time and monomer concentration, contact angles decrease to as low as 30°, demonstrating a significant improvement of surface hydrophilicity. In agreement with the decrease in contact angle, under identical conditions, the nitrogen concentration increases, suggesting the increase in grafting degree of the grafting polymerization. This investigation demonstrates a self-initiation of PEEK due to its BP-like structure in the backbone of the polymer. Though the graft polymerization proceeds more readily in the presence of BP, the self-initiated graft polymerization is clearly observed.展开更多
A couple of novel sulfobetaine copolymer is developed via Michael-type addition reaction. The comonomers, diamines and maleimide react via Michael reaction through UV irradiation using AIBN as photoinitiator producing...A couple of novel sulfobetaine copolymer is developed via Michael-type addition reaction. The comonomers, diamines and maleimide react via Michael reaction through UV irradiation using AIBN as photoinitiator producing polyamine chain. Further, sulfobetaine copolymers were obtained on treatment of the polyamine with sulfopropylating agent, 1,3-propane sultone. These novel sulfobetaine polymers were grafted on silica surface to produce responsive biocompatible surface. This easy straightforward, catalyst free facile protocol for synthesis of polymer grafted surface is useful for developing biomedical devices. Additionally, both the copolymers show fluorescence characteristics.展开更多
Surface initiated polymerization (SIP) is a valuable tool in synthesizing functional polymer brushes,yet the kinetic understanding of SIP lags behind the development of its application. We apply quartz crystal microba...Surface initiated polymerization (SIP) is a valuable tool in synthesizing functional polymer brushes,yet the kinetic understanding of SIP lags behind the development of its application. We apply quartz crystal microbalance (QCM) to address two issues that are not fully addressed yet play a central role in the rational design of functional polymer brushes,namely quantitative determination of the kinetics and the initiator efficiency (IE) of SIP. SIP are monitored online using QCM. Two quantitative frequencythickness (f-T) relations make the direct determination and comparison of the rate of polymerization possible even for different monomers. Based on the bi-termination model,the kinetics of SIP is simply described by two variables,which are related to two polymerization constants,namely a = 1/(kp,s,app-[M][R·]0) and b = kt,s,app/(kp,s,app[M]). Factors that could alter the kinetics of SIP are studied,including (i) the molecular weight of monomers,(ii) the solvent used,(iii) the initial density of the initiator,(iv) the concentration of monomer,[M],and (v) the catalyst system (ratio among the ingredients,metal,ligands,and additives). The dynamic nature of IE is also described by these two variables,IE = a/(a + bt). Instead of the molecular weight and the polydispersity,we suggest that film thickness,the two kinetic parameters (a and b),and the initial density of the initiator and IE be the parameters that characterize ultrathin polymer brushes. Besides the kinetics study of SIP,the reported method has many other applications,for example,in the fast screening of catalyst system for SIP and other polymerization systems.展开更多
Poly（glycidylmethacrylate） （PGMA） brushes were grafted from chloromethylated polysulfone （CMPSF） mem- brane surface by surface-initiated atom transfer radical polymerization （S1-ATRP）, and the grafting was fol...Poly（glycidylmethacrylate） （PGMA） brushes were grafted from chloromethylated polysulfone （CMPSF） mem- brane surface by surface-initiated atom transfer radical polymerization （S1-ATRP）, and the grafting was followed by hydrolysis of epoxy groups in the grafting chains to improve the membrane＇s hydrophilie property. Fourier trans- form infrared spectroscopy （FT-IR） and X-ray photoelectron spectroscopy （XPS） measurements confirmed the suc- cessful grafting and hydrolysis of PGMA. The grafting degree of the monomer, measured by periodic acid titration and gravimetric analysis, increased linearly with the polymerization time, while the static water contact angle of the membrane grafted with PGMA or hydrolyzed PGMA linearly decreased. In comparison with the PGMA-grafted membranes, the hydrolyzed PGMA-grafted membranes possess stronger hydrophilicity as indicated by their contact angle and hydration capacity, and as a result they have an improved antifouling property. Therefore, the control of the hydrophilicity of PSF membrane could be realized through adjusting the polymerization time and transforming the functional groups in the grafting chain.展开更多
A one-step procedure to hydrophilize monodisperse poly（chloromethyl-styrene-co-divinylbenzene） beads has been presented with 2-hydroxy-3-[4-（hydroxymethyl）-1H-1,2,3-triazol-1-yl]propy1 2-methylacrylate（HTMA） as ...A one-step procedure to hydrophilize monodisperse poly（chloromethyl-styrene-co-divinylbenzene） beads has been presented with 2-hydroxy-3-[4-（hydroxymethyl）-1H-1,2,3-triazol-1-yl]propy1 2-methylacrylate（HTMA） as monomer by surface-initiated atom transfer radical polymerization（SI-ATRP）.The length of the grafted poly（HTMA） chain was varied via controlling the ratio of HTMA to initiator on the surface of the beads.Using these grafted beads as the stationary phase in hydrophilic interaction chromatography,good separation was obtained for nucleosides in the mobile phase of acetonitrile-water.It was also found that the retention time and selectivity of solutes showed a positive relationship with the length of the grafted poly（HTMA） chain.展开更多
Polystyrene/SiO2 composite nanoparti- cles (PS-g-Silica) were prepared by an in-situ sur- face-initiated nitroxide-mediated radical polymeriza- tion. After SiO2 nanoparticles were treated by thionyl chloride (SOCl2), ...Polystyrene/SiO2 composite nanoparti- cles (PS-g-Silica) were prepared by an in-situ sur- face-initiated nitroxide-mediated radical polymeriza- tion. After SiO2 nanoparticles were treated by thionyl chloride (SOCl2), peroxide initiation groups were immobilized on their surfaces through a reaction with tertiary butyl hydroperoxide (TBHP). Then surface nitroxide-mediated radical polymerization was initi- ated and polystyrene was grafted on the surface of SiO2 particles. Composite nanoparticles were char- acterized by IR spectra, transmission electron mi- croscopy (TEM), atomic force microscopy (AFM) and thermogravimetry (TGA) and the results indicated that the surface-initiated nitroxide-mediated radical polymerization could be successfully used to synthe- size well-dispersive PS/SiO2 nanocomposites.展开更多
A novel chromatographic packing of chlorogenic acid（CGA） molecularly imprinted polymer（MIP） based on the 5.0 ~tm silica was prepared by surface initiated atom transfer radical polymerization（SI-ATRP） with 4-viny...A novel chromatographic packing of chlorogenic acid（CGA） molecularly imprinted polymer（MIP） based on the 5.0 ~tm silica was prepared by surface initiated atom transfer radical polymerization（SI-ATRP） with 4-vinylpyridine（4-VP） as functional monomer, ethyl glycol dimethacrylate（EDMA） as cross-linker in the mixture of methanol and water（7：3, volume ratio） under mild reaction conditions. The characteristics of CGA MIP were investi- gated by elemental analysis, thermogravimetric analysis（TGA）, Fourier transform infrared spectrometry（FTIR） and atomic force microscopy（AFM）. The effects of some chromatographic conditions such as mobile phase composition and temperature on the retention time were investigated. The adsorption capacity of the stationary phase for com- pounds was determined by frontal chromatographic technique. The results show that Freundlich isotherm fits the ex- perimental adsorption isotherm data better than Langmuir model does. The relatively high heterogeneity index values regressed with the Freundlich isotherm suggest the formation of fairly homogeneous MIP. Thermodynamic data（AAH and AAS） obtained by van＇t Hoff plots reveal an entropy-controlled separation. The CGA MIP column was shown to be successful for the separation and purification of chlorogenic acid from the extract of Honeysuckle.展开更多
基金This work was supported by the National Natural Science Foundation of China(No.20274018).
文摘Grafting of polystyrene with narrowly dispersed polymer microspheres through surface-initiated atom transferradical polymerization(ATRP)was investigated.Polydivinylbenzene(PDVB)microspheres were prepared by dispersionpolymerization with poly(N-vinyl pyrrolidone)(PVP)as stabilizer.The surfaces of PDVB microspheres werechloromethylated by chloromethyl methyl ether in the presence of zinc chloride as catalyst to form chloromethylbenzeneinitiating core sites for subsequent ATRP grafting of styrene using CuCl/bpy as catalytic system.Polystyrene was found to begrafted not only from the particle surfaces but also from within a thin shell layer,resulting in the formation of particles sizeincreased from 2.38-2.58 μm,which can further grow to 2.93 μm during secondary grafting polymerization of styrene.Thisdemonstrates that grafting polymerization proceeds through a typical ATRP procedure with living nature.All of the preparedmicrospheres have narrow particle size distribution with coefficient of variation around 10%.
基金Supported by the Scientific and Technological Development Programs of Beijing Municipal Education Commission, China (No.KM201010011004)the Scientific Research Foundation for the Returned Overseas Chinese Scholars, Ministry of Education, China, the 2011 Merit-based Research Funding for Picked Returned Overseas Scholars, Beijing Municipality, ChinaBeijing Technology and Business University Through a Research Project Approved for Undergraduates
文摘Photo-grafting of hydrophilic monomer was used to enhance the hydrophilicity of poly（ether ether ketone） （PEEK） with the aim of extending its applications to biological fields. PEEK sheets were surface modified by grafting of acrylamide（AAm） with ultraviolet（UV） irradiation in the presence or absence of benzophenone（BP）. The effects of BP, irradiation time and monomer concentration on the surface wettability of PEEK were investigated. Characteriza tion of modified PEEK using scanning electron microscopy（SEM）, energy-disperse spectrometer（EDS） and water contact angle measurements shows that AAm was successfully grafted on PEEK surface both in presence and absence of BP. With the increase in irradiation time and monomer concentration, contact angles decrease to as low as 30°, demonstrating a significant improvement of surface hydrophilicity. In agreement with the decrease in contact angle, under identical conditions, the nitrogen concentration increases, suggesting the increase in grafting degree of the grafting polymerization. This investigation demonstrates a self-initiation of PEEK due to its BP-like structure in the backbone of the polymer. Though the graft polymerization proceeds more readily in the presence of BP, the self-initiated graft polymerization is clearly observed.
文摘A couple of novel sulfobetaine copolymer is developed via Michael-type addition reaction. The comonomers, diamines and maleimide react via Michael reaction through UV irradiation using AIBN as photoinitiator producing polyamine chain. Further, sulfobetaine copolymers were obtained on treatment of the polyamine with sulfopropylating agent, 1,3-propane sultone. These novel sulfobetaine polymers were grafted on silica surface to produce responsive biocompatible surface. This easy straightforward, catalyst free facile protocol for synthesis of polymer grafted surface is useful for developing biomedical devices. Additionally, both the copolymers show fluorescence characteristics.
基金Supported by the Nationd Natural Science Foundation of China (Grant No. 20604402)Natural Science Foundation of Beijing (Grant No. 2072008)Na-tional Basic Research Program of China (Grant No. 2009CB320300)
文摘Surface initiated polymerization (SIP) is a valuable tool in synthesizing functional polymer brushes,yet the kinetic understanding of SIP lags behind the development of its application. We apply quartz crystal microbalance (QCM) to address two issues that are not fully addressed yet play a central role in the rational design of functional polymer brushes,namely quantitative determination of the kinetics and the initiator efficiency (IE) of SIP. SIP are monitored online using QCM. Two quantitative frequencythickness (f-T) relations make the direct determination and comparison of the rate of polymerization possible even for different monomers. Based on the bi-termination model,the kinetics of SIP is simply described by two variables,which are related to two polymerization constants,namely a = 1/(kp,s,app-[M][R·]0) and b = kt,s,app/(kp,s,app[M]). Factors that could alter the kinetics of SIP are studied,including (i) the molecular weight of monomers,(ii) the solvent used,(iii) the initial density of the initiator,(iv) the concentration of monomer,[M],and (v) the catalyst system (ratio among the ingredients,metal,ligands,and additives). The dynamic nature of IE is also described by these two variables,IE = a/(a + bt). Instead of the molecular weight and the polydispersity,we suggest that film thickness,the two kinetic parameters (a and b),and the initial density of the initiator and IE be the parameters that characterize ultrathin polymer brushes. Besides the kinetics study of SIP,the reported method has many other applications,for example,in the fast screening of catalyst system for SIP and other polymerization systems.
基金This work was supported by the National Natural Science Foundation of China （No. 20975080） and the key project of Chinese Ministry of Education （No. 212178）.
文摘Poly（glycidylmethacrylate） （PGMA） brushes were grafted from chloromethylated polysulfone （CMPSF） mem- brane surface by surface-initiated atom transfer radical polymerization （S1-ATRP）, and the grafting was followed by hydrolysis of epoxy groups in the grafting chains to improve the membrane＇s hydrophilie property. Fourier trans- form infrared spectroscopy （FT-IR） and X-ray photoelectron spectroscopy （XPS） measurements confirmed the suc- cessful grafting and hydrolysis of PGMA. The grafting degree of the monomer, measured by periodic acid titration and gravimetric analysis, increased linearly with the polymerization time, while the static water contact angle of the membrane grafted with PGMA or hydrolyzed PGMA linearly decreased. In comparison with the PGMA-grafted membranes, the hydrolyzed PGMA-grafted membranes possess stronger hydrophilicity as indicated by their contact angle and hydration capacity, and as a result they have an improved antifouling property. Therefore, the control of the hydrophilicity of PSF membrane could be realized through adjusting the polymerization time and transforming the functional groups in the grafting chain.
基金supported by National Natural Science Foundation of China(No.20975080)Program for New Century Excellent Talents in University(No.NCET-08-0892)+1 种基金Major State Basic Research Development Program of China(No.2009CB26608)Natural Science Foundation of Ningxia Province(No.NZ0914)
文摘A one-step procedure to hydrophilize monodisperse poly（chloromethyl-styrene-co-divinylbenzene） beads has been presented with 2-hydroxy-3-[4-（hydroxymethyl）-1H-1,2,3-triazol-1-yl]propy1 2-methylacrylate（HTMA） as monomer by surface-initiated atom transfer radical polymerization（SI-ATRP）.The length of the grafted poly（HTMA） chain was varied via controlling the ratio of HTMA to initiator on the surface of the beads.Using these grafted beads as the stationary phase in hydrophilic interaction chromatography,good separation was obtained for nucleosides in the mobile phase of acetonitrile-water.It was also found that the retention time and selectivity of solutes showed a positive relationship with the length of the grafted poly（HTMA） chain.
基金supported by the Project of Youth Teachers Foundation of the Ministry of Education of Chinathe National Natural Science Foundation of China(Grant No.20475044)the Invention Project of Science and Technology(Grant No.KJCXGC-01,NWNU).
文摘Polystyrene/SiO2 composite nanoparti- cles (PS-g-Silica) were prepared by an in-situ sur- face-initiated nitroxide-mediated radical polymeriza- tion. After SiO2 nanoparticles were treated by thionyl chloride (SOCl2), peroxide initiation groups were immobilized on their surfaces through a reaction with tertiary butyl hydroperoxide (TBHP). Then surface nitroxide-mediated radical polymerization was initi- ated and polystyrene was grafted on the surface of SiO2 particles. Composite nanoparticles were char- acterized by IR spectra, transmission electron mi- croscopy (TEM), atomic force microscopy (AFM) and thermogravimetry (TGA) and the results indicated that the surface-initiated nitroxide-mediated radical polymerization could be successfully used to synthe- size well-dispersive PS/SiO2 nanocomposites.
基金Supported by the National Natural Science Foundation of China（No.31271868） and the National Science and Technology Support Project of China（No.2012BAKI7B07）.
文摘A novel chromatographic packing of chlorogenic acid（CGA） molecularly imprinted polymer（MIP） based on the 5.0 ~tm silica was prepared by surface initiated atom transfer radical polymerization（SI-ATRP） with 4-vinylpyridine（4-VP） as functional monomer, ethyl glycol dimethacrylate（EDMA） as cross-linker in the mixture of methanol and water（7：3, volume ratio） under mild reaction conditions. The characteristics of CGA MIP were investi- gated by elemental analysis, thermogravimetric analysis（TGA）, Fourier transform infrared spectrometry（FTIR） and atomic force microscopy（AFM）. The effects of some chromatographic conditions such as mobile phase composition and temperature on the retention time were investigated. The adsorption capacity of the stationary phase for com- pounds was determined by frontal chromatographic technique. The results show that Freundlich isotherm fits the ex- perimental adsorption isotherm data better than Langmuir model does. The relatively high heterogeneity index values regressed with the Freundlich isotherm suggest the formation of fairly homogeneous MIP. Thermodynamic data（AAH and AAS） obtained by van＇t Hoff plots reveal an entropy-controlled separation. The CGA MIP column was shown to be successful for the separation and purification of chlorogenic acid from the extract of Honeysuckle.
