Crosslink polymerization kinetics of poly（acrylic acid-co-2-acrylamido-2-methylpropane sulfonic acid）,AA/AMPS hydrogels,was investigated by using dilatometry in the presence of sodium persulfate as initiator and N,N...Crosslink polymerization kinetics of poly（acrylic acid-co-2-acrylamido-2-methylpropane sulfonic acid）,AA/AMPS hydrogels,was investigated by using dilatometry in the presence of sodium persulfate as initiator and N,N＇-methylene bis（acrylamide） as crosslinker.It was found that the reaction for the crosslink polymerization of AA/AMPS hydrogels had orders of 0.58,1.14,and 0.86 with respect to the initiator,AMPS,and AA,respectively.From the Arrhenius plots,the activation energy of the crosslink polymerization was found to be about 140 and 89 kJ·mol-1 in the presence and absence of the crosslinker,respectively,in the temperature range from 45 to 65 °C.It was noted that the crosslinker had effects on the reaction order of the initiator and the activation energy due to the formation of cross-linked networks,which was verified by Fourier transfer infrared （FTIR） spectrum.To further confirm the influences of the cross-linked network structure on kinetic parameters of the crosslink polymerization,a mechanism was proposed,which highlights the different termination routes between free radical polymerization and crosslink polymerization.These results suggest that dilatometry provides a convenient tool for crosslink polymeri-zation study,and confirm that the cross-linked networks are formed in the crosslink polymerization.展开更多
The suspension polymerization with two organic phases was adopted to prepare spherical hyper- crosslinked resin by self-polycondensation of 4,4＇-bis-（chloromethyl）- 1, 1＇-biphenyl （CMB）. The chemical structure,m...The suspension polymerization with two organic phases was adopted to prepare spherical hyper- crosslinked resin by self-polycondensation of 4,4＇-bis-（chloromethyl）- 1, 1＇-biphenyl （CMB）. The chemical structure,morphology and pore characteristics of the novel spherical resin were characterized with Fourier transform infrared spectroscopy （FTIR）, micrograph and Brunauer-Emmett-Teller （BET）. It is found that the suspension system and stirring speed impose a great influence upon the regularity and size distribution of hypercrosslinked beads. To prepare CMB resin beads with diameter of about 300 μm, the optimal condition is as follows： stirring speed 300 r·min^-1, and the volume ratio of the two organic phases （nitrobenzene/dimethyl silicon oil） 1 ： 5. After the self-polycondensation and sqccedent post-crosslinking of CMB monomer, the spherical adsorbent presents high spec^al surface area （1190 m^2· g^-1） and abundant pore^volume （0.714 cm^3· g^-1）, and could be potentially applied qn the adsorption of various organic molecules and synthesis of porous ion exchanger.展开更多
Porous polymer supported palladium catalyst for cross coupling reactions with high activity has been successfully prepared by coordination of Pd 2+ species with Schiff bases functionalized porous polymer. The catalyst...Porous polymer supported palladium catalyst for cross coupling reactions with high activity has been successfully prepared by coordination of Pd 2+ species with Schiff bases functionalized porous polymer. The catalyst has been systemically investi-gated by a series of characterizations such as TEM, N 2 adsorption, NMR, IR, XPS, etc. TEM and N 2 isotherms show that the sample maintains the nanoporous structure after the modification and coordination. XPS results show that chemical state of palladium species in the catalyst is mainly +2. More importantly, the catalyst shows very high activities and excellent recycla-bility in a series of coupling reactions including Suzuki, Sonogashira, and Heck reactions. Hot filtration and poison of catalysts experiments have also been performed and the results indicate that soluble active species (mainly Pd(0) species) in-situ gener-ated from the catalyst under the reaction conditions are the active intermediates, which would redeposit to the supporter after the reactions.展开更多
基金Supported by the National Natural Science Foundation of China（20176007 20376087）
文摘Crosslink polymerization kinetics of poly（acrylic acid-co-2-acrylamido-2-methylpropane sulfonic acid）,AA/AMPS hydrogels,was investigated by using dilatometry in the presence of sodium persulfate as initiator and N,N＇-methylene bis（acrylamide） as crosslinker.It was found that the reaction for the crosslink polymerization of AA/AMPS hydrogels had orders of 0.58,1.14,and 0.86 with respect to the initiator,AMPS,and AA,respectively.From the Arrhenius plots,the activation energy of the crosslink polymerization was found to be about 140 and 89 kJ·mol-1 in the presence and absence of the crosslinker,respectively,in the temperature range from 45 to 65 °C.It was noted that the crosslinker had effects on the reaction order of the initiator and the activation energy due to the formation of cross-linked networks,which was verified by Fourier transfer infrared （FTIR） spectrum.To further confirm the influences of the cross-linked network structure on kinetic parameters of the crosslink polymerization,a mechanism was proposed,which highlights the different termination routes between free radical polymerization and crosslink polymerization.These results suggest that dilatometry provides a convenient tool for crosslink polymeri-zation study,and confirm that the cross-linked networks are formed in the crosslink polymerization.
基金Supported by the National Natural Science Foundation of China （21004055） and the Doctoral Discipline Foundation of Education Ministry （20104101110005）.
文摘The suspension polymerization with two organic phases was adopted to prepare spherical hyper- crosslinked resin by self-polycondensation of 4,4＇-bis-（chloromethyl）- 1, 1＇-biphenyl （CMB）. The chemical structure,morphology and pore characteristics of the novel spherical resin were characterized with Fourier transform infrared spectroscopy （FTIR）, micrograph and Brunauer-Emmett-Teller （BET）. It is found that the suspension system and stirring speed impose a great influence upon the regularity and size distribution of hypercrosslinked beads. To prepare CMB resin beads with diameter of about 300 μm, the optimal condition is as follows： stirring speed 300 r·min^-1, and the volume ratio of the two organic phases （nitrobenzene/dimethyl silicon oil） 1 ： 5. After the self-polycondensation and sqccedent post-crosslinking of CMB monomer, the spherical adsorbent presents high spec^al surface area （1190 m^2· g^-1） and abundant pore^volume （0.714 cm^3· g^-1）, and could be potentially applied qn the adsorption of various organic molecules and synthesis of porous ion exchanger.
基金supported by the National Natural Science Foundation of China (20973079 & 21003107)State Basic Research Project of China(2009CB623507)Fundamental Research Funds for the Central Universities (2010QNA3035)
文摘Porous polymer supported palladium catalyst for cross coupling reactions with high activity has been successfully prepared by coordination of Pd 2+ species with Schiff bases functionalized porous polymer. The catalyst has been systemically investi-gated by a series of characterizations such as TEM, N 2 adsorption, NMR, IR, XPS, etc. TEM and N 2 isotherms show that the sample maintains the nanoporous structure after the modification and coordination. XPS results show that chemical state of palladium species in the catalyst is mainly +2. More importantly, the catalyst shows very high activities and excellent recycla-bility in a series of coupling reactions including Suzuki, Sonogashira, and Heck reactions. Hot filtration and poison of catalysts experiments have also been performed and the results indicate that soluble active species (mainly Pd(0) species) in-situ gener-ated from the catalyst under the reaction conditions are the active intermediates, which would redeposit to the supporter after the reactions.
