An efficient route to macrocyclic polymers via “click” cyclization was presented.The α-bromine and ω-alkyne PMMA were prepared using the standard ATRP technique,initiated with propargyl 2-bromoisobutyrate,Cu(Ⅰ)Br...An efficient route to macrocyclic polymers via “click” cyclization was presented.The α-bromine and ω-alkyne PMMA were prepared using the standard ATRP technique,initiated with propargyl 2-bromoisobutyrate,Cu(Ⅰ)Br and N,N,N’,N″,N-pentamethyldiethylenetriamine(PMDETA).Azidation of the terminal bromine was followed in DMF with sodium azide,and α-azide,ω-alkyne PMMA precursor was obtained.Then the “click” cylcization of precursor between terminal azide and alkyne was carried out under the catalysis of CuBr/PMDETA,during the course of the reaction,a pseudo-high dilution technique was utilized to ensure the favored intramolecular cylcization.The nearly complete cylcization has been confirmed by a combination of IR,1H NMR and GPC analysis,and cyclo-PMMA with an Mn of 15000,PDI of 1.38 was obtained.展开更多
Effects of annealing temperature( T a) and annealing time( t a) on the liquid liquid transition and transition intensity of atactic poly(methyl methacrylate) were studied by means of differential scanning calorimetry....Effects of annealing temperature( T a) and annealing time( t a) on the liquid liquid transition and transition intensity of atactic poly(methyl methacrylate) were studied by means of differential scanning calorimetry. With the increase of T a from 393 to 443 K, T ll shifted to higher temperature with the decrease in transition intensity, on the contrary, when T a was over 443 K, T ll declined and transition intensity increased. When T a kept constant with the increase of t a, T ll and transition intensity varied as the results described above. Moreover, the variation extent of T ll and transition intensity increased with the increase of T a, in other words, the time needed reaching the maximum extent of variation of the two parameters was decreased with the increase of T a. The dependence of T ll and transition intensity on annealing conditions may be explained by the formation of local ordered structure, i.e . stereocomplex, during the annealing process by means of Van der Waals forces between isotacitic and syndiotactic segments of the same or different chains of atactic poly(methyl methacrylate).展开更多
基金National "Shi Wu"Supporting Key Item of China(No.2004BA720A15)Health Department Priority Supporting Item of Clinic Subject of China [No.(2004)468]Shenzhen Scientific Planning Supporting Item of China(No.200602099)~~
文摘An efficient route to macrocyclic polymers via “click” cyclization was presented.The α-bromine and ω-alkyne PMMA were prepared using the standard ATRP technique,initiated with propargyl 2-bromoisobutyrate,Cu(Ⅰ)Br and N,N,N’,N″,N-pentamethyldiethylenetriamine(PMDETA).Azidation of the terminal bromine was followed in DMF with sodium azide,and α-azide,ω-alkyne PMMA precursor was obtained.Then the “click” cylcization of precursor between terminal azide and alkyne was carried out under the catalysis of CuBr/PMDETA,during the course of the reaction,a pseudo-high dilution technique was utilized to ensure the favored intramolecular cylcization.The nearly complete cylcization has been confirmed by a combination of IR,1H NMR and GPC analysis,and cyclo-PMMA with an Mn of 15000,PDI of 1.38 was obtained.
文摘Effects of annealing temperature( T a) and annealing time( t a) on the liquid liquid transition and transition intensity of atactic poly(methyl methacrylate) were studied by means of differential scanning calorimetry. With the increase of T a from 393 to 443 K, T ll shifted to higher temperature with the decrease in transition intensity, on the contrary, when T a was over 443 K, T ll declined and transition intensity increased. When T a kept constant with the increase of t a, T ll and transition intensity varied as the results described above. Moreover, the variation extent of T ll and transition intensity increased with the increase of T a, in other words, the time needed reaching the maximum extent of variation of the two parameters was decreased with the increase of T a. The dependence of T ll and transition intensity on annealing conditions may be explained by the formation of local ordered structure, i.e . stereocomplex, during the annealing process by means of Van der Waals forces between isotacitic and syndiotactic segments of the same or different chains of atactic poly(methyl methacrylate).
