The fluorescence behaviours of a new polymer poly [oxy-2 (4-N, N-dimethylaminobenzyl) propane-1 , 3-diyloxy-terephthaloyl] (Ⅰ) in solution were studied. Inter-and intra -molecular exciplex is formed between the singl...The fluorescence behaviours of a new polymer poly [oxy-2 (4-N, N-dimethylaminobenzyl) propane-1 , 3-diyloxy-terephthaloyl] (Ⅰ) in solution were studied. Inter-and intra -molecular exciplex is formed between the singlet excited state of N, N- dimethylanilino group (abbreviated to DMA) and the ground state of terephthalate group (abbreviated to TP). The intensity ratio of the long wavelength exciplex fluorescence to the short wavelength emission of DMA group is used as an index for the inter-and intra-molecular interaction of chromophores. The results are compared with model polymer polyoxy-2-(4-N ,N-dimethylaminobenzyl) propanc-1 , 3-diyloxyadipoyl (Ⅱ), model monomer compound 4-N, N-dimethylaminobenzylmethyl terephthalate(Ⅲ) and diethyl 2-( 4-N, N-dimethylaminobenzyl) malonate (Ⅳ). Polymer association derived by electron donor and acceptor interaction (EDA) is further verified as a key role in the interpolymer exciplex formation . The fluorescence decay time of (Ⅰ) and monomer (Ⅲ) are measured in solutions.展开更多
A substituted glycolide, 3-benzyloxymethyl-1,4-dioxane-2,5-dione, was synthesized. It is a suitable precursor for the preparation of a new hydrophilic biodegradable poly(a-hydroxy acid). The polymerizations were carri...A substituted glycolide, 3-benzyloxymethyl-1,4-dioxane-2,5-dione, was synthesized. It is a suitable precursor for the preparation of a new hydrophilic biodegradable poly(a-hydroxy acid). The polymerizations were carried out in bulk in the presence of Sn(Oct)(2) at 120-140 degreesC. The resulting polymers were subjected to hydrogenolysis with a Pd/C catalyst in a mixed solvent to remove the protecting benzyl groups. A novel poly(a-hydroxy acid) with pendant hydroxy groups was obtained. The hydrophilicity of the resulting polymer was evaluated preliminarily.展开更多
A kind of novel heat-resistant, high performance engineering thermoplastic phthalazinone poly(aryl ether sulfone ketone) (PPESK) containing a carboxyl group in its side chain was prepared by the nucleophilic displacem...A kind of novel heat-resistant, high performance engineering thermoplastic phthalazinone poly(aryl ether sulfone ketone) (PPESK) containing a carboxyl group in its side chain was prepared by the nucleophilic displacement reaction of 4-(4-hydroxylphenyl)- 1 (2H)-phthalazinone with di(4-chlorophenyl) sulfone, 4,4'-difluoro-benzophenone and phenolphthalin in sulfolane in the presence of K2CO3 to produce high molecular weight polymers which can be dissolved in some polar solvents such as chloroform and nitrobenzene at room temperature and can be easily cast into flexible, yellowish and transparent films. PPESK is an amorphous polymer having a decomposition temperature above 400degreesC, which indicates that it has high thermal stability. At the same time, the thermal properties of PPESKs with dicyandiamide (DICY) as curing agent indicated that the heat-resistance properties of the PPESKs are improved after curing. The apparent activation energy (A-E) of the cross-linking reaction and the reaction order (n) of PPESK/DICY were found to be 52.2 kJ/mol and ca. 1.0, respectively. Therefore, the cross-linking reaction is approximately a first order reaction.展开更多
A fluorine containing monomer was synthesized and its polymer was prepared by aromatic nucleophilic substitution polycondensation of the monomer and 4,4′ difluorobenzophenone using potassium carbonate as the catalyst...A fluorine containing monomer was synthesized and its polymer was prepared by aromatic nucleophilic substitution polycondensation of the monomer and 4,4′ difluorobenzophenone using potassium carbonate as the catalyst and tetramethylene sulfone as solvent. The polymer properties were characterized by FTIR, NMR, DSC and the results showed that the T g of the polymer is 141 ℃ and the solubility of the polymer was obviously improved due to the introduction of (3 trifluoromethyl)phenyl group.展开更多
Two novel poly(aryl ether ketone)s based on (3 methyl)phenylhydroquinone were synthesized via aromatic nucleophilic substitution reaction. The high molecular polymers were easily obtained because of the high reaction ...Two novel poly(aryl ether ketone)s based on (3 methyl)phenylhydroquinone were synthesized via aromatic nucleophilic substitution reaction. The high molecular polymers were easily obtained because of the high reaction activity of bisphenol monomer. The traces of DSC showed that the T gs of m TPEEK and m TPEEKK were 421 and 432 K, respectively. The two polymers exhibit a high thermal stability and good solubility. The transparent and flexible films were readily prepared with chloroform solution. The film of m TPEEK had a low dielectric constant( ε =2 7).展开更多
合成了具有悬挂双键的苯乙烯-二乙烯基苯多孔微球,在悬挂双键处接枝甲基丙烯酸甲酯,制成了一系列不同接枝度的两亲性聚合物多孔微球。考察了悬挂双键数量、反应时间等因素对接枝率的影响以及接枝率对微球形貌的影响。实验中通过观测澄清...合成了具有悬挂双键的苯乙烯-二乙烯基苯多孔微球,在悬挂双键处接枝甲基丙烯酸甲酯,制成了一系列不同接枝度的两亲性聚合物多孔微球。考察了悬挂双键数量、反应时间等因素对接枝率的影响以及接枝率对微球形貌的影响。实验中通过观测澄清点,有效地控制了反应后期自加速现象对接枝率的影响。在反应时间25 m in时,制得了平均孔径为50 nm的两亲性多孔微球。将该微球用于对化妆品活性组分的负载,对极性物的负载率比接枝前高出2倍。展开更多
文摘The fluorescence behaviours of a new polymer poly [oxy-2 (4-N, N-dimethylaminobenzyl) propane-1 , 3-diyloxy-terephthaloyl] (Ⅰ) in solution were studied. Inter-and intra -molecular exciplex is formed between the singlet excited state of N, N- dimethylanilino group (abbreviated to DMA) and the ground state of terephthalate group (abbreviated to TP). The intensity ratio of the long wavelength exciplex fluorescence to the short wavelength emission of DMA group is used as an index for the inter-and intra-molecular interaction of chromophores. The results are compared with model polymer polyoxy-2-(4-N ,N-dimethylaminobenzyl) propanc-1 , 3-diyloxyadipoyl (Ⅱ), model monomer compound 4-N, N-dimethylaminobenzylmethyl terephthalate(Ⅲ) and diethyl 2-( 4-N, N-dimethylaminobenzyl) malonate (Ⅳ). Polymer association derived by electron donor and acceptor interaction (EDA) is further verified as a key role in the interpolymer exciplex formation . The fluorescence decay time of (Ⅰ) and monomer (Ⅲ) are measured in solutions.
基金This work was supported by the Major State Basic Research Program of China (No. G1999064704).
文摘A substituted glycolide, 3-benzyloxymethyl-1,4-dioxane-2,5-dione, was synthesized. It is a suitable precursor for the preparation of a new hydrophilic biodegradable poly(a-hydroxy acid). The polymerizations were carried out in bulk in the presence of Sn(Oct)(2) at 120-140 degreesC. The resulting polymers were subjected to hydrogenolysis with a Pd/C catalyst in a mixed solvent to remove the protecting benzyl groups. A novel poly(a-hydroxy acid) with pendant hydroxy groups was obtained. The hydrophilicity of the resulting polymer was evaluated preliminarily.
基金This project was supported by the National Ninth Five-Year-Plan Key Project "The pilot-scale production and the applied development of polyaryl ether concerning phthalazinone moiety" (No. 97-564-01-07).
文摘A kind of novel heat-resistant, high performance engineering thermoplastic phthalazinone poly(aryl ether sulfone ketone) (PPESK) containing a carboxyl group in its side chain was prepared by the nucleophilic displacement reaction of 4-(4-hydroxylphenyl)- 1 (2H)-phthalazinone with di(4-chlorophenyl) sulfone, 4,4'-difluoro-benzophenone and phenolphthalin in sulfolane in the presence of K2CO3 to produce high molecular weight polymers which can be dissolved in some polar solvents such as chloroform and nitrobenzene at room temperature and can be easily cast into flexible, yellowish and transparent films. PPESK is an amorphous polymer having a decomposition temperature above 400degreesC, which indicates that it has high thermal stability. At the same time, the thermal properties of PPESKs with dicyandiamide (DICY) as curing agent indicated that the heat-resistance properties of the PPESKs are improved after curing. The apparent activation energy (A-E) of the cross-linking reaction and the reaction order (n) of PPESK/DICY were found to be 52.2 kJ/mol and ca. 1.0, respectively. Therefore, the cross-linking reaction is approximately a first order reaction.
文摘A fluorine containing monomer was synthesized and its polymer was prepared by aromatic nucleophilic substitution polycondensation of the monomer and 4,4′ difluorobenzophenone using potassium carbonate as the catalyst and tetramethylene sulfone as solvent. The polymer properties were characterized by FTIR, NMR, DSC and the results showed that the T g of the polymer is 141 ℃ and the solubility of the polymer was obviously improved due to the introduction of (3 trifluoromethyl)phenyl group.
文摘Two novel poly(aryl ether ketone)s based on (3 methyl)phenylhydroquinone were synthesized via aromatic nucleophilic substitution reaction. The high molecular polymers were easily obtained because of the high reaction activity of bisphenol monomer. The traces of DSC showed that the T gs of m TPEEK and m TPEEKK were 421 and 432 K, respectively. The two polymers exhibit a high thermal stability and good solubility. The transparent and flexible films were readily prepared with chloroform solution. The film of m TPEEK had a low dielectric constant( ε =2 7).
文摘合成了具有悬挂双键的苯乙烯-二乙烯基苯多孔微球,在悬挂双键处接枝甲基丙烯酸甲酯,制成了一系列不同接枝度的两亲性聚合物多孔微球。考察了悬挂双键数量、反应时间等因素对接枝率的影响以及接枝率对微球形貌的影响。实验中通过观测澄清点,有效地控制了反应后期自加速现象对接枝率的影响。在反应时间25 m in时,制得了平均孔径为50 nm的两亲性多孔微球。将该微球用于对化妆品活性组分的负载,对极性物的负载率比接枝前高出2倍。
