Polyketone resins have been prepared by the Friedel-Crafts polymerization of dithiophenylidenecyclopentanone （I）, dithiophenylidenecyclohexanone （II） and dithiophenylideneacetone （III） with adipoyl, sebacoyl and...Polyketone resins have been prepared by the Friedel-Crafts polymerization of dithiophenylidenecyclopentanone （I）, dithiophenylidenecyclohexanone （II） and dithiophenylideneacetone （III） with adipoyl, sebacoyl and terephthaloyl dichlorides using boron trifluoride as catalyst and carbon disulphide as solvent. Polymers were characterized with IR, 1H- NMR, and the results showed the presence of carbonyl of ketonic groups in the main chain. The polyketones have inherent viscosities of 0.40-0.70 dL/g. All the polymers are semicrystalline and most of them are partially soluble in most common organic solvents but freely soluble in aprotic solvents. The temperatures of 50% weight loss are as high as 185℃ to 280℃ in air, indicating that these aromatic polyketones have excellent thermal stability. All the polyketones were tested for their antimicrobial activity against bacteria and fungi.展开更多
The copolymerization of CO and styrene catalyzed by Pd/C toward the formation of polyketones （PK）was studied in the N-valeronitrile-N＆#39;-methylimidazolium hexafluorophosphate （[C4CNmim]＋PF6-） medium. The synth...The copolymerization of CO and styrene catalyzed by Pd/C toward the formation of polyketones （PK）was studied in the N-valeronitrile-N＆#39;-methylimidazolium hexafluorophosphate （[C4CNmim]＋PF6-） medium. The synthe-sized PK was characterized by Fourier transform infrared（FTIR）, elemental analysis, 13C-nuclear magnetic resonance （13C-NMR）, differential scanning calorimetry （DSC）, thermogravimetric analysis （TGA） and gel permeation chro-matography （GPC）. The supported ionic liquid film on the surface of Pd/C catalyst can prevent the products from covering the hole of active carbon due to its chemical stability and weak coordination ability with metal ions, and thus efficiently improve the catalytic activity. The effects of different amounts of ionic liquid on the catalytic activity and reusability of the catalyst and the molecular weight of PK were discussed. When the usage of ionic liquid is 10wt%（0.1 g ionic liquid/1 g active carbon carrier） and the theoretical content of Pd2＋is 5wt%（0.05 g Pd2＋/1 g active car-bon carrier）, the highest catalytic activity 2 963.64 gSTCO/（gPd＆#183;h） is achieved with the molecular weight and polydispersity index of PK as Mn=9 684, Mw=13 452 and Mw/Mn=1.389.展开更多
Three types of organic compounds--two carboxylic acids and an anhydride, were used as additives for polyketone （PK）. The effect of the additive structure and their feed ratios on the melting temperature, crystalliza...Three types of organic compounds--two carboxylic acids and an anhydride, were used as additives for polyketone （PK）. The effect of the additive structure and their feed ratios on the melting temperature, crystallization temperature, and crystallization rate of PK were studied. We found that the crystallization temperature could be reduced significantly by introducing a small quantity of organic additive, in particular, an anhydride. On addition of 1 phr of anhydride, the crystallization temperature was reduced by 10.7 ℃. Therefore, the non-isothermal crystallization kinetics of aliphatic PKJanhydride blends with various feed ratios was investigated using DSC. The results were analyzed by various theoretical models, such as Avrami, Ozawa and combined Avrami-Ozawa models.展开更多
文摘Polyketone resins have been prepared by the Friedel-Crafts polymerization of dithiophenylidenecyclopentanone （I）, dithiophenylidenecyclohexanone （II） and dithiophenylideneacetone （III） with adipoyl, sebacoyl and terephthaloyl dichlorides using boron trifluoride as catalyst and carbon disulphide as solvent. Polymers were characterized with IR, 1H- NMR, and the results showed the presence of carbonyl of ketonic groups in the main chain. The polyketones have inherent viscosities of 0.40-0.70 dL/g. All the polymers are semicrystalline and most of them are partially soluble in most common organic solvents but freely soluble in aprotic solvents. The temperatures of 50% weight loss are as high as 185℃ to 280℃ in air, indicating that these aromatic polyketones have excellent thermal stability. All the polyketones were tested for their antimicrobial activity against bacteria and fungi.
基金Supported by the Tianjin Natural Science Foundation(No.07JCYBJC00600)
文摘The copolymerization of CO and styrene catalyzed by Pd/C toward the formation of polyketones （PK）was studied in the N-valeronitrile-N＆#39;-methylimidazolium hexafluorophosphate （[C4CNmim]＋PF6-） medium. The synthe-sized PK was characterized by Fourier transform infrared（FTIR）, elemental analysis, 13C-nuclear magnetic resonance （13C-NMR）, differential scanning calorimetry （DSC）, thermogravimetric analysis （TGA） and gel permeation chro-matography （GPC）. The supported ionic liquid film on the surface of Pd/C catalyst can prevent the products from covering the hole of active carbon due to its chemical stability and weak coordination ability with metal ions, and thus efficiently improve the catalytic activity. The effects of different amounts of ionic liquid on the catalytic activity and reusability of the catalyst and the molecular weight of PK were discussed. When the usage of ionic liquid is 10wt%（0.1 g ionic liquid/1 g active carbon carrier） and the theoretical content of Pd2＋is 5wt%（0.05 g Pd2＋/1 g active car-bon carrier）, the highest catalytic activity 2 963.64 gSTCO/（gPd＆#183;h） is achieved with the molecular weight and polydispersity index of PK as Mn=9 684, Mw=13 452 and Mw/Mn=1.389.
文摘Three types of organic compounds--two carboxylic acids and an anhydride, were used as additives for polyketone （PK）. The effect of the additive structure and their feed ratios on the melting temperature, crystallization temperature, and crystallization rate of PK were studied. We found that the crystallization temperature could be reduced significantly by introducing a small quantity of organic additive, in particular, an anhydride. On addition of 1 phr of anhydride, the crystallization temperature was reduced by 10.7 ℃. Therefore, the non-isothermal crystallization kinetics of aliphatic PKJanhydride blends with various feed ratios was investigated using DSC. The results were analyzed by various theoretical models, such as Avrami, Ozawa and combined Avrami-Ozawa models.
