A series of electron donors,including 1,1-cyclopentanecarboxylic acid diethyl ester (CPCADEE),1,1cyclopentanedimethanol acetic diester (CPDMAD),1,1-biethoxymethyl pentane (BEMP),2,2-diethyl diethylmalonate (DEDEM)and ...A series of electron donors,including 1,1-cyclopentanecarboxylic acid diethyl ester (CPCADEE),1,1cyclopentanedimethanol acetic diester (CPDMAD),1,1-biethoxymethyl pentane (BEMP),2,2-diethyl diethylmalonate (DEDEM)and 2,2-diethyl-1,3-propanediol acetic diester (DEPDADE),were synthesized by diethyl malonate (DEM).The purities and structures of the above products were characterized by gas chromatography (GC) and gas chromatography-mass spectrometer (GC-MS),respectively.Furthermore,the possible optimal three-dimensional structures of these donors were simulated by means of Gaussian 03 and Chem 3D.Then these electron donors were coordinated with tetrachloro titanium (TiCl 4) and chloride magnesium (MgCl 2)to obtain the catalysts for the polymerization of propylene.The catalytic activities and properties of polypropylene are greatly improved by adding external donor(ED) when CPCADEE or DEPDADE is used as internal donor(ID).However,when BEMP was used as ID,the highest catalytic activity is obtained without adding ED,which can reduce production costs and simplify catalytic synthesis.The experiments indicate that BEMP has the shortest distance of oxygen atoms and the highest electronegativity.展开更多
Silk was grafted using 2-hydroxyethyl methacrylate(HEMA)by atom transfer radical polymerization(ATRP)method.The amino groups and hydroxyl groups on the side chains of the silk fibroin was reacted with 2-bromoisobutyry...Silk was grafted using 2-hydroxyethyl methacrylate(HEMA)by atom transfer radical polymerization(ATRP)method.The amino groups and hydroxyl groups on the side chains of the silk fibroin was reacted with 2-bromoisobutyryl bromide(BriB-Br)to obtain efficient macroinitiator for ATRP.And the macroinitiator was grafted with HEMA in water aqueous using CuBr/N,N,N',N",N"-pentamethyldiethylenetriamine(PMDETA)as catalyst system.The effects of monomer concentration,the proportion of CuBr and PMDETA,grafting temperature and time on the silk grafting were discussed,and the optimal grafting technology was obtained.FT-IR characterization of the grafted silk showed a peak corresponding to HEMA,which indicated that HEMA was grafted onto the surface of silk.ATRP method could be applied on the silk modification and this technique provided a new way for silk grafting.展开更多
Hydrogel materials were prepared by thermopolymerization with different content of glyceryl methacrylate and hydroxyethyl methacrylate. The different states of water in swelling hydrogels were described and studied by...Hydrogel materials were prepared by thermopolymerization with different content of glyceryl methacrylate and hydroxyethyl methacrylate. The different states of water in swelling hydrogels were described and studied by differential scanning calorimetry(DSC). It was found that the hydrophilicity of GMA was stronger than HEMA,the water content and bound water of GMA hydrogel are higher than HEMA hydrogel.With the increase of GMA content, the content of free water in hydrogel increased. When GMA content was lower than 50%, the increase of GMA content also increased the content of bound water; but when GMA content was higher than 50%, the increase of GMA content decreased the content of bound water, which was caused by the chain hydrogen bond formed on the GMA chain with hydroxyl group each other.展开更多
基金Supported by National Natural Science Foundation of China (No. 20476080)Tianjin Natural Science Foundation (No. 07JCYBJC00600)
文摘A series of electron donors,including 1,1-cyclopentanecarboxylic acid diethyl ester (CPCADEE),1,1cyclopentanedimethanol acetic diester (CPDMAD),1,1-biethoxymethyl pentane (BEMP),2,2-diethyl diethylmalonate (DEDEM)and 2,2-diethyl-1,3-propanediol acetic diester (DEPDADE),were synthesized by diethyl malonate (DEM).The purities and structures of the above products were characterized by gas chromatography (GC) and gas chromatography-mass spectrometer (GC-MS),respectively.Furthermore,the possible optimal three-dimensional structures of these donors were simulated by means of Gaussian 03 and Chem 3D.Then these electron donors were coordinated with tetrachloro titanium (TiCl 4) and chloride magnesium (MgCl 2)to obtain the catalysts for the polymerization of propylene.The catalytic activities and properties of polypropylene are greatly improved by adding external donor(ED) when CPCADEE or DEPDADE is used as internal donor(ID).However,when BEMP was used as ID,the highest catalytic activity is obtained without adding ED,which can reduce production costs and simplify catalytic synthesis.The experiments indicate that BEMP has the shortest distance of oxygen atoms and the highest electronegativity.
基金National Natural Science Foundation of China(No.50673071,No.50973079)Natural Science Fund for Colleges and Universities in Jiangsu Province,China(No.07KJD540188,No.09KJA540001)
文摘Silk was grafted using 2-hydroxyethyl methacrylate(HEMA)by atom transfer radical polymerization(ATRP)method.The amino groups and hydroxyl groups on the side chains of the silk fibroin was reacted with 2-bromoisobutyryl bromide(BriB-Br)to obtain efficient macroinitiator for ATRP.And the macroinitiator was grafted with HEMA in water aqueous using CuBr/N,N,N',N",N"-pentamethyldiethylenetriamine(PMDETA)as catalyst system.The effects of monomer concentration,the proportion of CuBr and PMDETA,grafting temperature and time on the silk grafting were discussed,and the optimal grafting technology was obtained.FT-IR characterization of the grafted silk showed a peak corresponding to HEMA,which indicated that HEMA was grafted onto the surface of silk.ATRP method could be applied on the silk modification and this technique provided a new way for silk grafting.
文摘Hydrogel materials were prepared by thermopolymerization with different content of glyceryl methacrylate and hydroxyethyl methacrylate. The different states of water in swelling hydrogels were described and studied by differential scanning calorimetry(DSC). It was found that the hydrophilicity of GMA was stronger than HEMA,the water content and bound water of GMA hydrogel are higher than HEMA hydrogel.With the increase of GMA content, the content of free water in hydrogel increased. When GMA content was lower than 50%, the increase of GMA content also increased the content of bound water; but when GMA content was higher than 50%, the increase of GMA content decreased the content of bound water, which was caused by the chain hydrogen bond formed on the GMA chain with hydroxyl group each other.
