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硼改性HZSM-5沸石对甲苯乙基化的择形催化作用 被引量:3
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作者 曾昭槐 苏毅 《燃料化学学报》 EI CAS CSCD 北大核心 1989年第1期9-15,共7页
采用XRD、XPS、BET吸附、脉冲中毒、TPD、IR等方法,探讨了硼改性后HZSM-5沸石分子筛孔结构和表面酸性的变化对甲苯和乙醇烷基化反应活性和选择性的影响。BHZSM-5沸石催化剂能在活性稍有降低的基础上使甲乙苯产率和对甲乙苯选择性大大提... 采用XRD、XPS、BET吸附、脉冲中毒、TPD、IR等方法,探讨了硼改性后HZSM-5沸石分子筛孔结构和表面酸性的变化对甲苯和乙醇烷基化反应活性和选择性的影响。BHZSM-5沸石催化剂能在活性稍有降低的基础上使甲乙苯产率和对甲乙苯选择性大大提高。当烷基化剂乙醇含水量少于30%时,也得到相近的结果。处理剂H_3BO_3是以B_2O_3的形式分布于沸石晶内外的,使其晶面间距,比孔容、比表面减小,而Γ_(p-ET)/Γ_(m-Et)增大。表明沸石孔道变窄,对甲乙苯相对更易扩散。同时,B_2O_3也调变了HZSM-5沸石的表面酸性。外表面酸中心为B_2O_3所覆盖,以致脉冲中毒实验中,4-甲基喹啉基本不起作用。TPD谱中表征强酸中心的高温峰消失。IR谱中表征B酸中心、L酸中心的特征吸收带强度变弱,即B、L酸中心数同时减少。不是所有酸中心都是活性中心,只有处于一定大小空间、具有适当强度的酸中心才能满足对烷基化反应活性和选择性的要求。此外,ESR谱表明,L酸中心参与了甲苯烷基化过程。 展开更多
关键词 沸石 甲苯乙基化 择形催化 改性
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甲苯乙基化过程中ZSM-5分子筛的积炭 被引量:4
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作者 曾昭槐 詹必增 《Chinese Journal of Catalysis》 SCIE CAS CSCD 北大核心 1989年第1期83-86,共4页
积炭是分子筛催化剂失活的主要原因。目前,有关ZSM-5积炭的研究报道还不多,且多采用甲醇汽油化的反应作探针。我们利用甲苯乙基化反应研究ZSM-5分子筛的积炭,得到了一些有意义的结果。 NaZSM-5分子筛用NH<sub>4</sub>NO<... 积炭是分子筛催化剂失活的主要原因。目前,有关ZSM-5积炭的研究报道还不多,且多采用甲醇汽油化的反应作探针。我们利用甲苯乙基化反应研究ZSM-5分子筛的积炭,得到了一些有意义的结果。 NaZSM-5分子筛用NH<sub>4</sub>NO<sub>3</sub>进行交换,灼烧成氢型HZSM-5。镁改性采用浸渍法,改性后的样品记为MgHZSM-5。乙基化反应在小型积分反应器上进行。 展开更多
关键词 甲苯乙基化 分子筛催化剂 积炭
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ZSM-5分子筛催化剂酸性对积炭的影响 被引量:5
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作者 詹必增 胡锷 曾昭槐 《燃料化学学报》 EI CAS CSCD 北大核心 1992年第3期232-236,共5页
研究了几种分子筛在乙基化反应中的积炭过程,并与分子筛的酸性、孔结构等参数关联,阐明了ZSM-5分子筛催化剂的酸中心对积炭起着主要作用。酸强度越高,越容易积炭,酸量越大积炭越多。积炭的形成部位与酸中心在晶内外的分布关系密切。分... 研究了几种分子筛在乙基化反应中的积炭过程,并与分子筛的酸性、孔结构等参数关联,阐明了ZSM-5分子筛催化剂的酸中心对积炭起着主要作用。酸强度越高,越容易积炭,酸量越大积炭越多。积炭的形成部位与酸中心在晶内外的分布关系密切。分子筛外表面酸中心比晶内的更易生成积炭,体现了积炭的择形性。 展开更多
关键词 甲苯乙基化 分子筛 催化剂 ZSM-5
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复合改性对分子筛性能的影响 被引量:4
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作者 詹必增 曾昭槐 《高等学校化学学报》 SCIE EI CAS CSCD 北大核心 1991年第11期1535-1536,共2页
对ZSM-5烷基选择性的研究已有较多报道,但在提高对位选择性的同时,往往导致活性的损失,产生“反向效应”,本文试图用复合改性来探讨解决这种效应的可能性 1 实验部分 氢型分子筛加粘接剂成型(Hz),于873 K下通水蒸气处理(HZ·H_2O),... 对ZSM-5烷基选择性的研究已有较多报道,但在提高对位选择性的同时,往往导致活性的损失,产生“反向效应”,本文试图用复合改性来探讨解决这种效应的可能性 1 实验部分 氢型分子筛加粘接剂成型(Hz),于873 K下通水蒸气处理(HZ·H_2O),采用浸渍法制得P或Mg改性催化剂,改性物的含量分别为4%P_2O_5(P_1HZ)、10%P_2O_5(P_2HZ)。 展开更多
关键词 ZSM-5 分子筛 P-Mg改性 甲苯乙基化
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Effects of 2-[p-(Dimethylamino)Styrl] PyridineMethiodide on Slow Response Action Potentialand Slow lnward Current of Guinea PigPapillary Muscles
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作者 毛新民 李迪民 +2 位作者 周承明 王晓雯 张克锦 《Journal of Chinese Pharmaceutical Sciences》 CAS 1995年第1期12-16,共5页
The effects of 2-[p-(Dimethylamino)styryl] pyridine methiodide(DSPM)on slow response action potential(SRAP)and slow inward current(Isi) of guinea pig papillary muscles were studied by intracellular microelectrodes and... The effects of 2-[p-(Dimethylamino)styryl] pyridine methiodide(DSPM)on slow response action potential(SRAP)and slow inward current(Isi) of guinea pig papillary muscles were studied by intracellular microelectrodes and voltage clamp techniques.The APA and V_(max) of SRAP induced by high K ̄+were decreased after 50 min of perfusion with DSPM solu- tion. Isi was suppressed from a peak value of8.8± 1.6μA to 5.7± 1.8μA, The results indicated that DSPM has a selective blocking effect on calcium channel. 展开更多
关键词 p-(Dimethylamino)styryl] pyridine methiodide(DSPM) Verapamil Calcium chloride Papillary muscle Calcium channel Voltage clamp Action potential
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Synthesis and characterization of copolymers of poly(m-xylylene adipamide) and poly(ethylene terephthalate) oligomers by melt copolycondensation 被引量:2
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作者 Fenglei Bi Jianqiang Shao +2 位作者 Zhenhao Xi Ling Zhao Di Liu 《Chinese Journal of Chemical Engineering》 SCIE EI CAS CSCD 2016年第9期1290-1297,共8页
Poly(m-xylylene adipamide)/poly(ethylene terephthalate)(MXD6/PET) copolymers are synthesized by melt copolycondensation with 1–5 wt% low molecular weight PET oligomers into the MXD6 oligomers at 260 ℃.FR-IR an... Poly(m-xylylene adipamide)/poly(ethylene terephthalate)(MXD6/PET) copolymers are synthesized by melt copolycondensation with 1–5 wt% low molecular weight PET oligomers into the MXD6 oligomers at 260 ℃.FR-IR and1 H NMR analysis results indicate that the interchange reaction has occurred between MXD6 oligomers and PET oligomers. The thermal behavior of copolymers shows that the melting temperature of MXD6/PET copolymers decreases with the increasing of amount of PET oligomers, while the crystallization temperature accordingly increases. And the equilibrium temperature Tm0 is evaluated to be 251.8 ℃ for the copolymers with5 wt% PET oligomer adding, which is very close to that of neat MXD6. The tensile and impact strength of MXD6/PET copolymers are significantly improved than that of pure MXD6 by mechanical properties test, and the microfibril structure in the impact fracture sample's surface reveals the feature of ductile fracture. 展开更多
关键词 Polymerization Poly(m-xylylene adipamide) Poly(ethylene terephthalate) Crystallization Mechanical properties
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Synthesis, characterization of triphenyltin grafted on SBA-15mesoporous silica and its catalytic performance for the synthesis of 4-methylacetophenone
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作者 邓启刚 覃志乐 +1 位作者 杨颖 宋伟明 《Chinese Journal of Chemical Engineering》 SCIE EI CAS CSCD 2015年第2期384-388,共5页
The production of Ph3Sn–O–SBA-15(Ph3Sn SBA)was achieved by heating triphenyltin chloride and SBA-15in N-methylpyrrolidone at 190°C for 5 h using triethylamine as a catalyst.The composition,structure,and surface... The production of Ph3Sn–O–SBA-15(Ph3Sn SBA)was achieved by heating triphenyltin chloride and SBA-15in N-methylpyrrolidone at 190°C for 5 h using triethylamine as a catalyst.The composition,structure,and surface physical and chemical properties of Ph3Sn SBA were characterized using inductively coupled plasma-atomic emission spectroscopy(ICP-AES),13C,119Sn and29Si solid-state nuclear magnetic resonance(NMR)spectroscopy in situ pyridine infrared spectroscopy(Py-IR),N2adsorption–desorption isotherms,X-ray diffraction(XRD)and transmission electron microscopy(TEM).The results of ICP-AES and organic elemental analysis showed that the grafting yield of Sn was 17%(by mass)for Ph3Sn SBA.The elemental analysis and solid-state NMR results for Ph3Sn SBA were consistent with grafting of triphenyltin on SBA-15.The N2adsorption–desorption,XRD and TEM analyses showed that Ph3Sn SBA retained an ordered hexagonal mesoporous structure,resulting in decreases in the surface area,pore size and mesopore volume,and an increase in acidity as compared with SBA-15.The Hammett acidity function(H0)value and the number of acid sites for Ph3Sn SBA,obtained by the Hammett methods,were 2.77–3.30 and 2.07 mmol·g-1,respectively.The Friedel–Crafts acylation of toluene and acetic anhydride over Ph3Sn SBA was investigated.The yield of methylacetophenone(MAP)and the selectivity for 4-methylacetophenone(PMAP)were 79.56%and 97.12%,respectively,when the conditions were n(toluene):n(anhydride)=2.0:1.0 with 6%(by mass)catalyst,and heating under reflux for 5 h.The PMAP selectivity still reached 93.11%when Ph3Sn SBA was used for the fifth time under the same reaction conditions. 展开更多
关键词 SBA-15 Triphenyltin chloride Grafting reaction CATALYSIS Friedel–Crafts
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Synthesis and Crystal Structure of cis-[1,2-Bis(phenyl-thiomethyl)benzene]dichloroplatinum(Ⅱ)·0.5acetonitrile
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作者 郑艳 李建荣 +2 位作者 邹如强 陈久桐 卜显和 《Chinese Journal of Structural Chemistry》 SCIE CAS CSCD 北大核心 2003年第3期305-308,共4页
The title complex was prepared from the reaction of 1,2-bis(phenylthiomethyl)- benzene L with K2PtCl4 at room temperature and its structure has been determined by single-crystal X-ray diffraction. There exist two inde... The title complex was prepared from the reaction of 1,2-bis(phenylthiomethyl)- benzene L with K2PtCl4 at room temperature and its structure has been determined by single-crystal X-ray diffraction. There exist two independent cis-[1,2-bis(phenylthiomethyl)benzene]dichloro- platinum(Ⅱ) [PtCl2L] molecules without significant structural difference and a molecule of acetonitrile in one crystallographic asymmetric unit. Crystallographic data: triclinic, space group Pī, a = 11.010(3), b = 12.080(3), c = 16.095(4) ? = 94.728(5), = 90.129(5), = 99.274(5)? C20H18Cl2NPtS20.5CH3CN, Mr = 608.98, V = 2105(1) ?, Z = 4, Dc = 1.921 g/cm3, (Mo-K) = 7.122 mm1, F(000) = 1172, R = 0.0503 and wR = 0.0848 for 3929 observed reflections with I > 2s(I). The title complex is a neutral molecule in which the central Pt(Ⅱ) ion is four-coordinated with two S-donors of the ligand and two Cl anions, forming a distorted square planar geometry. In the crystal, there exist two kinds of molecular packing patterns. One [PtCl2L] molecule is connected to the other one through the weak interactions of Pt…Pt, Pt…S and Pt…Cl, forming a supramolecular quasi-dimer. The other one complex molecule is connected with the CH3CN molecule by weak Cl…N interaction. 展开更多
关键词 synthesis crystal structure 1 2-bis(phenylthiomethyl)benzene platinum complex
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FLUORESCENCE STUDIES ON MORPHOLOGICAL CHANGE OF ST/DVB CROSSLINKED GELS DURING CHLOROMETHYLATION
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作者 ZHANG Jixiang LI Hexian +3 位作者 WANG Guochang WANG Lin WANG Ying HE Binglin 《Chinese Journal of Reactive Polymers》 2002年第2期185-191,共7页
The morphological change of St/DVB crosslinked gels during chloromethylation wasstudied by fluorescence spectroscopy using St/DVB crosslinked and hypercrosslinked gels as controlsamples. It has been found that with in... The morphological change of St/DVB crosslinked gels during chloromethylation wasstudied by fluorescence spectroscopy using St/DVB crosslinked and hypercrosslinked gels as controlsamples. It has been found that with increase of chlorine content, the excimer emission band (~325nm)approaches to vanish, while the intensity of multi-ring aggregate emission band (~420nm) quicklyreaches a maximum, and then decreases sharply accompanied by appearance ofa new broad bandcentred at ca 488nm which roughly coincides with the typical emission band of hypercrossllinkedSt/DVB gels. Mearwhile, the result of IR measurement suggests that methylene bridge between phenylrings forms and increases with chloromethylation process. These results are explained in terms ofaside reaction of post-crosslinking, which densifies the loosely crosslinked networks and undoes thedensely entangled microgel nuclei. As a result, the morphology of the crosslinked gels becom es morehomogeneous with chloromethylation. 展开更多
关键词 Crosslinked Polystyrene CHLOROMETHYLATION Fluorescence Spectroscopy Hypercrosslinked Gels
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Synthesis and characterization of 2-hydroxy-N-methyl-N-phenyl-acetamide
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作者 周忠诚 舒万艮 《Journal of Central South University of Technology》 2002年第1期25-29,共5页
2-hydroxy N methyl N phenyl acetamide was synthesized by using N methylaniline, chloracetyl chloride, anhydrous sodium acetate and methanol through the acetylation, esterfication and ester interchange steps. The acety... 2-hydroxy N methyl N phenyl acetamide was synthesized by using N methylaniline, chloracetyl chloride, anhydrous sodium acetate and methanol through the acetylation, esterfication and ester interchange steps. The acetylation of N methylaniline with chloracetyl chloride, catalyzed by triethylamide with mole ratio n (C 6H 5NHCH 3)∶ n (ClCH 2C(O)Cl)∶ n (N(C 2H 5) 3)=1∶1.05∶1, the yield of 2 chloro N methyl N phenyl acetamide(Ⅰ) was 93.8%; Then the esterification of Ⅰ with anhydrous sodium acetate in the presence of phase transfer catalyst tetrabutyl ammonia bromide gave 97.3% yield of 2 acetoxyl N methyl N phenyl acetamide (Ⅱ); The ester interchange of with methanol catalyzed by potassium hydroxide gave 2 hydroxy N methyl N phenyl acetamide (Ⅲ) in 96.4% yield. And the total yield was 88.0%. IR and MS spectroscopy of products were analyzed and their characteristic peaks were assigned. Combining the results of elemental analysis, the molecular structure of Ⅰ, Ⅱ and Ⅲ was identified. 展开更多
关键词 -N-methyl N phenyl acetamide synthesis ACETYLATION esterfication ester interchange characterization
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