尖晶石型衍生的Ni/Al2O3催化剂低温催化顺酐加氢合成丁二酸酐

开发高活性的顺酐加氢制丁二酸酐和γ-丁内酯催化剂具有重要的工业意义.顺酐加氢多采用Cu基和Ni基催化剂,但一般Cu基和Ni基催化剂存在反应温度高(170–260℃)和稳定性差等缺点,很有必要开发高活性的顺酐加氢催化剂.我们以拟薄水铝石作为Al2O3载体的前驱体,采用浸渍法制备了一系列镍铝尖晶石型衍生的不同Ni含量的Ni/Al2O3催化剂,并研究了它们在顺酐加氢反应中的催化性能.还原前Ni/Al2O3催化剂的X射线衍射结果表明,催化剂含有NiAl2O4物种.氮吸附结果显示,不同Ni含量的催化剂均具有介孔结构.氢-程序升温还原研究发现,Ni/Al2O3催化剂经750℃还原2 h后,其表面上NiAl2O4物种能被高效还原.X射线粉末衍射结果表明,750℃还原的Ni/Al2O3催化剂中金属Ni颗粒尺寸随着Ni负载量升高而增大.利用一氧化碳-程序升温脱附对750℃还原的Ni/Al2O3催化剂进行研究,发现750℃还原的催化剂上金属Ni物种含量从高到低依次为:Ni(7.5%)/Al2O3>Ni(5%)/Al2O3>Ni(2.5%)/Al2O3.采用CO化学吸附获得的Ni(2.5%)/Al2O3,Ni(5%)/Al2O3和Ni(7.5%)/Al2O3催化剂上金属Ni颗粒尺度分别为8.0,12.8和15.7 nm.活性研究结果表明,750℃还原的Ni(5%)/Al2O3催化剂具有最高的催化活性,这可能是由于Ni(5%)/Al2O3催化剂具有较多的Ni活性位点和较合适的Ni颗粒粒度所致.进一步研究发现,在650–750℃还原温度下,Ni(5%)/Al2O3催化剂的还原度随着还原温度的升高而升高,Ni分散度随着还原温度的升高而降低.活性结果研究表明,700℃还原的Ni(5%)/Al2O3催化剂具有较多的Ni活性位点和较合适的Ni颗粒粒度,具有最高的加氢催化活性,其在120℃,H2压力为0.5 MPa和质量空速为2 h?1的反应条件下,能获得近100%的顺酐转化率和90%的丁二酸酐选择性,同时该催化剂具有优良的稳定性.以上结果表明,尖晶石型衍生的Ni/Al2O3催化剂是一个十分有应用前景的顺酐加氢催化剂.     

助剂对可生物降解聚碳酸亚丙酯/聚丙烯非织造布切片性能的影响

采用熔融共混法研究助剂马来酸酐(MAH)、马来酸酐接枝聚丙烯(PP-2)对可生物降解聚碳酸亚丙酯(PPC)/聚丙烯(PP)非织造布切片结构与性能的影响.红外谱图表明MAH和PP-2的酸酐官能团与PPC发生了开环反应.MAH、PP-2可显著提高切片的拉伸强度,当MAH,PP-2用量为1%和2%时,切片拉伸强度较不添加助剂时分别提高了116%和101%.MAH,PP-2的加入降低了切片的熔体流动速率,提高了特性黏数,同时提高了切片的玻璃化转变温度(Tg)和热分解温度,扩大了切片的使用和加工温度范围.当MAH用量为1%时,切片Tg提高了4℃.当MAH,PP-2用量为1%和2%时,切片5%热分解温度分别提高了44℃和20℃.加入MAH、PP-2的切片断面的微观形貌图显示切片内部凹陷和空洞较少,较为平整,PP-2改善切片相容性的效果优于MAH.PPC和PP置于磷酸缓冲液中30天的降解率分别为4.30%和0%,说明PP在磷酸缓冲液中几乎不降解.加了助剂的切片30天的降解率在3.80%以上,说明制备的PPC/PP非织造布切片是可降解的,对环境友好.开环反应、增加切片界面黏附力、降低界面张力等可能是助剂提高切片性能的作用机理.     

TiOx(x＜2)表面修饰Ni/TiO2-SiO2催化顺酐液相选择加氢合成γ-丁内酯

以TiO2-SiO2复合氧化物气凝胶为载体,制备了一系列Ni/TiO2-SiO2催化剂,并采用N2物理吸附-脱附、H2程序升温还原/脱附、X射线衍射及原位漫反射傅里叶变换红外光谱等技术对催化剂进行了表征,考察了载体中钛含量对催化剂结构、表面性质及其催化顺酐液相选择加氢合成γ-丁内酯反应性能的影响.结果表明,较小的Ni0...     

酸酐固化环氧树脂/蒙脱土复合材料的等温固化动力学

用等温差示扫描量热法(DSC)研究了酸酐固化环氧树脂/蒙脱土复合材料的等温固化过程，考察了未处理的蒙脱土(MMT)和有机蒙脱土(OMMT)对环氧树脂固化动力学的影响. 实验表明， 环氧树脂的固化过程包含自催化机理，加入蒙脱土没有改变固化反应机理. 用Kamal方程对该体系的固化过程进行拟合，得到反应级数m、n，反应速率常数k1、k2，总反应级数(m + n)在2.4～3.0之间. MMT的加入使环氧树脂体系的k1、k2有所降低，而OMMT的加入对体系的k1、k2影响较为复杂，加入蒙脱土对环氧树脂固化体系的活化能影响较小.     

An efficient and facile one-pot synthesis of cyanohydrin esters from carbonyl compounds catalyzed by iron(III) chloride

A variety of cyanohydrin esters were readily prepared from carbonyl compounds with trimethylsilyl cyanide and acid anhydride under the influence of a catalytic amount of iron(III) chloride in a convenient one-pot procedure.     

聚丙烯—马来酸酐接枝共聚物的固态NMR谱研究

马来酸酐接枝聚丙烯的方法曾有过研究,但主要是熔融法和溶液法,反应温度在160℃以上,得到PP—g—MA共聚物。Russeli等曾对马来酸酐接枝二十烷烃作模型化合物进行过研究,~(13)C—NMR谱的结果表明在正二十烷烃主链上形成的主要为单马来酸环支链,未发现形成长链的马来酸酐均聚物,其原因为反应温度已超过马来酸酐聚合的最高温度(150℃)。     

Catalytic Polymerization of Methyl-phenyldisilazanes and Alkylphenyl-N-phenylaminosilanes

The reaction of polymerization of methylphenyldisilazanes and alkyl-phenyl-N-phenylaminosilanes under the action of alkalis at high temperature was studied. It was demonstrated that polymerization of the above compounds is accompanied by the evolution of benzene as a result of splitting off of phenyl groups from silicon atoms and of hydrogens from nitrogen atoms. When hydrogen atoms bound with nitrogen were exhausted, in the case of polymerization of symmetrical tetramethylphenyl-and dimethyl-tetraphenyldisilazanes, 1,1,3-trimethyl-1,3,3-triphenyldisilazane, and methyldiphenylphenylaminosilane, the reaction was kept going by the interaction of phenyls with the protons of the methyl groups. Polymers of a complex structure were obtained as a result.     

Green Synthesis of New Boron-Containing Quinazolines: Preparation of Benzo[d][1,3,2]diazaborinin-4(1H)-one Derivatives

A series of new boron-containing quinazolinones, benzo[d][1,3,2]diazaborinin-4(1H)-one derivatives, were synthesized by the sequential one-pot reaction of isatoic anhydride, amines, and arylboronic acids in the absence of a catalyst and solvent. Heating isotoic anhydride and amines led to the formation of 2-aminobenzamide intermediates, which reacted easily with boronic acids to obtain the title compounds in good yields. Solvent-free conditions provided a unique procedure because the corresponding products were not obtained using various solvents either under reflux conditions or at room temperature.

[Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications® for the following free supplemental resource: Full experimental and spectral details.]     

On the use of succinic anhydride as acylating agent for practical resolution of aryl-alkyl alcohols through lipase-catalyzed acylation

A comparison is carried out of the E-values recorded in the lipase-catalyzed resolution of a series of secondary aryl-alkyl alcohols with enol esters versus succinic anhydride. Whereas all the substrates could be resolved by a proper choice of the lipase/enol ester couple with moderate (E=50) to good (E>100) enantioselectivities, only some of them showed satisfactory enantioselectivity (E>50) with the use of succinic acid as acylating agent. Notably, indanol and 1-quinolin-3-yl-ethanol were resolved in a practical way, with E>100 and E>80, respectively.     

钯催化的酸酐C-O键的活化及反应

综述了钯催化的酸酐碳—氧键的活化和反应 ,及由羧酸直接制备相应的醛、酮且不需要卤原子和碱参与的方法