HY沸石上2，6—二叔丁工萘的择形合成

研究了脱铝HY沸石（n(Si)/n(Al)=3.8）上萘（naph）的选择性叔丁基化反应。结果表明，八面沸石对该反应过程有较好的择形催化作用，两种异构化产物（2，6－二叔丁基萘和2，7－二叔丁基萘)之间存在着热力学平衡，即两种异构化产物可在酸性中心上相互转化，在以叔丁醇为烷基化试剂，WHSV＝2h^-1，n(t-BuOH)/n(naph）＝3，反应温度为120℃的反应条件下，萘的转化率可达98．43％，β－位选择性可高达100％，二叔丁基萘收率可达74．34％，2，6－二叔丁基萘／2，7－二叔丁基萘/2,7-叔丁基萘质量比为6．24。     

沸石分子筛催化剂上萘的择形异丙基化反应性能

 研究了HY,Hβ,HM和HZSM－5沸石分子筛对萘择形异丙基化反应的催化性能．结果发现,这些沸石分子筛的活性顺序为HY＞Hβ＞HM＞HZSM－5,对2,6－二异丙基萘的选择性顺序为HM＞Hβ＞HY．除沸石分子筛的酸量与酸分布外,其孔道结构与大小是影响萘异丙基化反应的主要因素．脱铝能选择性地降低沸石外表面的酸性,且对沸石的催化性能有较大影响．常压水蒸气脱铝结合强酸再处理有利于催化剂催化性能的提高．提高反应温度有利于萘的转化,但温度过高会引发许多副反应,适宜的反应温度约为523K．反应时间对产物分布的影响不明显．异丙醇／萘摩尔比应小于2．     

化学液相沉积法改性HY沸石及其对萘与叔丁醇择形烷基化反应的催化性能

采用化学液相沉积法,经异丁基三乙氧基硅烷修饰并用高温水蒸气处理得到了改性HY沸石.采用X射线衍射、低温N2吸附和脉冲式质量分析技术研究了改性样品骨架结构、比表面积、孔结构参数和吸附性质的变化,并考察了HY沸石及其改性后样品对萘与叔丁醇烷基化制备2,6-二叔丁基萘(2,6-DTBN)反应的催化性能.结果表明,改性后HY沸石的骨架结构基本不变,但比表面积增大,平均孔径缩小,孔口尺寸得到了一定调变.在改性后HY沸石催化剂上萘与叔丁醇烷基化反应活性下降,但催化剂择形性能明显提高,其2,6-DTBN/2,7-DTBN比可以达到6.62。     

萘与不同烷基化试剂在一些沸石上的烷基化反应

萘与不同烷基化试剂在沸石上的烷基化反应栗同林刘希尧朴玉玲蔡春飞（北京燕山石化公司研究院，北京１０２５４９）王祥生（大连理工大学化工学院，大连１１６０１２）关键词萘，甲醇，乙醇，异丙醇，叔丁醇，烷基化，沸石催化剂分类号Ｏ６４３单环芳烃的选择性烷基化尤其...     

甲胺在择形分子筛催化剂上的选择性合成

考察了同晶置换改性丝光沸石和金属表面活性改性ＨＺＳＭ－５对甲醇胺化反应的催化性能，发现两种改性方法都可以降低三甲胺（ＴＭＡ）选择性，提高一甲胺（ＭＭＡ）与二甲胺（ＤＭＡ）的选择性，两种方法都是通过分子筛外表面改性以实现择形性调变的，同晶置换改性可使丝光沸石的强酸性发生显著变化，而强Ｂ酸中心是丝光沸石催化胺化反应的活性中心。     

萘与丙烯在脱铝丝光沸石上的烷基化反应

Shape selective alkylation of polynuclear aromatics has begun to receive increasing attention. 2,6 dialkylnaphthalenes are important raw materials for manufacturing high quality polyester fibers and plastics. Understanding of the reaction and the catalysis for conversion of polycyclic aromatic hydrocarbons is needed both from fundamental and practical view points. In this paper, alkylation of naphthalene with propene over a series of dealuminated mordenite with different Si/Al ratios was carried out in an autoclave with an electromagnetical stirrer. Textural property of the dealuminated mordenite was determined by nitrogen adsorption. The amount of the acid sites was measured by NH 3 TPD. The catalytic activity of HM and β shape selectivity for products increased with increasing the Si/Al ratio in HM. Moreover, the selectivity for alkylation with propene was also increased by dealumination treatment. The increase of the catalytic activity was attributed to the formation of mesopores, which significantly promoted the diffusion of reactants and products in mordenite. It was suggested that the increase of β selectivity resulted from the elimination of acid sites from the external surface, and the selectivity for alkylation with propene was improved owing to the creation of the interconnection between 12 ring and 8 rimg channels by dealumination.     

煤焦油萘择形异丙基化产物组成的气相色谱/质谱分析

 采用毛细管气相色谱 /质谱 (CGC/MS)联用技术 ,经计算机质谱库检索并结合人工谱图解析 ,研究了在不同沸石分子筛催化剂上煤焦油萘择形异丙基化产物的组成。研究结果表明 ,煤焦油萘异丙基化产物主要由一取代萘、二取代萘以及少量三取代萘组成 ;除 HZSM-5活性较低以外 ,其它催化剂均有较高的反应活性 ,其中 HY和 Hβ反应活性最高 ,萘转化率分别达 75 .1 5 %和 5 5 .96% ,但β位产物的选择性较差 ;ZM类催化剂既有一定的活性 ,又有较高的β选择性 ,是萘择形异丙基化反应理想的备选催化剂。     

Hβ-沸石的氧化物改性对由β-甲基萘选择性合成2,6-二甲基萘反应的影响

Ｈβ－沸石的氧化物改性对由β－甲基萘选择性合成２，６－二甲基萘反应的影响栗同林刘希尧１）（北京燕山石化公司研究院北京１０２５４９）王祥生（大连理工大学工业催化研究所大连１１６０１２）关键词β－甲基萘β沸石氧化物改性歧化烷基化分类号Ｏ６４３．３２在Ｃ－...     

Beta沸石上合成对叔丁基苯酚和2,4—二叔丁基苯酚

首次在三相条件下,在Ｂｅｔａ沸石催化剂上研究了苯酚与异丁烯烷基化合成对叔丁基苯酚和２,４－二叔丁基苯酚。通过对Ｈｂｅｔａ沸石高温焙烧和吡啶中毒试验研究了烷基化反应活性和选择性的变化规律;用ＮＨ３－ＴＰＤ和Ｐｙ－ＩＲ测定了试样的酸量和酸种类,结果表明Ｈｂｅｔａ沸石具有很好的烷基化活性,苯酚的转化率可达９２％,经１１２３Ｋ焙烧后苯酚转化率为８８％,对叔丁基苯酚和２,４－二叔丁基苯酚的选择性分别为７０～７５％和１４～２０％,中等强度的Ｂｒｎｓｔｅｄ酸是苯酚与异丁烯烷基化反应的活性中心。粘合剂含量低于３０％对烷基化活性基本无影响     

HY分子筛催化1,3-苯并二噁茂烷类化合物合成的研究

研究了HY分子筛催化邻苯二酚与环己酮、丁酮、丙酮、丙醛、丁醛、异丁醛、戊醛、异戊醛、正己醛、正辛醛、苯甲醛、二苯甲酮等十余种醛(酮)的缩合反应。考察了反应时间、酚与醛(酮)的配比、HY分子筛用量等因素对酚与醛(酮)反应的影响。实验发现,当邻苯二酚与醛(酮)摩尔比为1∶1.0、催化剂用量为每mol邻苯二酚2.5g、反应4h,选择性一般在97%以上,醛(酮)的转化率一般在57%以上,表明HY分子筛对邻苯二酚与醛(酮)的反应有较好的催化性能。     

HY分子筛催化1,3-苯并二(噁)茂烷类化合物合成的研究

研究了HY分子筛催化邻苯二酚与环己酮、丁酮、丙酮、丙醛、丁醛、异丁醛、戊醛、异戊醛、正己醛、正辛醛、苯甲醛、二苯甲酮等十余种醛（酮）的缩合反应.考察了反应时间、酚与醛（酮）的配比、HY分子筛用量等因素对酚与醛（酮）反应的影响.实验发现,当邻苯二酚与醛（酮）摩尔比为1：1.0、催化剂用量为每mol邻苯二酚2.5g、反应4h,选择性一般在97%以上,醛（酮）的转化率一般在57%以上,表明HY分子筛对邻苯二酚与醛（酮）的反应有较好的催化性能.     

甲醇及合成气制二甲醚中不同粒径的 HY 分子筛及复合 Cu-Mn-Zn/HY 催化剂

 通过改变导向剂的老化时间, 制备了一系列不同粒径的 HY 分子筛作为脱水催化剂, 考察了甲醇脱水反应性能; 将其与铜基甲醇合成活性组分 Cu-Zn-Mn 组成双功能催化剂, 考察了催化剂对合成气直接制二甲醚反应的催化性能. 结果表明, 粒径为 820 nm 的 HY 分子筛在甲醇脱水中表现出较高的催化活性; 以其作为脱水组分的双功能 Cu-Zn-Mn/HY 催化剂也表现出较高的催化活性和良好的稳定性.     

1,4-二(2-萘基)的环乙烷的合成及顺, 反异构体的结构鉴定

Hassel和Barton成功地研究了环己烷的构象变化,为研究单糖、多糖以及甾体等天然化合物的结构和性质奠定了基础。近年来的研究表明,含环己烷环的液晶化合物中六员环的构型直接影响液晶的性质。例如,反式1-烷基-4-(对-氰基)苯基环已烷可以形成液晶,而顺式异构体分子不能有序排列。De Schryver     

改性纳米HZSM-5催化剂上甲苯与甲醇的烷基化反应

以Si,P,Mg复合改性的纳米HZSM-5为催化剂,进行了甲苯与甲醇的烷基化反应;并采用X射线衍射,NH3程序升温脱附,红外和低温N2吸附等方法研究了改性前后催化剂酸性质和孔结构的变化.在小型固定床反应器上,考察了载气量、反应温度和重时空速等反应条件对烷基化反应性能的影响.在2h-1,460℃,甲苯/甲醇比,水/烃比和...     

合成甲基叔丁基醚的分子筛催化剂研究

通过对ＨＺＳＭ－５,ＨＺＲＰ－１和Ｈβ三种类型分子筛催化剂上合成甲基叔丁基醚的活性测定和结构表征,初步考察了分子筛孔结构对催化活性的影响。在此基础上,对适宜孔结构的分子筛进行了水热改性,考察了改性条件对分子筛催化剂的性质及其合成甲基叔丁基醚反应催化活性的影响,得到了催化活性较好的分子筛催化剂。     

Synthesis and properties of aromatic polyamides derived from 2,6-bis(4-aminophenoxy)naphthalene and various aromatic dicarboxylic acids

2,6-Bis(4-aminophenoxy)naphthalene (2,6-BAPON) was synthesized in two steps from the condensation of 2,6-dihydroxynaphthalene with p-chloronitrobenzene in the presence of potassium carbonate, giving 2,6-bis(4-nitrophenoxy)naphthalene, followed by hydrazine hydrate/Pd—C reduction. A series of new polyamides were synthesized by the direct polycondensation of 2,6-BAPON with various aromatic dicarboxylic acids in the N-methyl-2-pyrrolidone (NMP) solution containing dissolved metal salts such as CaCl₂ or LiCl using triphenyl phosphite and pyridine as condensing agents. The polymers were obtained in quantitative yields with inherent viscosities of 0.62–2.50 dL/g. Most of the polymers were soluble in aprotic dipolar solvents such as N,N-dimethylacetamide (DMAc) and NMP, and they could be solution cast into transparent, flexible, and tough films. The casting films had yield strengths of 84–105 MPa, tensile strengths of 68–95 MPa, elongations at break of 8–36%, and tensile moduli of 1.4–2.1 GPa. The glass transition temperatures of the polyamides were in the range 155–225°C, and their 10% weight loss temperatures were above 505°C in nitrogen and above 474°C in air. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2147–2156, 1997     

Synthesis and properties of poly(ether imide)s derived from 2,6-bis(3,4-dicarboxyphenoxy)naphthalene dianhydride and aromatic diamines

A new naphthalene unit-containing bis(ether anhydride), 2,6-bis(3,4-dicarboxyphenoxy)naphthalene dianhydride, was synthesized in three steps starting from the nucleophilic nitrodisplacement reaction of 2,6-dihydroxynaphthalene and 4-nitrophthalonitrile in N,N-dimethylformamide (DMF) solution in the presence of potassium carbonate, followed by alkaline hydrolysis of the intermediate bis(ether dinitrile) and subsequent dehydration of the resulting bis(ether diacid). High-molar-mass aromatic poly(ether imide)s were prepared using a conventional two-step polymerization process from the bis(ether anhydride) and various aromatic diamines. The intermediate poly(ether amic acid)s had inherent viscosities of 0.65–2.03 dL/g. The films of poly(ether imide)s derived from two rigid diamines, i.e. p-phenylenediamine and benzidine, crystallized during the thermal imidization process. The other poly(ether imide)s belonged to amorphous materials and could be fabricated into transparent, flexible, and tough films. These aromatic poly(ether imide) films had yield strengths of 104–131 MPa, tensile strengths of 102–153 MPa, elongation to break of 8–87%, and initial moduli of 1.6–3.2 GPa. The glass transition temperatures (T_g's) of poly(ether imide)s were recorded in the range of 220–277°C depending on the nature of the diamine moiety. All polymers were stable up to 500°C, with 10% weight loss being recorded above 550°C in both air and nitrogen atmospheres. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1657–1665, 1998