N—乙酰基己内酰胺的合成研究

概述了Ｎ－乙酰基己内酰胺的应用和合成工艺。详细研究了己内酰胺和乙酸酐反应的各种影响因素,通过正交实验得到了合成Ｎ－乙酰基己内酰胺的最佳工艺条件为：乙酸酐：己内酰胺＝１．２：１,反应时间２ｈ,产率达８７％。     

1—（4—烷氧基）烷基己内酰胺的合成

１－（４－正庚氧基）丁基己内酰胺１可由正庚醇与１，４－二卤代丁烷反应后，再与己内酰胺反应制得。每步均在混合无机碱ＫＯＨ／Ｋ２ＣＯ３（作为碱性试剂）和季铵盐（作为固－液相转移催化剂）存在下进行反应。     

皮肤给药助渗剂氮酮的合成研究

介绍了皮肤给药用助渗剂———氮酮的合成工艺过程,并对合成工艺参数进行了研究。结果表明,在溴十二烷∶己内酰胺∶甲醇钠＝１∶１．０５∶１．４７（ｍｏｌ）、溴十二烷∶６号溶剂油∶ＰＥＧ６０００＝１∶０．６∶０．０３（ｍ）、搅拌速度５０ｒ／ｍｉｎ下反应５５ｈ,得到的产品含量达９８３％,收率８４５％。     

金属减活剂N,N′—二乙酰基己二酰二肼的合成及应用

研究了由己二酸二乙酯与水合肼反应合成己二酰二肼，再用乙酸酐酰化己二酰二肼得到金属减活剂Ｎ，Ｎ′－二乙酰基己二酰二肼的工艺条件，并测试了其应用性能。     

1－（4－烷氧基）烷基己内酰胺的合成

１－（４－正庚氧基）丁基己内酰胺１可由正庚醇与１，４－二卤代丁烷反应后，再与己内酰胺反应制得。每步均在混合无机碱ＫＯＨ／Ｋ２ＣＯ３（作为碱性试剂）和季铵盐（作为固－液相转移催化剂）存在下进行反应。     

N-(p-溴苯基)-2-(p-氯苯氧乙酰基)氨基脲的合成与表征

用 Ｎ － （ｐ － 溴苯基） 三氯乙酰胺与ｐ － 氯苯氧乙酰肼反应,合成了一种新的取代氨基脲, Ｎ － （ ｐ － 溴苯基） － ２ － （ ｐ － 氯苯氧乙酰基） 氨基脲,其结构经 Ｉ Ｒ 、１ Ｈ Ｎ Ｍ Ｒ 和元素分析证实。     

3-乙酰基吡咯的合成

用吡咯和对甲苯磺酰氯在钾的催化作用下合成１－对甲苯磺酰基吡咯（Ⅰ）,用Ⅰ与乙酸酐在ＡｌＣｌ３催化下进行傅－克酰化反应合成了１－对甲苯磺酰基－３－乙酰基吡咯（Ⅱ）,将Ⅱ碱式水解可得到３－乙酰基吡咯。用ＦＴ－ＩＲ和＾１ＨＮＭＲ对产物的结构进行了表征。     

N（—p—溴苯基）—2—（p—氨苯氧乙酰基）氨基脲的合成与表征

用Ｎ－（ｐ－溴苯基）三氯乙酰胺与ｐ－氯苯氧乙酰肼反应,合成了一种新的取代氨基脲,Ｎ－（ｐ－溴苯基）－２－（ｐ－氯苯氧乙酰基）氨基脲,其结构经ＩＲ、＾１ＨＮＭＲ和元素分析证实。     

壬基酚聚氧乙烯（4）醚磺基琥珀酸单酯二钠盐的合成与性能研究

考察了壬基酚聚氧乙烯（４） 醚磺基琥珀酸单酯二钠盐的合成工艺条件,并测定其表面化学性能。最佳合成工艺条件：ｎ（ 酚醚）∶ｎ（ 顺酐） ＝ １∶１ ．０５ ,酯化温度１２０ ℃,酯化时间４．０ ｈ ,ｎ（ 顺酐）∶ｎ（ 亚硫酸钠） ＝ １∶１．０５ ,磺化温度８０ ℃,时间２ ．０ ｈ;整个反应在氮气保护下进行,终产物得率＞ ９６ ％ 。产物主要表面化学性能：临界表面张力２ ．９５×１０ － ２ Ｎ·ｍ －１ ,临界胶束浓度７ ．９４ ×１０－ ４ ｍｏｌ·Ｌ－ １ ,钙皂分散力ＬＳＤＰ为３２ ％ ,乳化性能２ ．４８ ｍｉｎ ,去污力９０ｓ。     

N－乙酰基二茂铁吡啶季铵盐的合成

Ｎ－乙酰基二茂铁吡啶季铵盐的合成王仁章，吴士杰（四平师范学院化学系，四平１３６０００）Ｎ－烷基吡啶季铵盐是重要的亲核试剂［１］。我们以一种简便方法合成了Ｎ－乙酰基二茂铁吡啶季铵盐，并研究了它的某些物理性质。在Ｎ－乙酰基二茂铁吡啶季铵盐中，Ｎ原子带正电...     

Adiabatic anionic polymerization of caprolactam in the presence of N-acylated caprolactam macroactivator: Kinetic study

In this study, bis ?-caprolactam bis-diphenyl methane diisocyanate polypropylene glycol 1000 used as the macroactivator was prepared and well characterized prior to use. The anionic polymerization of ?-caprolactam with the macroactivator as a function of the macroactivator concentration was adiabatically carried out. The adiabatic temperature rise method as well as the macrokinetics were used for elucidation of the kinetics of the polymerization. A nonlinear regression technique was used for determining the parameters of the macrokinetic equation. The equilibrium conversion and equilibrium time obtained were 94–96% and 2–9 min depending on the macroactivator concentration. The effects of the concentrations of macroactivator and ?-caprolactam on the initial rate, apparent overall reaction rate, and the empirical parameters were studied. A side reaction induced by the transfer of the proton in the isocyanurate group of the macroactivator to caprolactam anion was found. According to this finding, a new reaction kinetic model was proposed by properly modifying the macrokinetic equation. © 1993 John Wiley & Sons, Inc.     

A Novel Route to One-step Formation of ɛ-caprolactam from Cyclohexane and Nitrosyl Sulfuric Acid Catalyzed by VPO Composites

A series of VPO composites were employed to catalyze the reaction of cyclohexane with nitrosyl sulfuric acid in the presence of fuming sulfuric acid. To our delight, ɛ-caprolactam was for the first time directly obtained through such one-step catalytic process. VPO composite catalysts were proven to be efficient for the reaction, especially, the transition metals introduced to Al–VPO composite catalysts could improve the reactions selectivity to some extent. Among them, the Mn–Al-VPO composite catalyst gave the best results with 11.65% of conversion and 34.70% of selectivity to ɛ-caprolactam. While the conversion and selectivity are too low at this time to be commercially viable, this discovery establishes a potential new single step process for making ɛ-caprolactam from cyclohexane. A reaction mechanism is proposed.     

Polymerization of lactams, 38. Copolymerization of 6-caprolactam with some of its non-homopolymerizing derivatives

It was demonstrated that non-homopolymerizing derivatives of 6-caprolactam: 7-cyclohexyl-1-aza-2-cycloheptanone (I) and 7-isopropyl-5-methyl-1-aza-2-cycloheptanone (II) were polymerizing with 6-caprolactam under conditions of the socalled hydrolytic polymerization. With its increasing content in the initial reaction mixture the copolymerization rate, the equilibrium content of the copolymer, and the reduced viscosity decreased. Lactam (I) was a more reactive comonomer in comparison with lactam (II).     

On the synthesis of poly(ε-caprolactam)—poly(butadiene-co-acrylonitrile) block copolymers for the reaction injection molding process

The liquid rubbers Hycar ATBN and HTBN were used in the preparation of poly(ε-caprolactam)—poly(butadiene-co-acrylonitrile) block copolymers intended for reaction injection molding by the anionic polymerization of ε-caprolactam. The conversion of Hycar end groups to polymerization growth centers and the conditions of polymerization influence the crystallization, morphology, and mechanical properties of the product through its molecular structure. The contribution of individual reactions to this molecular structure is discussed.     

Die polymerisation der lactame VI. Die copolymerisation von 6-caprolactam und 8-capryllactam

The process of incorporating 6-caprolactam and 8-capryllactam into polymer chains was studied during the hydrolytic, cationic, and anionic copolymerization in the case of equimolar ratio of the above mentioned monomers. At the beginning of the hydrolytic copolymerization at temperatures between 200 and 260°C, 6-caprolactam was more rapidly incorporated into the chains. Decreasing temperature led to a decrease in the total rate of polymerization with increasing difference between rates of incorporating the two components. Contrary to this, at the initial stage of the cationic copolymerization, the incorporation of 8-capryllactam was faster by orders of magnitude than that of 6-caprolactam, the changes of the copolymer composition being independent of temperature. Under the conditions of interest, in the course of the anionic copolymerization the two monomers were characterized with the same rates of incorporation into the polymer chains. Different melting points of products separated at various stages of the copolymerization process corresponded to the above mentioned differences in rates of incorporating individual monomers into polymer chains when different reaction mechanisms were employed.     

Die polymerisation der lactame XIV. Einfluß des hexamethylguanidiniumchlorides auf die aktivierte anionische polymerisation der lactame

It was proved that hexamethylguanidiniumchloride (HMGC) exhibited a pronounced accelerating effect on the activated anionic polymerization of 2-pyrrolidone (40°C) and 6-caprolactam initiated by alkali metal salts of the corresponding lactams. The accelerating effect of HMGC was not specific for a certain type of alkali metal salt of lactams as initiator, it was proved that the effect is operative for polymerization of 6-caprolactam when using sodium or cesium salt of 6-caprolactam. It was proved that HMGC does not form growing centers under reaction conditions studied. The initial polymerization rate in the homogeneous phase is a linear function of square root of HMGC concentration at constant concentrations of initiator and activator. On the basis of this finding it was possible to suggest a plausible mechanism of HMGC influence on the polymerization process.     

Vapor phase reaction of cyclohexanone oxime over boria modified HSZM-5 zeolites

The vapor phase Beckmann rearrangement of cyclohexanone oxime has been carried out over zeolites and boria modified HZSM-5 zeolites to elucidate the effects of acidity and acid strength distribution on the conversion and ε-caprolactam selectivity. Although ε-caprolactam selectivity was increased with the SiO₂Al²O³ ratio in a HZSM-5 zeolite, the highest selectivity in the study was accomplished over a boria modified HZSM-5. The selectivity was dependent on the ratio of weak acid sites to strong acid sites. The boria played an important role in controlling the acid strength distribution of the zeolites. It was found that the production of a polymer over strong acid sites caused a decrease in ε-caprolactam selectivity during the reaction.     

Study the liquid-phase Beckmann rearrangement on the surface of SBA-15-SO<Subscript>3</Subscript>H catalyst

Hybrid inorganic–organic solid acid material SBA-15-Ph–SO₃H was synthesized by the co-condensation of tetraethoxysilane and 2-(4-chlorosulfonylphenyl) ethyltrimethoxysilane in the presence of a Poly (alkylene oxide) block copolymer under acid conditions. The catalytic activity of the obtained materials was studied in liquid-phase Beckmann rearrangement of cyclohexanone oxime to ε-caprolactam. The results show that there exists an obvious “Solvent effect” in this reaction system and the strong Bronsted acid is proofed again to be at the origin of the formation of ε-caprolactam. Moreover, we tentatively proposed a reaction mechanism involving a five-member ring intermediate product when toluene was used as solvent.     

Polymerization of lactams, 49. Hydrolytic polymerization of 6-caprolactam in the presence of its cyclic dimer

The hydrolytic polymerization of 6-caprolactam has been studied at 260–280°C in the presence of 5, 10 and 15 mol-% of cyclic dimer of 6-caprolactam and 2 mol-% of 6-aminocaproic acid as an initiator. The content of monomer and cyclic oligomers, including pentamer, was determined by HPLC. It has been proved that the rate of polymerization decreases with increasing content of cyclic dimer in the initial mixture and the time required to attain the equilibrium content of polymer increases as much as by an order of magnitude. The cyclic dimer is incorporated into the polymer above all in the final reaction stage.     

The kinetics of hydrolytic polymerization of ε-caprolactam. II. Determination of the kinetic and thermodynamic constants by least-squares curve fitting

The kinetic and thermodynamic constants of the hydrolytic polymerization of ?-caprolactam were determined by least-squares curve fitting. The calculations were carried out using observed kinetic data such as concentration of ?-caprolactam ([CL]), endgroup ([EG]), and ?-aminocaproic acid ([ACA]) and time derivatives of each concentration (rates) ?[CL]/?t, ?[EG]/?t, and ?[ACA]/?t. The sets of the converged constants are obtained for the initial water concentrations of 0.42, 0.82, and 1.18 mole/kg. An averaged set of the constants applicable for this range of the initial composition was also evaluated. The compatibility between observed and calculated concentration and rate curves was improved by the use of the newly developed sets of the constants. The mechanism of the polycondensation reaction is also discussed, based on the rate and kinetic constants obtained by this work.