胺法制碱的国内外状况

本文叙述了胺法制碱的国内外动态,着重讨论了国外几种胺法制碱工艺路线,指出了各自的优缺点,为开展胺法制碱的研究提??有用的资料。同时,简要地介绍了作者进行的试验工作。     

胺类环氧固化剂胺值测定方法的探讨

介绍了伯胺值、仲胺值和叔胺值的测定方法,以及改性胺固化剂理论用量的计算公式。     

合成胺的工业化过程

回顾了最近十几年中甲胺、C2～C5的烷基胺、环已胺的合成工艺，重点讨论了技术的发展。研究过的新技术包括沸石催化的甲胺合成，异丁烯直接胺化制叔丁胺，以及催化精馏制丁胺和环已胺。还讨论了过程发展的方向。     

乙撑胺制造技术进展与需求动向

介绍了乙撑胺的种类和性质,制造工艺技术进发、产品应用领域和需求动向。     

N~1-(4-氨基丁基)-N~4-(9-蒽甲基)-1,4-丁二胺的合成

以N-叔丁氧羰基-1,4-丁二胺和N-(4-溴丁基)邻苯二甲酰亚胺为原料,经取代及保护两步反应合成N1-(4-邻苯二甲酰亚胺)丁基-N1,N4-二叔丁氧羰基-1,4-丁二胺(Ⅳ),然后肼解得N1-氨基丁基-N1,N4-二叔丁氧羰基-1,4-丁二胺(Ⅴ),3步反应总收率38%;Ⅴ与9-蒽甲醛缩合后用NaBH4还原,产物提纯后脱保护得目标产物N1-(4-氨基丁基)-N4-(9-蒽甲基)-1,4-丁二胺盐酸盐(Ⅶ),3步反应总收率约7 5%。化合物Ⅳ~Ⅶ的结构经13CNMR,1HNMR和ESI-MS确证,并对反应条件进行了初步优化。     

胺和环氧氯丙烷的反应

以不同结构的胺合成了一系列缩水甘油胺，讨论了胺的结构对其所合成的缩水甘油胺的影响，并对其产生的原因作了论述。     

脂肪醇的胺化反应

本文对长链脂肪醇胺化反应的热力学和反应途径作分析，在此基础上研究了改进铜镍胺化催化剂选择性的方法，发现某些稀土元素有显著的抑制高沸物生成的作用，分析了催化剂失活的原因，新开发的铜镍／载体催经剂能够达到醇转化剂≥９９％，选择性≥９８％，叔胺收率≥９７％水平。     

The production of biobased diamines from renewable carbon sources: Current advances and perspectives

Bio-based diamines are considered to be a promising alternative to traditional fossil-fuel-based diamines, the important platform chemical for the synthesis of polymer materials. In this review, the current status of the art of the synthesis of aliphatic and aromatic diamines from renewable biomass are considered. In the case of aliphatic diamines, we describe strategies for biologically producing diamines with different carbon numbers including 1,3-diaminopropane, 1,4-butanediamine, 1,5-pentanediamine, 1,6-diaminohexane, 1,8-diaminooctane, 1,10-diaminodecane, and 1,12-diaminododecane. In addition, aromatic diamines produced from various kinds of renewable biomass, including lignin, cashew nut shell, and terpenoids, are reviewed here. Furthermore, the application of typical diamines in synthesis of polyurethane and polyamide are also reviewed.     

Synthesis and characterization of a water-soluble rigid-rod polymer

Water-soluble polyaramides have been prepared from 2,5-diaminobenzene-sulphonic-acid activated by TMSCl and terephthalic-acid-chloride. Using this method, we achieved molecular weights of our polymers up to 18,000 g mol⁻¹. Two model compounds were synthesized in order to establish the effect of trimethylsilyl-chloride, which was used as the activating agent for this reaction. The resulting sulphonated poly-aramides were characterized by: inherent viscosity measurements, size exclusion chromatography (SEC), DMA, TGA, flame absorbance atomic spectroscopy (FAAS), NMR spectroscopy and optical polarisation microscopy. In all cases, the polymers were easily soluble in hot water up to concentrations of 20 wt%. Upon cooling lyotropic alignment of molecular aggregates is observed at low polymer concentrations, typically 2–5 wt%. Polymers with low molecular weights do not show this behaviour. Films made from these sulphonated aramide polymers showed good thermal stability, and have interesting mechanical properties. Our results indicate the presence of a structure consisting of molecular aggregates.     

Synthesis and characterization of 2-D and 3-D covalent networks derived from triazine central cores and bridging aromatic diamines

Nucleophilic substitutions of the reactive chlorine atoms in either cyanuric or phosphonitrilic chloride by the bridging 1,4-phenylenediamine and benzidine units lead to the formation of two- (2-D) or three-dimensional (3-D) covalent networks, according to the spatial arrangement of the chlorine atoms in each particular triazine core. The materials are electrochemically active and stable, and exhibit interesting optical properties. The UV-visible spectral absorptions are significantly red-shifted and can been altered upon chemical oxidation. Furthermore, a three-band absorption spectrum typical of polaronic nature is observed in the case of the layered benzidine/cyanuric chloride network. Either spherical (2-D) or cubic (3-D) morphologies were revealed by SEM analysis, while the XRD patterns indicated partial crystallinity. Due to the inherited ion-exchange properties of the 2-D and 3-D ionic networks, the materials can be regarded as the organic analogues of conventional inorganic layered or zeolitic ion-exchangers.     

Polyamides incorporating furan moieties. 5. Synthesis and characterisation of furan-aromatic homologues

2,2′-Bis (5-chloroformyl 2-furyl) propane and various aromatic diamines were used as monomers in the study of their interfacial polycondensation and the properties of the ensuing furanic-aromatic polyamides. The effects of such variables as the nature of the organic phase, the temperature, the reaction time, and the type and concentration of the catalyst were investigated as well as the properties of the polyamides in terms of structure, average chain length, T_g, T_m and thermal stability.     

Dimer acid-based thermoplastic bio-polyamides: Reaction kinetics, properties and structure

New dimer acid-based-polyamides were synthesized with rapeseed oil-based dimer acid (DA) and 1,2-diaminoethane, 1,6-diaminohexane or 1,8-diaminooctane to form DAPAe, DAPAh and DAPAo, respectively. Effects of diamine chain lengths on kinetics evolution as well as on the thermal, physical and mechanical properties of the different polyamides synthesized were investigated. DAPAo was found to be the most reactive diamine because of its higher nucleophilic character. Differential scanning calorimetry (DSC) combined with X-ray diffraction revealed a low-order semi-crystalline structure for all polyamides. A tentative schema for the structural organization of these DAPA is proposed and shows a specific organization with local semi-crystalline segregation domains. DAPAe was found to possess the higher melting temperature likely due to higher crystal cohesion, which was confirmed by higher Young modulus in stress-strain experiments. Rheological data showed an increase of the glass transition temperature concomitantly with the increase of diamine chain length. They also revealed an increase of complex viscosity with the diamine chain length. Investigation of thermal stability showed that DAPAe degrades before DAPAh and DAPAo in connection with the number of methylene units per diamine.     

A new synthetic approach for difficult benzoxazines: Preparation and polymerization of 4,4′-diaminodiphenyl sulfone-based benzoxazine monomer

The first successfully synthesized benzoxazine in high purity from 4,4′-diaminodiphenyl sulfone (DDS), paraformaldehyde and phenol using high boiling point nonpolar solvent is reported. The solution method for benzoxazine synthesis is modified by using a nonpolar solvent of high boiling point. For comparison, the synthesis of such difficult benzoxazine monomer was prepared in high boiling point polar solvent, dimethylsufoxide. ¹H NMR indicates the purity of the monomer prepared by this novel method to be quite high in comparison with that obtained using dimethylsulfoxide (DMSO). The thermally activated polymerization of the monomer affords polybenzoxazine with T_g at ca. 203 °C. The 5% and 10% decomposition temperatures of the polymer are 324 and 368 °C with 58% char yield, reflecting the excellent thermal stability than the typical polybenzoxazine based on bisphenol-A and aniline.     

Thermal Stability and Mechanical Properties of Organo-Soluble and Processable Polyimides for High-Temperature Materials

A new series of organo-soluble polyimides with pendant groups of methoxy or methyl of azomethine diamine were synthesized through two-step process by chemical imidization. Such polyimides were tested for thermal and mechanical properties. Their thermal stability was studied in terms of temperature at 10% weight loss which ranged between 475 and 498°C with T_g around 240–278°C. Activation energy, enthalpy of the polyimides were calculated and ranged 31.12–43.59?kJmol^?1 and 29.46–41.93?kJmol^?1. Thermal, mechanical, and thermodynamic parameters demonstrated that the resulting polyimides can hold excellent application in the fields of high-performance, advanced composites, and high-temperature microelectronics.     

非基因毒性二氨基类直接染料的合成与研究

利用非基因毒性的2,2′-二甲基-5,5′-二丙氧基对二氨基联苯和5,5′-二丙氧基对二氨基联苯作为中间体,合成了四种直接染料。光谱分析确定了它们的最大吸收波长(分别为518nm、554nm、530nm和578nm)和上染率(最高可达90.3%,最低值为78.5%)。质谱确定了它们的结构。经色牢度分析可知这些染料有较好的着色能力和色牢度。     

Synthesis and characterization of organo‐soluble fluorinated polyimides

A novel fluorinated diamine monomer with a keto group, 4‐[4‐amino‐2‐trifluoromethyl phenoxy]‐4′‐[4‐aminophenoxy]benzophenone (ATAB) was prepared by reacting dihydroxybenzophenone with 4‐chloronitrobenzene and 2‐chloro‐5‐nitrotrifluoromethylbenzene in the presence of potassium carbonate followed by catalytic reduction with palladized carbon (10%). Fluorinated polyimides IVa–e were synthesized from the diamine mentioned above via a two‐step method (thermal and chemical imidization). Polyimides IVa–e have inherent viscosities in the range 0.65–1.06 dL g^?1 (thermal imidization) and 0.82–1.56 dL g^?1 (chemical imidization). The polyimides prepared by chemical imidization exhibit excellent solubility. Polyimide films exhibit tensile strength, elongation and tensile modulus in the ranges 96–106 MPa, 9–13% and 1.1–1.7 GPa, respectively. The T₁₀ values of the polyimides are in the range 540–598 °C in nitrogen and 545–586 °C in air, with more than 50–60% char yield. They have T_g values between 244 and 285 °C. The prepared polyimides show cut‐off wavelengths in the range 365–412 nm and transmittance at 450 nm in the range 80.9–94.2%. The dielectric constants of the polyimide films are in the range 3.10–3.77 at 1 kHz and 3.04–3.66 at 10 kHz, with moisture absorption of 0.14–0.40%. Copyright © 2006 Society of Chemical Industry     

Polymeric schiff bases bearing furan moieties 2. Polyazines and polyazomethines

Several furanic polyazines and polyazomethines were prepared by solution condensation of 2,5-furandicarboxaldehyde (FDC) with hydrazine, 1,4-phenylene diamine and O-O′(bis-2-aminopropyl)polyethylene oxide (Jeffamine) and thoroughly characterized. Their thermal and photochemical properties were also studied. Model compounds were used in order to prove the feasibility of the reaction and facilitate the characterization of the polymers. An improvement in the solubility of these furanic poly-Schiff bases could be achieved by the use of oligomeric intermediates or furanic polyketazines.