N-(2-苦胺基乙基)单氮杂冠醚的合成

研究并比较了氮支套索型生色冠醚1a和1b两条不同的合成路线, 结果表明, 由N-苦基乙二胺(2)与1,11-二碘-3,6,9-三氧杂十一烷进行N-烷基化环化反应, 可方便地制备N-(2-苦胺基乙基)单氮杂-12-冠-4(1a), 但按此法未能获得更大环的-15-冠-5(1b);若从N-对甲苯磺酰基乙二胺(6)或N-(2-对甲苯磺酰胺基乙基)二乙醇胺(7)出发, 经环化, 脱除对甲苯磺酰基而制得的N-(2-氨基乙基)单氮杂冠醚5a和5b分别与苦基氯反应, 则可获得高产率的生色生色冠醚11a和1b.     

An Endo-Selective Epoxide-Opening Cascade for the Fast Assembly of the Polycyclic Core Structure of Marine Ladder Polyethers

The rapid synthesis of marine ladder polyethers from polyepoxide precursors (in analogy with the biosynthetic pathway hypothesized by Nakanishi) is hampered by the fact that the exo-selective epoxide-opening cyclization cascade that gives THF-type polyethers is preferred over the endo-selective cascade that gives the desired products. We found that perfluoro-tert-butanol (PFTB) cooperating with 1-ethyl-3-methylimidazolium tetrafluoroborate ([EMIM]BF₄) can promote endo-selective epoxide-opening cyclization reactions of trisubstituted epoxy alcohols. Starting from readily accessible homochiral polyepoxy alcohols with a methyl group at all the endo-cyclization sites, we were able to construct polyethers up to five consecutive fused 6-, 7-, and/or 8-membered rings in one step. Notably, molecules with the 7/7/6/6 and 7/7/6/7/6 polyether frameworks of hemibrevetoxin B and brevenal, respectively, could be synthesized in 40 % and 17 % chemical yields.     

超支化聚醚涂层毛细管柱在线推扫富集检测6种有机磷农药

合成了3种不同支化度的超支化聚醚,采用化学键合的方法将其涂覆于石英毛细管电泳柱内壁,制备了一种新型的毛细管电泳涂层柱。利用该涂层柱通过胶束电动毛细管色谱在线推扫富集技术对6种有机磷农药进行了富集和检测。结果表明:由于超支化聚醚涂层柱显著降低了电渗流,其富集倍数远高于未涂层柱,有效提高了检测的灵敏度。其中支化度为0.43的S3涂层柱的富集倍数高达530倍,是未涂层柱的4倍。利用S3涂层柱建立了分析6种有机磷农药的方法,检出限为0.03～0.08mg/L;加标回收率为85.8%～104.6%;RSD为3.0%～8.4%。此超支化聚醚涂层柱的稳定性良好。     

Glycidyl Tosylate: Polymerization of a “Non‐Polymerizable” Monomer permits Universal Post‐Functionalization of Polyethers

Glycidyl tosylate appears to be a non‐polymerizable epoxide when nucleophilic initiators are used because of the excellent leaving group properties of the tosylate. However, using the monomer‐activated mechanism, this unusual monomer can be copolymerized with ethylene oxide (EO) and propylene oxide (PO), respectively, yielding copolymers with 7–25 % incorporated tosylate‐moieties. The microstructure of the copolymers was investigated via in situ ¹H NMR spectroscopy, and the reactivity ratios of the copolymerizations have been determined. Quantitative nucleophilic substitution of the tosylate‐moiety is demonstrated for several examples. This new structure provides access to a library of functionalized polyethers that cannot be synthesized by conventional oxyanionic polymerization.     

Demulsification and Interfacial Properties of Crosslinking Phenol-Amine Resin Block Polyether Demulsifiers

Six novel crosslinking phenol-amine resin block polyether demulsifiers were synthesized for demulsification of surfactant-polymer flooding emulsion. The demulsification performances of these demulsifiers were investigated by conventional graduated bottle test. Their interfacial behaviors at water-oil interface were explored by dynamic interfacial tension and interfacial dilational viscoelasticity measurements. The results show that the demulsification efficiency is dependant on the hydrophilic-hydrophobic balance (HLB) value of these demulsifiers. It was also correlated to the interfacial activity and the dilational elasticity at the water-oil interface. The higher the HLB value of demulsifiers, the better the demulsification efficiency is.     

汽车空调器压缩机用冷冻机油的研究

采用三氟化硼乙醚 (BF3·Et2 O)催化体系合成较高粘度的环氧丙烷均聚醚 ,观察了不同反应参数对聚醚粘度的影响。同时考察了不同催化剂对聚醚酯性能的影响。结果表明 ,用固体钨硅酸合成的聚醚酯较对甲苯磺酸的性能好     

Synthesis and Preliminary Demulsification Efficiency Evaluation of New Demulsifiers Based on Fatty Oils

Three raw fatty oils were used as precursors for demulsifiers. The hydrolyzed form of each oil was adducted with maleic anhydride then modified by esterification with polyethylene glycols or ethyleneoxide-propyleneoxide block copolymers. The demulsfication efficiency, coalescence rate, some surface active, thermodynamic properties, and partition coefficient of a selected demulsifier were investigated. The best demulsifier shows 100% demulsification after 19 minutes at 300 ppm. A correlation between demulsification efficiency and rheological properties of the investigated demulsifier was investigated. Also, emulsification kinetics were followed by microscopic photography. A mechanism following coalescence and flocculation of water droplets is proposed.     

Synthesis and characterization of 1,3,4,-thiadiazole-containing polyethers from 2,5-bis (4-fluorophenyl)-1,3,4-thiadiazole and various aromatic diols

Seven 1,3,4-thiadiazole-containing polyethers with reduced viscosities of 0.27–1.44 dL/g were synthesized by the high-temperature solution polycondensation of novel activated difluoride, 2,5-bis (4-fluorophenyl)-1,3,4-thiadiazole, with aromatic diols possessing a variety of ring structures. The expected chemical structures were confirmed by IR and ¹H-NMR spectroscopy and elemental analysis. Of all the polymers, three polyethers were highly crystalline and soluble only in limited solvents such as concentrated sulfuric acid. The other polyethers were amorphous and dissolved easily in a variety of organic solvents including N-methyl-2-pyrrolidone (NMP), phenols, and chlorinated hydrocarbons. Colorless to slightly yellow-colored, transparent, and tough films could be cast from the NMP solutions of the amorphous polyethers. The mechanical properties of the films were excellent, and their tensile strength, elongation at break, and tensile moduli were in the ranges of 48–72 MPa, 5–7%, and 1.3–1.9 GPa, respectively. The amorphous polyethers had high glass transition temperatures of 204–299°C. All the polyethers were highly thermally and thermooxidatively stable and exhibited no weight loss up to 400°C, with 10% weight loss being recorded at 464–513°C in air. © 1994 John Wiley & Sons, Inc.     

盐酸奈法唑酮的合成

盐酸奈法唑酮是一类新型抗抑郁药.先用间氯苯胺与二乙醇胺环化合成1-(3-氯苯基)哌嗪,再与1-溴-3-氯丙烷反应制得1-(3-氯丙基)-4-(3-氯苯基)哌嗪盐酸盐,最后与5-乙基-4-(2-苯氧乙基)-1,2,4-三唑-3-酮反应得到盐酸奈法唑酮.产物结构经IR,MS,1H NMR及13C NMR确证.     

二乙醇胺改性聚乳酸的直接熔融聚合法合成及其表征

以乳酸(LA)、二乙醇胺(DEA)为原料,采用熔融聚合法直接合成了二乙醇胺改性聚乳酸,并用特性粘数、FT-IR、1H NMR、GPC、DSC、XRD等手段进行表征,探讨了催化剂种类和用量、熔融聚合反应时间、反应温度以及不同投料比、不同构型乳酸对聚合物合成的影响.在单体投料摩尔比n(DEA):n(L-LA)=1:200、160℃、70Pa、催化剂SnO用量0.7(wt)%、熔融聚合8h条件下,聚合物重均相对分子质量(Mw)可达8100.随着投料比中DEA的增加,产物特性粘数逐步降低,Mw逐渐减小,玻璃化温度(Tg)有降低的趋势.以L-LA聚合得到的聚合物的Mw、分散度(Mw/Mn)和结晶度均比由D,L-LA得到的产物的更高.因此,笔者认为,由于D,L-A与L-LA存在反应速率差异,因而二者有不同的反应历程.新合成方法有利于降低二乙醇胺改性聚乳酸作为药物缓释载体等生物医学材料的合成成本.     

The synthesis and the bulk rheological properties of the highly-branched block polyethers

Several kinds of highly-branched block polyethers were synthesized via anion ring-opening polymerization of propylene oxide (PO) and ethylene oxide (EO), using phenol-amine resin (PA) as the initiator. The rheological properties determined by rotational rheometer all followed the regular rules of polymer systems: under a certain conditions, the bulk polyethers were pseudoplastic and non-Newtonian fluid, and with the increasing of the shear rate and temperature, the apparent viscosity of the block copolymers were reduced. In addition, modulus determination showed that such polyether molecules presented preferable viscosity compared to the elasticity, meanwhile, storage modulus, loss modulus and compound viscosity all decreased with the increasing of temperature. Storage modulus and loss modulus increased along with the scanning frequency increasing. But compared with the same kind of linear polymers, the significant difference was the low melt viscosity, which attributed to the special three-dimension space structure hindering the entanglement of chains. Furthermore, the rheological properties among the several block polyethers showed differences obviously. In other words, the number of block and the content of EO all have a significant effect on the rheological properties, specifically, the modulus will increase with the increasing of the block number and the EO content.     

The structures of noncyclic polyether carriers exhibiting lithium ion-selective transport

Several noncyclic polyether compounds containing oxytrimethylene groups and o-carboxyphenyl terminal group were synthesized. It has been found that they can transport lithium ion selectively in the competitive alkali metal ion transport through liquid membranes. The results of the spectroscopic study, together with inspection on the basis of the CPK model building suggest that these polyethers can form a pseudocavity, in which lithium ion best fits, and then the terminal aromatic rings overlap one another face-to-face to form a stacking structure. By using newly synthesized polyethers, which were designed on the basis of the conformational information, the significant contribution of the structures of these polyethers could be verified.     

N,N-二羟乙基十二烷基胺的合成及性能

以二乙醇胺和溴代十二烷为原料,在无水乙醇介质中合成了脱模剂用新型原材料N,N-二羟乙基十二烷基胺.通过正交试验法对合成工艺进行了优化,研究了各种因素对合成产率的影响,确定了在无水乙醇介质中合成该化合物的最佳工艺条件;表征了合成产物的结构,并测定了其理化性能和表面化学性能.结果表明:在无水乙醇介质中合成N,N-二羟乙基十二烷基胺简单易行,产率为85.37%.合成产物在水溶液中的临界胶束浓度为2.92×10-3mol/L,所对应的液体表面张力为20.875 mN/m.以合成产物为原材料制备的固化薄膜的表面能为14.57 mN/m,小于聚氨酯塑料的表面能29 mN/m,是聚氨酯塑料和弹性体脱模剂的理想原材料.     

Synthesis of the metabolites of 4-(2-methyl-1H-imidazol-1-yl)-2,2-diphenylbutanamide (KRP-197/ONO-8025)

We synthesized the six presumed metabolites (2--7) of 4-(2-methyl-1H-imidazol-1-yl)-2,2-diphenylbutanamide [KRP-197/ONO-8025, 1], a urinary incontinence therapeutic agent, in order to confirm the structures of the metabolites. Metabolite (2) was synthesized via glucuronidaion of compound (1) and methyl 2,3,4-tri-O-benzoyl-1-methanesulfonyl-alpha-D-glucopyranuronate. Metabolite (3) was synthesized via 3-(tert-butoxycarbonyl)-2-methyl-1,3-imidazolidine-4,5-dione. Metabolites (4--7) were synthesized via 4-amino-2-diphenylbutanamide, respectively. The structures of the metabolites (2--7) in humans were identified by means of synthesis of the authentic compounds.     

Energetic features of copper and lead sorption by innovative aminoalcohol-functionalized cobalt phyllosilicates

Inorganic-organic cobalt phyllosilicate hybrids were synthesized by the sol-gel procedure under mild non-hydrothermal conditions with a silicon precursor, formed through individual reactions between the silane 3-glycidoxypropyltriethoxysilane and the aminoalcohols ethanol- or diethanolamine. These procedures generated talc-like phyllosilicates containing pendant organic chains with nitrogen and oxygen basic centres located in the interlamellar region. For organofunctionalized phyllosilicates the lamellar structure obtained through the sol-gel method was confirmed by X-ray powder diffraction, while elemental analysis indicated that the densities of the organic groups attached to the new matrices were 3.31 ± 0.05 and 3.08 ± 0.07 mmol g(-1) for hybrids functionalized with ethanol- and diethanolamines, respectively. Infrared spectroscopy and nuclear magnetic resonance in the solid state for (13)C and (29)Si showed that the organic groups are indeed covalently bonded to the inorganic structures and the process of functionalization did not affect the original structures of the silylating agents employed. The thermally stable hybrids presented well-formed particles with a homogeneous distribution of cobalt and nitrogen atoms. Their abilities for copper removal from aqueous solutions gave maximum capacities of sorption of 2.01 ± 0.11 and 2.55 ± 0.15 mmol g(-1) for phyllosilicates containing ethanol- and diethanolamine groups, respectively. For lead sorption the values of 2.59 ± 0.11 and 2.43 ± 0.12 mmol g(-1) were found for this same sequence. These sorption data were adjusted to the non-linear regression of the Langmuir equation. Energetic features related to the interactions between the cations and the pendant basic centres were determined through calorimetric titrations. The acid-basic interactions reflect the spontaneity of the reactions, which are also enthalpically and entropically favourable for these chelating processes at the solid-liquid interface.     

Synthesis and Evaluation of New Demulsifiers Incorporating Linear Alkyl Benzene Moiety for Treating Water-in-Oil Emulsion

In the present study, five types of water soluble demulsifiers based on linear alkyl benzene were prepared. The chemical structures of the prepared demulsifiers were elucidated using Fourier transform-infrared (FTIR) and ¹H NMR spectra. Different factors affecting demulsification efficiency such as; water content, demulsifier concentration, hydrophilic lipophilic balance (HLB), and ethylene oxide unit were investigated. Also, the rheological properties in relation to demulsification efficiency were studied. The surface and thermodynamic parameters of the prepared demulsifiers were determined at 25°C including, surface tension (γ) and effectiveness, maximum surface excess (Γ_max), and minimum surface area (A_min). From the obtained data, it was found that the demulsification efficiency increases with increasing the water content and concentration of the demulsifiers. Primarily evaluation study of demulsification performance of the new demulsifiers showed that as the ethylene oxide unit in the demulsifiers increase (10–40 ethylene oxide units), the performance of the demulsifiers increasing, however, it decrease in case of demulsifiers with (80 ethylene oxide unit).     

Synthesis and characterization of liquid crystalline diethanolamine‐based dendrimers

Three generations of diethanolamine‐based dendrimers containing nitroazobenzene were synthesized. Firstly, G₁ was prepared by the diazotation of p‐nitroaniline, and then the obtained salts reacted with n‐phenyl‐2,2′‐iminodiethanol. The reaction of hydroxyl groups of diethanolamine of G₁ and G₂ with acryloyl chloride resulted in G_1.5 and G_2.5. Then, G₂ and G₃ were synthesized using Michael addition of amino group of diethanolamine and G_1.5 and G_2.5. The Williamson etherification and azo‐reaction were employed in the preparation of the mesogenic unit 4‐[4‐(6‐bromohexyloxy)phenylazo]nitrobenzene (N₆‐Br). Secondly, mesogen‐functionalized dendrimers were synthesized via the coupling of the hydroxyl group of G₁, G₂, G₃, and bromine from mesogenic units (N₆‐Br). The polarizing optical microscopy (POM) and differential scanning calorimetry (DSC) were used for the investigation of the liquid crystalline properties of the mesogen‐functionalized dendrimers. The structures of obtained compounds were investigated using common spectroscopy methods and CHN analysis. Copyright © 2009 John Wiley & Sons, Ltd.     

Synthesis of block polyethers with various structures and their application in dispersing single-walled carbon nanotubes

The block polyethers with different structure and composition were synthesized by anionic polymerization and used to disperse single-walled carbon nanotubes (SWNTs). The block polyethers with the structure of branch or benzene ring had better dispersion ability than the commercial Pluronic block polyethers (L64 and F127). In order to compare the parameters, dispersion limit and efficiency of polyethers for SWNTs were defined. UV?Cvis?Cnear infrared absorbance spectra showed that eight-branch polyether AE82 had much larger dispersion limit and efficiency than five-branch AE52. BPE containing benzene rings in the molecule had a slightly lower dispersion limit but larger dispersion efficiency than AE82. The defect density of SWNTs dispersed in polyether aqueous solutions was investigated by Raman spectroscopy. The polyethers AE83 and BEP with the structure of poly(ethylene oxide)?Cpoly(propylene oxide) dispersed less defective SWNTs than AE82 and BPE, indicating that the variation of polyether structure and composition could influence the defect density of SWNTs besides dispersion limit and efficiency.     

Molecular wheels: new Mn12 complexes as single-molecule magnets

The preparation, structure and magnetic properties of three new wheel-shaped dodecanuclear manganese complexes, [Mn12(Adea)8(CH3COO)14] x 7 CH3CN (1 x 7CH3CN), [Mn12(Edea)8(CH3CH2COO)14] (2) and [Mn12(Edea)8(CH3COO)2(CH3CH2COO)12] (3), are reported, where Adea(2-) and Edea(2-) are dianions of the N-allyl diethanolamine and the N-ethyl diethanolamine ligands, respectively. Each complex has six Mn(II) and six Mn(III) ions alternating in a wheel-shaped topology, with eight n-substituted diethanolamine dianions. All variable-temperature direct current (DC) magnetic susceptibility data were collected in 1, 0.1, or 0.01 T fields and in the 1.8-300 K temperature range. Heat capacity data, collected in applied fields of 0-9 T and in the 1.8-100 K temperature range, indicate the absence of a phase-transition due to long-range magnetic ordering for 1 and 3. Variable-temperature, variable-field DC magnetic susceptibility data were obtained in the 1.8-10 K and 0.1-5 T ranges. All complexes show out-of-phase signals in the AC susceptibility measurements, collected in a 50-997 Hz frequency range and in a 1.8-4.6 K temperature range. Extrapolation to 0 K of the in-phase AC susceptibility data collected at 50 Hz indicates an S = 7 ground state for 1, 2, and 3. Magnetization hysteresis data were collected on a single crystal of 1 in the 0.27-0.9 K range and on single crystals of 2 and 3 in the 0.1-0.9 K temperature range. Discrete steps in the magnetization curves associated with resonant quantum tunneling of magnetization (QTM) confirm these complexes to be single-molecule magnets. The appearance of extra QTM resonances on the magnetic hysteresis of 1 is a result of a weak coupling between two Mn ions at opposite ends of the wheel, dividing the molecule into two ferromagnetic exchange-coupled S = 7/2 halves. The absence of these features on 2 and 3, which behave as rigid spin S = 7 units, is a consequence of different interatomic distances.     

Recent Developments in Polyether Synthesis

Polyethers, both aliphatic, such as poly(ethylene oxide), poly(propylene oxide), etc., and wholly aromatic ones, such as poly(phenylene oxide)s, are commercially important materials. Polymers belonging to the former class are primarily synthesized via a ring‐opening polymerization route, while those belonging to the latter are prepared via either oxidative coupling or nucleophilic aromatic substitution approaches. Polyethers that contain both aromatic and aliphatic units in their backbone are far less common. This review will discuss some of the recent advances in the preparation of polyethers, primarily focussing on those where the ether linkage is generated during polymerization. Although the standard ring‐opening polymerization (ROP) route toward aliphatic polyethers has witnessed several interesting developments in recent years, it will not be covered in this review. The last section deals with a new melt‐transetherification approach for the preparation of poly(xylylene alkylene ether)s developed in our laboratory.