聚酯二元醇合成工艺的研究

由于二元醇在合成过程中的损失,造成实际相对分子质量与理论相对分子质量相差较大,因此,为弥补二元醇的损失,一般将二元醇的质量过量．用共沸蒸馏、一步投料的方法,对二元醇过量的质量及其出水速率进行了初步的研究．研究结果表明：①二元醇过量H〈0．011mol,则实际相对分子质量远远大于设计的相对分子质量;反之,若H〉0．011mol,则实际相对分子质量比设计的相对分子质量要小．②出水速率如果过快,即7h就达到理论出水量的90％,则实际相对分子质量与设计相对分子质量相差较大;而出水速率是0．84mL／h,12h达到理论出水量的90％,实际相对分子质量与设计相对分子质量比较接近．确定了二元醇过量的质量为H=0.011mol、出水速率控制在0．84mL／h时为最佳条件,从而实现了最终产物相对分子质量接近按投料比计算设计的相对分子质量的试验设计方案,为聚酯二元醇的合成提供参考依据．     

Aerobic Oxidation of Vicinal Diols Catalyzed by an Anderson‐Type Polyoxometalate, [IMo6O24]5–

An Anderson‐type polyoxometalate, [I^VIIMo₆O₂₄]^5–, has been used as a catalyst for the aerobic oxidation at 80 °C of vicinal diols (glycols). This is the first report on the use of such a polyoxometalate as an oxidation catalyst. Reactivity and selectivity were dependent on the substrate. Thus, aryl‐substituted diols yielded mostly the carbon‐carbon bond cleavage products, while 1,2‐cyclohexanediol yielded cyclohexanone‐2‐ol and 1,2‐cyclohexanedione. Aliphatic diols were less reactive but yielded carbon‐carbon bond cleavage products in the presence of additional acid. An abbreviated mechanistic study was carried out indicating that the polyoxometalate oxidizes the diol to the various products even under anaerobic conditions. The reduced polyoxometalates (heteropoly blues and heteropoly browns) formed in the oxidation of the diols are re‐oxidized by the molecular oxygen.     

Base‐Catalyzed Cascade 1,3‐H Shift/Cyclization Reaction to Construct Polyaromatic Furans

A convenient new method was developed to prepare unfused polyaromatic furan derivatives from diynyl‐1,6‐diols through a novel base‐catalyzed cascade 1,3‐H shift/cyclization process. Deuterium experiments were performed to determine that the 1,3‐H shift was the rate‐determining step.     

生物质多元醇选择性催化氢解制小分子二元醇研究进展

乙二醇、1,2-/1,3-丙二醇等小分子二元醇在精细和有机化工、生物医药等领域应用广泛。与石化路径相比,以可再生的生物质多元醇（丙三醇、山梨醇/木糖醇）为原料选择性催化氢解制取上述小分子二元醇具有过程简单、绿色高效等显著优势,已成为生物质催化转化的研究热点。本文综述了典型生物质多元醇山梨醇/木糖醇和丙三醇选择性催化氢解为乙二醇、1,2-/1,3-丙二醇等小分子二元醇,重点阐述了丙三醇选择性氢解制1,2-丙二醇、1,3-丙二醇和山梨醇/木糖醇选择性氢解制小分子二元醇的催化剂体系和反应机理,并对该领域的发展前景作了展望,提出开发高效稳定的催化剂体系和工艺是未来的研究重点。     

Studies on thermoplastic polyurethanes based on new diphenylethane‐derivative diols. III. The effect of molecular weight and structure of soft segment on some properties of segmented polyurethanes

Two series of poly(ether urethane)s and one series of poly(ester urethane)s were synthesized, containing, respectively, poly(oxytetramethylene) diol (PTMO) of M _n = 1000 and 2000 and poly(ε‐caprolactone) diol of M _n = 2000 as soft segments. In each series the same hard segment, i.e., 4,4′‐(ethane‐1,2‐diyl)bis(benzenethiohexanol)/hexane‐1,6‐diyl diisocyanate, with different content (～ 14–72 wt %) was used. The polymers were prepared by a one‐step melt polymerization in the presence of dibutyltin dilaurate as a catalyst, at the molar ratio of NCO/OH = 1 (in the case of the polymers from PTMO of M _n = 1000 also at 1.05). For all polymers structures (by FTIR and X‐ray diffraction analysis) and physicochemical, thermal (by differential scanning calorimetry and thermogravimetric analysis), and tensile properties as well as Shore A/D hardness were determined. The resulting polymers were thermoplastic materials with partially crystalline structures (except the polymer with the highest content of PTMO of M _n = 2000). It was found that the poly(ether urethane)s showed lower crystallinity, glass‐transition temperature (T_g), and hardness as well as better thermal stability than the poly(ester urethane)s. Poly(ether urethane)s also exhibited higher tensile strength (up to 23.5 MPa vs. 20.3 MPa) and elongation at break (up to ～ 1950% vs. 1200%) in comparison with the corresponding poly(ester urethane)s. Among the poly(ether urethane)s an increase in soft‐segment length was accompanied by an increase in thermal stability, tensile strength, and elongation at break, as well as a decrease in T_g, crystallinity, and hardness. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Cyclohexa‐3,5‐diene‐1,2‐trans‐diols – Synthesis and Application in Target‐Oriented Syntheses

An exhaustive overview of the field of cyclohexa‐3,5‐diene‐1,2‐trans‐diols is given. Early and recent methods for the formation of the compounds are reviewed and the various syntheses in which the title compounds have been applied are presented. Special emphasis is given to naturally occurring epoxides, which have been the dominant target molecules since the 1970s. Finally, recent advances in biotechnology are highlighted; with the increased availability of the enantiomerically pure cyclohexa‐3,5‐diene‐1,2‐trans‐diols, new synthetic endeavours were initiated.     

聚碳酸酯二醇型水性聚氨酯的制备

以异佛尔酮二异氰酸酯(IPDI)、聚碳酸酯二醇(PCDL)、二羟甲基丙酸(DMPA)、1,4-丁二醇(BDO)和甲基丙烯酸羟乙酯(HEMA)为原料制备一系列水性聚氨酯(WPU)乳液。以粒径、黏度、耐水性、力学性能、热稳定性等为指标,对原料的用量及配比进行选择。结果表明:当聚碳酸酯二醇相对分子质量为1000,—NCO与PCDL中—OH物质的量比为2.8,DMPA、BDO、HEMA用量分别为5.0%、4%、4%时,制备的WPU性能较佳。     

Synthesis of oligocarbonate diols from ethylene carbonate and aliphatic diols catalyzed by alkali metal salts

The influence of alkali metal salt catalysts and reaction conditions on the oxyethylene units formation in the synthesis of oligocarbonate diols from five-membered cyclic carbonates and aliphatic diols is presented. The reaction mechanism, involving the alkoxide group formation from cyclic carbonate and alkali metal salts has been proposed and discussed. The oligomeric products were analyzed by means of MALDI-TOF mass spectrometry and NMR spectroscopy.     

Sterols and triterpene diols in olive oil as indicators of variety and degree of ripening

Sterols and triterpene diols in olive oil as indicators of variety and degree of ripening derived from three olive varieties and produced at three different harvesting periods were studied. In order to test the stability of the proposed indicators, oils obtained were stored for 12 months at three different temperatures. Thirty-six samples in total were subjected to GC analysis and results were processed by multivariate chemometric methods (MANOVA, PCA, and SLDA). Campesterol, β-sitosterol, Δ⁷-campesterol/Δ^5,24-stigmastadienol, clerosterol, uvaol, and campestanol/Δ⁷-avenasterol were established as the indicators of variety of fresh oils, while when stored oils were included in the model, the final three compounds were substituted by 24-methylene-cholesterol/stigmasterol. The most important variables for differentiating fresh oils according to degree of ripening were Δ⁷-campesterol/β-sitosterol, uvaol/stigmasterol, clerosterol/Δ⁵-avenasterol and sitostanol/uvaol, while stored oils were differentiated by campestanol/stigmasterol, erythrodiol, stigmasterol/Δ⁷-campesterol, Δ⁵-avenasterol, 24-methylene-cholesterol/β-sitosterol and 24-methylene-cholesterol. Results demonstrated that sterols and triterpene diols can be used as indicators of variety and degree of ripening among virgin olive oils.     

Alkylation of aromatics with diols in superacidic media

Friedel–Crafts alkylation of simple aromatics (benzene, toluene, o-, m- and p-xylene) with various types of diols in the presence of superacidic trifluoromethanesulfonic acid was studied. 1,2- and 1,3-diols were found to bring about only monoalkylation yielding unusual monoalkylated products: bis(1-methyl-2-phenylpropyl) ether was formed in the reaction of 2,3-butanediol, and 2,4-dimethyl-2,4-pentanediol produced mono- and di-tert-butyl-substituted benzenes. Higher diol homologues, in turn, undergo electrophilic cyclialkylative ring closure (cyclialkylation) to form tetralin derivatives with high selectivities and in good yields. Additional primary alkylation processes are monoalkylation to yield alkylbenzenes and the formation of diphenylalkanes. The products thus formed may participate in secondary transformations, which are a second cyclialkylation (formation of octahydroanthracene and -phenanthrene derivatives), isomerization and dehydrogenation. Mechanistic studies with stereoisomeric 2,5-hexanediols point to the involvement of open dicationic intermediates in the alkylation process. This revised version was published online in June 2006 with corrections to the Cover Date.