BrФnsted-Lewis双酸性离子液体催化合成二苯甲烷二氨基甲酸甲酯

合成了具有不同ZnCl2摩尔分数的BrФnsted-Lewis双酸性离子液体[HO3S-(CH2)4-mim]Cl-xZnCl2,采用Hammett指示剂与紫外联用法测定了其酸强度,考察了其在苯氨基甲酸甲酯(MPC)与甲醛(HCHO)缩合制备二苯甲烷二氨基甲酸甲酯(MDC)反应中的催化性能,并考察了反应条件对MDC收率和MPC转化率的影响。结果表明,当x=0.7时该离子液体的催化活性最高。以[HO3S-(CH2)4-mim]Cl-0.7ZnCl2为催化剂兼溶剂,在反应温度70℃、反应时间60min、MPC与HCHO的摩尔比为10、离子液体与MPC的质量比为2的条件下,MDC收率最高可达99.1%。用水处理反应液并通过减压蒸馏回收的离子液体可以循环使用5次,其催化活性基本不变。     

酯交换法合成碳酸二苯酯的工艺进展

综述了酯交换法合成碳酸二苯酯(DPC)的常见工艺路线,指出了碳酸二甲酯(DMC)和苯酚酯交换合成路线是当前的研究热点,并对一步法工艺和两步法合成DPC的工艺路线作了详尽的介绍;对产品的后续提纯方面进行归纳总结,阐述了减压精馏法和结晶分离法的研究现状。最后对各个工艺路线的优缺点进行了简要总结与对比。     

混合酸催化合成二苯甲烷二氨基甲酸甲酯

以混合酸为催化剂,水作溶剂,对苯氨基甲酸甲酯(MPC)和甲醛溶液或三聚甲醛缩合制备二苯甲烷二氨基甲酸甲酯(MDC)的反应进行了考察,考察了混合酸浓度、反应时间、原料配比、催化剂用量等条件对反应的影响。以甲醛为甲基化试剂的最佳反应条件为:混合酸浓度30%、反应时间2h、n(MPC)/n(HCHO)=1/1、反应温度100℃,MDC收率为89 47%;以三聚甲醛(STO)为甲基化试剂时,最佳反应条件为:混合酸浓度30%、反应时间5h、反应温度105℃、n(MPC)/n(STO)=15/4,MDC产率为75 81%。     

钯负载铁酸盐催化苯酚氧化羰基化合成碳酸二苯酯

为了将负载铁酸盐催化剂应用于磁稳定床中催化合成碳酸二苯酯,考察了焙烧温度(400～800℃)和焙烧时间(1～4h)对铁酸锰载体结构特征、磁学性质以及相应催化剂在催化苯酚氧化羰基化合成碳酸二苯酯中的催化特性的影响,采用柠檬酸络合法制备出尖晶石铁酸盐载体铁酸锰,通过沉淀法负载活性组分钯制备了钯负载铁酸锰催化剂,使用X-射线衍射(XRD)、比表面积孔径分析仪(BET)、扫描电镜(SEM)和振动样品磁强计(VSM)对其进行了相应的表征.结果显示,铁酸锰载体焙烧温度对催化剂的结构特征、磁性以及催化活性均有较大影响,而焙烧时间对其相应的影响则相对较小;其中,载体在500℃下焙烧2h,具有单一的尖晶石结构,较大的比表面积以及良好的孔结构;比饱和磁化强度可达40.2emu/g,其剩磁小于5.0emu/g,矫顽力小于15kA/m,符合磁稳定床中对于磁性固体颗粒磁学特性的要求;相应催化剂具有最大的收率5.15%.负载铁酸盐催化剂应用于磁稳定床中催化合成碳酸二苯酯的最佳工艺条件是:铁酸锰载体的焙烧温度为500℃,焙烧时间为2h.     

精确合成多溴代二苯醚类化合物

用间氯过氧苯甲酸和三氟甲磺酸作为酸性氧化体系,以多种溴代碘苯及溴代苯合成了溴代二苯基碘盐.再以其与溴代苯酚在碱性条件下反应,精确合成各种多溴代二苯醚.该方法简便、反应条件温和、后处理简单、产品纯度好、收率高.     

Enhanced triolein removal using microemulsions formulated with mixed surfactants

In previous work, a microemulsion-based formulation approach yielded excellent laundry detergency with hydrophobic oily soils hexadecane and motor oil. In this work, the same approach is used in detergency of triolein, which is a model triglyceride, some of the most difficult oils to be removed from fabric. The linker concept was applied in formulation of the microemulsion system. Three different surfactants were used: (i) dihexyl sulfosuccinate, an ionic surfactant with a moderate hydrophile-lipophile balance (HLB); (ii) secondary alcohol ethoxylate, a lipophilic nonionic surfactant with a very low HLB; and (iii) alkyl diphenyl oxide disulfonate (ADPODS), a hydrophilic anionic surfactant with a very high HLB. The phase behavior and interfacial tension (IFT) of the surfactant systems were determined with different concentrations of ADPODS. The results indicate that as the HLB of the system increases, a higher salinity is required to shift the phase transition from Winsor Type I to Type III to Type II. The three formulations at different salinities were used in detergency experiments to remove triolein from polyester/cotton sample fabric. The results showed that there were two peaks of maximum detergency in the range of salinity from 0.1% to 10% NaCl. The higher the hydrophilicity of the system, the higher the salinity required for maximum detergency. The results of the dynamic IFT and the detergency performance from two rinsing methods lead to the hypothesis that one of these maxima in detergency results from a spreading or wetting effect. The other maximum in detergency is believed to be related to ultralow IFT associated with oil/water middle-phase microemulsion formation. Triolein removal exceeding 80% was attained, validating the microemulsion approach to detergency.     

二苯胍的研制

对二苯胍的制备工艺进行了研究，即用氧化锌脱硫剂，在０．２－０．３ＭＰａ的压力一，由Ｎ，Ｎ’－二苯基硫脲合成二苯胍。对最佳工艺条件及工艺条件对收率的影响进行了研究。     

Synthesis and properties of new aromatic poly(ester‐imide)s derived from 4‐p‐biphenyl‐2,6‐bis(4‐trimellitimidophenyl) pyridine and various dihydroxy compounds

A novel class of wholly aromatic poly(ester‐imide)s, having a biphenylene pendant group, with inherent viscosities of 0.32–0.49 dL g^?1 was prepared by the diphenylchlorophosphate‐activated direct polyesterification of the preformed imide‐ring‐containing diacid, 4‐p‐biphenyl‐2,6‐bis(4‐trimellitimidophenyl)pyridine (1) with various aromatic dihydroxy compounds in the presence of pyridine and lithium chloride. A reference diacid, 2,6‐bis(trimellitimido)pyridine (2) without a biphenylene pendant group and two phenylene rings in the backbone, was also synthesized for comparison purposes. At first, with due attention to structural similarity and to compare the characterization data, a model compound (3) was synthesized by the reaction of compound 1 with two mole equivalents of phenol. Moreover, the optimum condition of polymerization reactions was obtained via a study of the model compound synthesis. All of the resulting polymers were characterized by Fourier transform infrared and ¹H NMR spectroscopy and elemental analysis. The ultraviolet λ_max values of the poly(ester‐imide)s were also determined. All of the resulting polymers exhibited excellent solubility in common organic solvents, such as pyridine, chloroform, tetrahydrofuran, and m‐cresol, as well as in polar organic solvents, such as N‐methyl‐2‐pyrrolidone, N,N‐dimethylacetamide, N,N‐dimethylformamide, and dimethyl sulfoxide. The crystalline nature of the polymers obtained was evaluated by means of wide‐angle X‐ray diffraction. The resulting poly(ester‐imide)s showed nearly an amorphous nature, except poly(ester‐imide) derived from 4,4′‐dihydroxy biphenyl. The glass transition temperatures (T_g) of the polymers determined by differential scanning calorimetry thermograms were in the range 298–342 °C. The 10% weight loss temperatures (T_10%) from thermogravimetric analysis curves were found to be in the range 433–471 °C in nitrogen. Films of the polymers were also prepared by casting the solutions. Copyright © 2006 Society of Chemical Industry     

Preparation and properties of a novel polytriazole resin

A novel polytriazole resin prepared from p‐xylylene diazide (XDA) and N,N,N′,N′‐tetrapropargyl‐p,p′‐diaminodiphenylmethane (TPDDM) was synthesized and characterized. The resin is soluble in common solvents like acetone. The results show that the polytriazole resin can be cured at 70°C. The glass transition temperature and thermal decomposition temperature of the cured resin are 218 and 350°C, respectively. The tensile and flexural strengths of the cured resin achieve 99.0 and 200 MPa, respectively. It is potential as a low cost and easy processing thermal resistant polymer matrix for advanced composite applications. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1038–1042, 2007     

Poly(1,3‐disila‐1,3‐diphenyl‐2‐oxaindane)‐diphenylsiloxane‐poly(dimethylsiloxane) block copolymers

The heterofunctional condensation of 1,3‐dichloro‐1,3‐disila‐1,3‐diphenyl‐2‐oxaindane with dihydroxydiphenylsilane at various ratios of initial compounds in the presence of amines was carried out, and α,ω‐dihydroxy(1,3‐disila‐1,3‐diphenyl‐2‐oxaindane)‐diphenylsiloxane oligomers with various degrees of condensation were obtained. Corresponding block copolymers were obtained by heterofunctional polycondensation of synthesized α,ω‐dihydroxy(1,3‐disila‐1,3‐diphenyl‐2‐oxaindane)‐diphenylsiloxane oligomers with α,ω‐dichlorodimethylsiloxanes in the presence of amines. Thermogravimetry, gel permeation chromatography, differential scanning calorimetry, and wide‐angle X‐ray analysis were carried out on the synthesized block coplymers. Differential scanning calorimetry and wide‐angle X‐ray studies of these copolymers showed that their properties were determined by the ratio of the lengths of the flexible linear poly(dimethylsiloxane) and rigid poly(1,3‐disila‐1,3‐diphenyl‐2‐oxaindane)‐diphenylsiloxane fragments in the main macromolecular chain. Two‐phase systems were obtained with specific flexible and rigid fragment length values in synthesized block copolymers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3462–3467, 2006