Isolation,spectra, structure,and ring-opening polymerization of strained macrocyclic aryl(ether ketone) dimer

Macrocyclic arylene ether ketone dimer was isolated from a mixture of cyclic oligomers obtained by the nucleophilic substitution reaction of bisphenol A and 4,4′-difluorobenzophenone and easily polymerized to high molecular weight linear poly-(ether ketone). The cyclic compound was characterized by FTIR, ¹H- and ¹³C-NMR, and single-crystal x-ray diffraction. Analysis of the spectral and crystal structure reveals extreme distortions of the phenyl rings attached to the isopropylidene center and of the turning points of the molecular polygons. The release of the ring strain on ring-opening combined with entropical difference between the linear polymer chain and the more rigid macrocycle at temperatures of polymerization may be the proposed motivating factors in the polymerization of this precursor to high molecular weight poly(ether ketone). © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 1753–1761, 1997     

Preparation and thermal properties of asymmetrically substituted poly(silylenemethylene)s

Poly(silylenemethylene)s of the types [SiMeRCH₂]_n and [SiHRCH₂]_n were prepared by the ring-opening polymerization (ROP) of 1,3-disilacyclobutanes (DSCBs) containing n-alkyl substituents, such as C₂H₅, n-C₃H₇, n-C₄H₉, n-C₅H₁₁, and n-C₆H₁₃, or a phenyl group on the Si. These new polymers include a monosilicon analog of poly(styrene), [SiHPhCH₂]_n. Improved synthesis routes to the DSCB monomers were developed which proceed through Grignard ring closure reactions on alkoxy-substituted chlorocarbosilanes. All of these asymmetrically substituted polymers were obtained in high molecular weight form, except for [SiHPhCH₂]_n. The configurations of all of the polymers were found to be atactic. The aryl-substituted polymers have higher glass transition temperatures (T_gs) and thermal stability than those of the alkyl-substituted poly(silylenemethylene)s. Unlike the polyolefins of the type [C(H)(R)CH₂]_n, where T_g drops continuously from R = Me to n-Hex, the T_gs of the n-C_nH_2n+1 (n = 2–6)-substituted [SiMeRCH₂]_n PSM's appear to reach a maximum (at −61°C) for the R = n-Pr-substituted polymer. Moreover, where it was possible to make direct comparisons among similarly substituted atactic polymers, all of the poly(silylenemethylene)s were found to have lower T_gs than their all-carbon analogs. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3193–3205, 1997     

光化学-荧光分析法研究——Ⅲ.片剂及注射液中安定的测定

本文提出了测定安定的光化学—荧光分析新方法。安定在含有十二烷基硫酸钠的稀硫酸介质中,经紫外光照射后,产物能发射荧光(=368nm,=476nm)。安定浓度在0～2.5μg/ml范围内,荧光强度与浓度成良好的线性关系。方法的相对标准偏差为1.5％,检出限为0.044μg/ml,可用于片剂及注射液中安定含量的测定。     

稳定回归法用于复方氯丙嗪片的测定

本文应用稳定回归法用于紫外重叠光谱的分析。以复方氯丙嗪为例,不经分离,测定了盐酸氯丙嗪和盐酸异丙嗪的含量。与最小二乘回归法比较,提高了测定结果的准确度和精密度。结果满意。     

铝(Ⅲ)-桑色素-十二烷基硫酸钠体系在滤纸基质的荧光反应研究及其分析应用

本文探讨了在滤纸基质上表面活性剂SLS对铝-桑色素荧光反应的增敏作用及最佳实验条件。铝含量在0～6.0ng范围的工作曲线呈良好的线性关系(r=0.9998),方法的检测限为0.001ng。含铝4.0ng的溶液11次测定结果的相对标准偏差为4.3％。方法用于含铝水样的测定获得满意结果,回收率为96.0～100.5％。     

一类新的表面活性剂——长链烷基三苯基鏻——Ⅵ.稳态荧光猝灭法测定十二烷基三苯基溴化鏻胶束的平均簇集数

研究了十二烷基三苯基溴化鏻(C_(12)PBr)胶束中N,N-二甲基苯胺(DMA)和二苯甲酮(DPK)对芘的荧光猝灭,发现DMA的猝灭行为不符合Stern-Volmer动态猝灭和Turro静态猝灭模型;DPK的猝灭行为不符合Stern-Volmer猝灭模型,但遵从Turro静态猝灭模型。根据DPK的静态猝灭性质测得C_(12)PBr胶束的平均簇集数为15士2,并相应地得到C_(12)PBr的临界胶束浓度为(1.77±0.09)×10~(-3)mol/L,后者与文献值一致。     

Multi-bond network hydrogels with robust mechanical and self-healable properties

Multi-bond network(MBN) which contains a single network with hierarchical cross-links is a suggested way to fabricate robust hydrogels. In order to reveal the roles of different cross-links with hierarchical bond energy in the MBN, here we fabricate poly(acrylic acid) physical hydrogels with dual bond network composed of ionic cross-links between carboxylFe3+ interactions and hydrogen bonds, and compare these dually cross-linked hydrogels with singly and ternarily cross-linked hydrogels. Simple models are employed to predict the tensile property, and the results confirm that the multi-bond network with hierarchical distribution in the bond energy of cross-links endows hydrogel with effective energy-dissipating mechanism. Moreover, the dually cross-linked MBN gels exhibit excellent mechanical properties(tensile strength up to 500 k Pa, elongation at break ~ 2400%) and complete self-healing after being kept at 50 °C for 48 h. The factors on promoting self-healing are deeply explored and the dynamic multi-bonds are regarded to trigger the self-healing along with the mutual diffusion of long polymer chains and ferric ions.     

无粘结剂ZSM-11催化剂上异丁烯直接胺化生成叔丁胺

叔丁胺是一种重要的化工原料和中间体,广泛应用于制备橡胶促进剂、医药、农药和着色剂等下游产品.异丁烯在分子筛催化剂上直接胺化生产叔丁胺是一个经济环保过程,其中ZSM-5和BEA分子筛的催化性能优于其它系列分子筛.ZSM-11与ZSM-5分子筛具有相似的孔道结构,我们以前的实验结果表明,与ZSM-5相比,ZSM-11表现出更优越的芳构化反应性能,在干气中乙烯低温芳构化方面也有明显优势.在此基础上,我们进行无粘结剂ZSM-11分子筛催化剂合成,并应用于异丁烯直接胺化生产叔丁胺反应.传统水热技术合成的分子筛通常为粉末,机械强度不能达到实际应用的要求,在工业化过程中分子筛粉末一般需要加入粘结剂成型使其具备一定的机械强度和形状,但是粘结剂会降低分子筛催化剂的活性和选择性,有可能会引发一些副反应,因此无粘结剂分子筛催化剂引起人们广泛关注.无粘结剂分子筛是指分子筛颗粒中不含惰性粘结剂或只含有少量粘结剂,主要依靠分子筛晶粒间的相互作用支撑存在,具有一定形状、尺寸和机械强度的催化材料.无粘结剂分子筛催化剂中分子筛含量较高,可利用的有效表面积较大,在离子交换及工业催化等方面具有明显优势.本文采用水热合成的ZSM-11分子筛原粉与二氧化硅机械混合(ZSM-11/SiO2=70/30)挤条后,通过气固相合成法制备了无粘结剂ZSM-11分子筛催化剂(Cat-C).作为对比,还分别制备了ZSM-11和SiO2机械混合(ZSM-11/SiO2=70/30)样品HZSM-11+SiO2及ZSM-11和氧化铝机械混合(ZSM-11/Al2O3=70/30)样品HZSM-11+Al2O3.利用X射线衍射、透射电镜、NH3程序升温脱附和吸附吡啶红外光谱等对分子筛催化剂的物理化学性能进行了表征.同时,以这些分子筛样品为催化剂,在固定床反应装置上进行了异丁烯胺化反应评价,反应条件为270℃,5.0 MPa,氨烯比为4和异丁烯空速0.5 h?1.结果表明,与HZSM-11+SiO2和HZSM-11+Al2O3相比,Cat-C上叔丁胺生成速率最高.关联催化剂物化性能和反应性能发现,催化剂孔道结构与叔丁胺生成并不存在明显的关联性,而较多的Br?nsted酸和较少的Lewis酸才是Cat-C具有良好反应性能的主要原因.具有一定机械强度的无粘结剂ZSM-11分子筛催化剂制备简单,在异丁烯直接胺化过程中叔丁胺生成速率高,具有很好的工业化应用前景.