4，4’——二溴甲基二苯醚的合成

报道了以对氯甲苯和对甲苯酚为主要原料，经过常压下的Williamm反应和与NSB的自由基溴化反应，合成4，4’——二溴甲基二苯醚的方法，经元素分析和^1HNMR对产物结构进行了确认。实验考察了催化剂、反应温度和反应时间等对收率的影响。两步反应产物总收率达64％。     

溴合二氧六环同苯酚溴化反应条件的研究

对文献报道的制备方法进行了改进。在激烈搅拌下将液溴滴加至等摩尔量的二氧六环中,直至完全固化,用乙醚溶解固体产物,再同苯酚进行溴化反应,同时考察了反应条件对反应的影响。反应产物以对澳苯酚为主,其最高收率可达91.4%。     

4-二乙（甲）胺基苯甲醛溴代反应研究

以NBS为溴代剂,使用单因素法考察原料比、反应时间、反应温度和反应溶剂等工艺条件对4-二乙（甲）胺基苯甲醛溴代反应收率的影响,并对其合成工艺进行了优化。使用核磁、GC-MS、红外等对产物结构进行确认和表征,同时测定了固体产物的熔点。实验发现4-二乙（甲）胺基苯甲醛在溴代反应中,伴随着甲基或乙基的断裂。     

3,6-二溴-9-(4-溴苯基)-9H-咔唑的合成

以咔唑为原料,经两步反应和一锅法分别合成目标产物3,6-二溴-9-(4-溴苯基)-9H-咔唑。N-芳基化反应和N-溴代丁二酰亚胺(NBS)的亲电取代反应均采用N,N-二甲基甲酰胺做溶剂,并使用将反应母液加入甲醇的方法,以69.6%的收率得到目标产物3,6-二溴-9-(4-溴苯基)-9H-咔唑。     

2,2′,6,6′-四甲氧基-4,4′-二(二苯基氧膦)-3,3′-联吡啶的合成

以2,6 二氯吡啶为起始原料,首先合成了2,6 二甲氧基吡啶,而后经过-20～-40℃下吡啶环的溴化反应,合成了中间产物2,6 二甲氧基 3 溴吡啶,收率为74 8%;进而,在-78℃条件下利用Ph2PCl作为亲电试剂进行亲电取代反应制备了中间产物2,6 二甲氧基 3 溴 4 二苯基膦吡啶,收率为77 4%;最后,利用0℃下三价膦的氧化反应合成了2,6 二甲氧基 3 溴 4 二苯基氧膦吡啶及150℃下吡啶环的偶合反应,合成出了目标产物2,2′,6,6′ 四甲氧基 4,4′ 二(二苯基氧膦) 3,3′ 联吡啶,收率分别为95 3%和62 5%,整个合成过程的总收率为27 8%。在合成过程中采用氢谱、碳谱等核磁共振方法鉴定了一些重要中间产物和目标产物的分子结构。     

五溴苄基溴的合成及表征

以五溴甲苯和溴为原料,合成了五溴苄基溴。考察了原料配比、反应温度及反应时间对反应收率的影响,确定的最佳反应条件为:n(溴)∶n(五溴甲苯)=1.4∶1,反应温度80℃,反应时间2 h,收率达88.5%。并用IR,1HNMR和DSC对产物结构进行了表征。     

溴代丙酮酸的合成研究

本文对丙酮酸的溴代反应进行了探讨,选择不同的条件,比较其对反应速度和产物的产率影响,从而找到最佳实验方案,得到超过文献值的最好收率96％～98％。     

溴硝醇的合成研究

以硝基甲烷和甲醛为原料 ,在碱性条件下经烷羟基化和溴化两步反应合成了溴硝醇。考察了反应温度、反应时间、溶剂中水与醇的体积比以及溶剂用量对产品收率的影响。最佳反应条件为 :V(水 )∶V(醇 ) =0 4∶1 0 ,V(溶剂 )∶V(反应原料 ) =2 1∶1 0 ,烷羟基化反应时间为 1 5h ,反应温度为 5℃ ;溴化反应时间为 0 5h ,反应温度为 10℃。产品收率可达到 78% ,质量分数为98%。产物经高效液相色谱、红外、质谱确证。     

五氟溴苯合成工艺研究

五氟溴苯是一种非常重要的化工中间体,五氟苯甲酸通过脱羧、溴化两步反应最终可得到五氟溴苯,分别研究了脱羧和溴化反应中各反应条件对目的产物收率的影响.     

4-叔丁基邻苯二甲腈的合成

以叔丁基苯为原料经溴化、氰基化合成4-叔丁基邻苯二甲腈,优化了反应条件。溴化45℃下反应4小时,收率74.6％。氰化反应摩尔比为溴化物:CuCN:PTC=1:2.9:0.05,反应温度165℃,反应时间4小时,收率60.9％。     

Gas chromatographic determination of biphenyl and phenyl ether in oil

Oils containing 0~100 ppm biphenyl and phenyl ether were analyzed by a new gas chromatographic method. Correlation coefficients (r) between gas chromatographic peak heights and biphenyl and phenyl ether concentrations were 0.99 and 0.98, respectively. As little as 5 ppm biphenyl and phenyl ether in oils could be determined rapidly and efficiently in 90 min by this new method.     

固体环氧树脂水性涂料的研制

利用双酚A型固体环氧树脂、二乙烯三胺、三乙烯四胺、正丁基缩水甘油醚和聚乙二醇二缩水甘油醚合成了自乳化环氧树脂乳液和水溶性固化剂。并制备了水性环氧树脂涂料,考察了水性环氧树脂的稳定性和涂料组分对性能的影响。     

4,4''-双(氯甲基)联苯的合成综述

简要介绍了4，4’-双(氯甲基)联苯(BCMB)的用途、性质及其合成特点。以列表的方式综述了以多聚甲醛，联苯等为原料，氯化锌为催化剂经氯甲基化反应制备BCMB的合成和后处理技术。依据催化剂特性和相关反应理论，重点分析了催化剂和催化机理及关注点，讨论了反应温度和反应时间之间的关系及后处理和二氯甲醚的去除。最后，对BCMB今后的合成研究提出了建议。     

Sulphonated Biphenylated Poly(aryl ether ketone)s for Fuel Cell Applications

New series of fully aromatic poly(ether ketone)s with a biphenyl pendant groups were synthesised. A direct comparison of sulphonation reaction among monophenylated poly(ether ether ketone) (Ph‐PEEK), biphenylated poly(ether ether ketone) (BiPh‐PEEK) and PEEK (Victrex) was thoroughly investigated. Several advantages of the pendant‐phenyl poly(ether ketone)s compared with commercial PEEK were identified, including ready control over the site of sulphonation and degree of sulphonation (DS), and mild and rapid sulphonation. The basic membrane physical properties comprising of thermal and mechanical properties, dimensional stability and proton conductivity were studied. One new membrane, sulphonated biphenylated poly(ether ether ketone) (BiPh‐SPEEKDK) having a good combination of membrane properties was fabricated into a membrane electrode assembly (MEA), and it showed excellent direct methanol fuel cell (DMFC) performance.     

Reaction rate enhancement during swollen-state polymerization of poly(ethylene terephthalate)

Experimental data are obtained for the extent of swelling and progress of the step-growth swollen-state polymerization (SwSP) of polyethylene terephthalate (PET). The SwSP is carried out in biphenyl and diphenyl ether mixture (26 : 74 w/w) solvent under appropriate conditions designed to understand the factors responsible for enhanced reaction rates. The kinetics rate constants, evaluated in terms of simple model, are found to be 2.5–5 times higher for SwSP as compared to the solid-state polymerization (SSP). As the diffusional/mass transfer effects are eliminated in our experiments, this increase in rate constants can be attributed to increased mobility of reactive chain ends. Polymerization rate is found to be further enhanced by addition of a polycondensation catalyst (Sb₂O₃) to the solvent during SwSP. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1589–1595, 1998     

Magnolia virginiana Neolignan compounds as chemical barriers to swallowtail butterfly host use

The role of toxins and deterrents in preventingtroilus group species (Lepidoptera, Papilionidae) from feeding on magnoliaceous hosts was investigated using bioassay-directed isolation ofMagnolia virginiana allelochemicals. A fraction consisting of three neolignan compounds significantly reduced survival of first instarP. palamedes, atroilus group member. Two of these compounds, magnolol and a biphenyl ether, were tested individually and were both toxic toP. palamedes. The larval survival ofP. troilus, anothertroilus group species, was also significantly reduced by magnolol but not by the biphenyl ether. In contrast,P. glaucus, a polyphagousglaucus group species that feeds on magnoliaceous hosts, was not affected by either compound. The effect of these compounds against a. polyphagous nonpapilionid was examined using the fall webworm (Hyphantria cunea, Lepidoptera: Arctiidae). The biphenyl ether but not magnolol significantly lowered webworm first-instar survival, demonstrating that polyphagy does not preadapt lepidopterans to feeding on this neolignan. These results demonstrate that although phagostimulants play a role in the specialization of thetroilus group on the Lauraceae, the presence of toxins and/or deterrents in nonhosts is also important in determining food plant patterns in these species.     

Mechanical and Thermal Properties of Poly(phthalazinone biphenyl ether sulfone)/PEEK Blends

A series of blends with various compositions are prepared by melt extrusion on the basis of novel copoly(phthalazinone biphenyl ether sulfone) (PPBES) and poly(ether ether ketone) (PEEK). The melt flowability, mechanical and thermal properties of the blends are studied. The results show that the incorporated PEEK has a large influence on the melt viscosity and thermal stability of blends. The tensile strength of the blends remains at about 90 MPa at room temperature; PPBES improves the mechanical properties of PEEK at 150°C. The flexural strength and modulus of the PPBES/PEEK blends also increase with the addition of PEEK.     

Comparative Detoxification of Plant (Magnolia virginiana) Allelochemicals by Generalist and Specialist Saturniid Silkmoths

The foliage of sweetbay magnolia (Magnolia virginana) contains at least two biologically active phenylpropanoid compounds (magnolol and a biphenyl ether) that are toxic to a number of generalist insect herbivores. These compounds have little effect on caterpillars of the sweetbay silkmoth, C. securifera, which is a specialist on sweetbay, but they are toxic to two closely related silkmoths, C. angulifera and C. promethea. To understand the influence of phytochemistry on the evolution of host use and feeding specialization in Callosamia, the detoxification capability of C. securifera was compared with that of C. angulifera and C. promethea. Degradation of magnolol and the biphenyl ether by midgut homogenate of the sweetbay specialist was NADPH-dependent and inhibited by piperonyl butoxide, suggesting the involvement of cytochrome P-450 detoxification enzymes. Both were degraded three times faster in the specialist compared to the unadapted herbivores. Higher rates of degradation could not be induced in the polyphagous C. promethea by a mixture of magnolol and the biphenyl ether or by the P-450 inducer pentamethylbenzene, nor did activity vary significantly when larvae were reared on different host plants. Use of sweetbay by Callosamia silkmoths appears to be dependent on their ability to degrade host toxins rapidly via midgut detoxification enzymes. Moreover, the intraspecific comparisons contradict the common prediction that higher levels of cytochrome P-450 activity are found in more polyphagous species; instead, P-450 activity is more closely associated with specific chemical attributes of the herbivores' host plants.     

N,O-Diarylation of N-Hydroxycarbamates. Rearrangement and Cleavage Reactions of the Intermediate N,O-Diarylhydroxylamines

The reactions of benzyl N-hydroxycarbamate with 2- and 4-nitrofluorobenzene yielded the corresponding benzyl N-(nitrophenoxy)carbamates. Their reaction with nitrofluorobenzenes yielded derivatives of biphenyl and of diphenyl ether. The formation of these products has been rationalized by assuming the existence of N,O-diphenylhydroxylamines as intermediates which undergo rearrangement analogous to the benzidine rearrangement.     

Kinetics of isothermal and nonisothermal crystallization of novel poly(arylene ether ether sulfide)s

The kinetics of crystallization have been studied for a series of novel poly(ether ether sulfide)s based on a biphenyl moiety in the backbone (M_n = 14.3K, 19.1K), referred to as biphenyl sulfide (T_g = 142°C, T_m = 347°C) and phenyl moieties in the backbone (M_n = 8.1K, 19.9K, 34K), referred to as phenyl sulfide (T_g = 100°C, T_m = 243°C). Isothermal melt crystallization kinetics were analyzed based on the Avrami equation. Avrami exponents close to three were obtained for the phenyl sulfides, independent of molecular weight or crystallization temperature, which implies growth of three-dimensional spherulitic superstructures following heterogeneous nucleation. For the biphenyl sulfides, values closer to 2 were obtained for the exponent, also independent of molecular weight or crystallization temperature, which could imply the incomplete development of three-dimensional superstructures following heterogeneous nucleation. Nonisothermal crystallization kinetics were also studied by cooling from the melt; in all cases studied, the Ozawa analysis could not well describe the evolution of crystallinity, probably because of the inapplicability of some of the inherent assumptions in this type of analysis. The data were analyzed using the conventional form of the Avrami equation, which yielded good fits. This semiquantitative method of analysis yields a reduced rate constant that was found to increase with increasing cooling rate and decreasing molecular weight. The results of the isothermal and nonisothermal crystallization studies carried out on the poly(ether ether sulfide)s have been compared wherever possible to the results available for PPS and PEEK.