6,7-二氨基-2-(2′,4′-二甲基)苯基-1H-苯并[de]异喹啉-1,3(2H)-二酮的合成

苊经发烟硝酸硝化，稀硝酸氧化得到６，７－二硝基－１Ｈ，３Ｈ－萘并［１，８－ｃｄ］吡喃－１，３－二酮，它与２，４－二甲基苯胺缩合后用氯化亚锡还原得到６，７－二氨基－２－（２′，４′－二甲基）苯基－１Ｈ－苯并［ｄｅ］异喹啉－１，３（２Ｈ）－二酮。与６－氨基－２－（２′，４′－二甲基）苯基－１Ｈ－苯并［ｄｅ］异喹啉－１，３（２Ｈ）－二酮（Ｃ．Ｉ．溶剂黄４４，或Ｃ．Ｉ．分散黄１１）相比，其在ＤＭＦ中的最大吸收波长红移了１７．６ｎｍ，最大荧光波长蓝移了４２．７ｎｍ，荧光量子产率有所增大。     

一种水不溶性聚季lin盐型杀菌剂及其制备

一种水不溶性聚季Ｌｉｎ盐型杀菌剂，是通过先在氯甲基化的树脂上固载烷基多胺，再通过Ｃ－Ｎ键固载季Ｌｉｎ盐官能团制得。其结构式为：「Ｐ」－ＣＨ２－「Ｙ」Ｍ－（）∈ＣＨ∈ｎＰ＋Ｒ１－Ｒ２－Ｒ３」ｋＸ＾－ａｋ／ａ其中（Ｐ）为树脂，Ｙ为Ｒ１′（ＮＣＨＣＨ２）ｘＨｘ－１ＮＲ２′，Ｒ１′、Ｒ２′中至少有一个为Ｃ６～Ｃ２０的烷基，另一个可以为Ｈ或Ｃ１～Ｃ６的烷基，Ｘ为１或２，Ｒ１、Ｒ２、Ｒ３为Ｃ１～Ｃ４的烷基，ｎ     

从丙烯二聚制4－甲基戊烯－1

用Ｎａ－Ｋ型催化剂，反应温度１４０～１６０℃，反应压力７０～１１０ｋｇ／ｃｍ￣２，液体空速２．０～１．０ｈ￣（－１）时，通过丙烯二聚可制得４－甲基戊烯－１。丙烯二聚反应的最优条件为反应温度１５０℃，反应压力１００ｋｇ／ｃｍ￣２，丙烯液体空速１．０ｈ￣（－１）。此时丙烯的转化率高于４６％，而４－甲基戊烯－１的选择性高于９１％。讨论了反应速度。     

1-氧-乙酰基-2,3,5-三-氧-苯甲酰基-4-(1′-胸腺嘧啶)-T-L-来苏糖的超声波化学合成

首次应用超声波新技术合成了１－氧－乙酰基－２，３，５－三－氧－苯甲酰基－４－（１′－胸腺嘧啶）－α－Ｌ－来苏糖，反应时间１．５ ｈ，产率５５％ ，和通常的化学合成方法比较反应速度和产率有较大的提高。     

4-甲基-2-己基-1,3-二噁戊烷的合成

在对甲苯磺酸和硫酸铝复合催化剂存在下,以正庚醛（Ａ）和１．２-丙二醇（Ｂ）为原料经脱水缩合合成了新型香料４－甲基－２－己基－１,３－二噁戊烷。优化试验结果表明：在ｎ（Ａ）： ｎ（Ｂ）＝１：１．１、催化剂用量为主原料总质量的０．３５％、反应时间为６ｈ、反应温度为９０～９８℃,产物收率达９４．２％。产物经理化检测和红外光谱确证。     

N,N′—1,2—双烷—双（5,6—二溴降冰片烷—2,3—二酰亚胺）的合成

以环戊二烯二聚体,顺丁烯二酸酐,溴,乙二胺为主要原料,经五步反应合成了Ｎ,Ｎ′－１,２－乙烷－双（５,６－二溴降冰片烷－２,３－二酰亚胺）（Ｉ）。其中前四步反应与文献（１）相同,第五步反应,取２２．５ｇＮ,Ｎ′－１,－２乙烷－双（５,６－二溴－３－羧基－降冰片烷－２－酰胺）（ＩＩ）于三口烧瓶中,加入８５ｍｌ二甲苯,３２ｍｌ丙酸,４滴磷酸,加热,搅拌回流脱水５ｈ,冷却,过滤,依次用甲苯－丙酸混合液和     

1-羟乙基-2-苯并咪唑氨基甲酸甲酯和1-乙基(2’一丙烯酸酯-1’-基)-2-苯并咪唑氨基甲酸甲酯的合成及用薄层一紫外分光光度法测定其含量

１－乙基（２’－丙烯酸酯－１’－基）－２－苯并咪唑氨基甲酸甲酯是合成多菌灵高 分子化学型缓释剂的重要单体。本文报道了１－乙基（２’－丙烯酸酯－１’－基）－２－苯并 咪唑氨基甲酸甲酯及其制备过程中的中间体－１－羟乙基－２－苯并咪唑氨基甲酸甲酯的 合成和分析方法。     

Alphabutol工艺乙烯二聚制丁烯－1技术的评析

Ａｌｐｈａｂｕｔｏｌ工艺技术是目前工业上由乙烯二聚制丁烯－１的主要工艺。本文介绍了这种工艺的反应机理、流程、特点和操作控制措施。评述了国内引进的这种工艺装置的考核及运行情况。还就工业生产丁烯－１两种主要工艺的流程、产品质量和投资等方面进行了对比和评价。     

新型磷-氮阻燃剂N,N′-双(2-氧-5,5-二甲基-1,3,2-二氧磷杂环己烷)-2,2′-间苯二胺的合成研究

以氯氧化磷、新戊二醇、间苯二胺等为原料合成了未见文献报道的Ｎ，Ｎ′－双（２－氧－５，５－二甲基－１，３，２－二氧磷杂环己烷）－２，２′－间苯二胺（二新戊二醇间苯二胺双膦酸酯），探讨出最佳工艺条件，并通过ＦＴＩＲ、１ＨＮＭＲ、元素分析验证了产物结构。     

有机闪烁剂2—（4′—叔丁基苯基）—5—4（4″—联苯基）恶二唑—1,3,4的合成…

本工艺首先合成联苯乙酮，联苯甲酸乙酯，再从对－叔丁基苯基酰氯合成Ｎ－（４－叔丁基苯甲酰基）－Ｎ－（４′－联苯基酰基）－肼，然后完成２－（４′－叔丁基苯基）－５－（４′－联苯基）恶二唑－１，３，４（以下间称Ｂｕ－ＰＢＤ）的合成。     

A new processable donor–acceptor polymer displaying neutral state yellow electrochromism

We report here the synthesis of a new solution processable neutral state yellow polymeric electrochromic material containing 2,5-bis-dithienyl-1H-pyrrole (SNS)-donor and 1,8 naphthalimide-acceptor (SNS–NI) as a subunit. The electrochemical and optical properties were investigated via cyclic voltammetry (CV), UV–Vis absorption and fluorescence emission measurements, respectively. Besides, electrochromic performance of poly(SNS–NI) has been compared to the both the film preparation method and poly(1-phenyl-2,5-dithiophen-2-ylpyrrole) [poly(SNS–P)] as a standard polymer. In the poly(SNS–NI), yellow color of the polymer film at neutral state converted to green and then dark blue upon the polymer film fully oxidized in the positive regime. SNS–NI polymer film prepared via spin casting process exhibits a high contrast ratio in the near-IR region (ΔT% = 56% at 890 nm), a response time of about 1 s, high coloration efficiency (299 cm² C⁻¹) and retained its performance by 98.6% even after 5000 cycles. Finally, the results clearly indicate that both electronic nature of the molecule and film preparation method have a major impact on electrochromic performance of these polymers.     

Proton conducting polymer blends from poly(2,5‐benzimidazole) and poly(2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid)

Proton conducting polymer electrolyte membranes were produced by blending of poly(2,5‐benzimidazole) (ABPBI) and poly(2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid) (PAMPS) at several stoichiometric ratios with respect to polymer repeating units. The membranes were characterized by using Fourier transform infrared spectroscopy for interpolymer interactions and scanning electron microscope for surface morphology. Thermal stability of the materials was investigated by thermogravimetric analysis. Glass transition temperatures of the samples were measured via differential scanning calorimetry. The spectroscopic measurements and water uptake studies indicate a complexation between ABPBI and PAMPS that inhibited polymer exclusion up on swelling in excess water. Proton conductivities of the anhydrous and humidified samples were measured using impedance spectroscopy. The proton conductivity of the humidified ABPBI:PAMPS (1 : 2) blend showed a proton conductivity of 0.1 S/cm, which is very close to Nafion 117, at 20°C at 50% relative humidity. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Polymerizations of nitrogen-containing heterophanes by vapor deposition method,transformation to polymeric films bearing a conjugated structure,and their properties

Summary The polymerizations of three nitrogen-containing heterophanes such as [2.2](2,5)pyridinophane (1), [2.2](2,5)pyrazinophane (2) and N, N-dimethyl-[2.2](2,5)pyrrolophane (3) by the vapor deposition method were carried out. Compounds1, 2 and3 gave poly(2,5-pyridinediyl-ethylene), poly(2,5-pyrazinediylethylene), and poly(N-methyl-2,5-pyrrolediyl-ethylene) as tough films, respectively. The transformation of the ethylene unit in the polymer films to the vinylene one by the dehydrogenation reaction using 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) failed in the former two polymeric films and succeded to a certain extent in the latter one. The electrical conductivity of a poly(N-methyl-2,5-pyrrolediyl-vinylene) film obtained by the dehydrogenation reaction was measured to be 4×10^-4 S/cm at room temperature and increased up to 1×10^-2 S/cm on doping with iodine.     

窄能隙共轭聚合物:聚{[(3-辛基)噻吩-2,5-二基][(对二甲氨基)苯甲烯]}的合成与表征

聚噻吩甲烯是一类具有极低能隙的共轭聚合物,为了提高其溶解性和成膜性,采用3 辛基噻吩与对二甲氨基苯甲醛进行聚合反应得到了聚(3 辛基)噻吩对二甲氨基苯甲烷(POTDMAB),然后在氧化剂四氯苯醌的作用下进行脱氢反应得到聚(3 辛基)噻吩对二甲氨基苯甲烯(POTDMABQ)。用红外光谱、紫外-可见吸收光谱对POTDMAB和POTDMABQ的结构进行了表征。红外光谱上1653cm-1处的小吸收峰,紫外-可见吸收光谱上450～600nm的吸收说明POTDMAB含有部分醌化的成分。与POTDMAB相比,POTDMABQ的红外谱图在1653cm-1处的吸收强度增加,紫外-可见吸收光谱上450～600nm吸收强度的增加以及核磁共振氢谱都说明了醌化反应的发生和共轭结构的形成。热重分析表明POTDMABQ在200℃以上开始分解。采用了两种模型对POTDMABQ薄膜的光学禁带宽度进行了测量,发现具有很低的禁带宽度,分别为1 32eV(r=1)和1 69eV(r=2),具有用作三阶非线性聚合物光学材料的潜在能力。     

Zur Synthese und Funktionalisierung neuer Poly[(silylen)‐2,5‐thiophene]

Treatment of 2,5‐dilithiothiophene with (dimethylamino) methylsilylbis(triflates) gave poly[(dimethylamino‐silylene)‐2,5‐thiophene] 4 in high yield. The amino–silyl bond was cleaved selectively by triflic acid leading to triflate substituted poly[(silylene)‐2,5‐thiophene] 5 . Conversions of this polymers with nucleophiles gave other functionalized derivatives 6 – 9 . Hydrosilylation reaction between silicon–vinyl and silicon–hydrogen derivatives results in polymer networks which may serve as interesting preceramic materials. The structures of the polymers were proven by NMR spectroscopy (²⁹Si, ¹³C, ¹H).     

Preparation of π-conjugated polymers consisting of 2-decylbenzimidazole and thiophene units and chemical properties of the polymers

Polycondensation by Stille coupling of 2-decyl-4,7-dibromobenzimidazoles and N-methyl-2-decyl-4,7-dibromobenzimidazole with 2,5-bis(trimethylstannyl)thiophene and 5,5′-bis(trimethylstannyl)-2,2′-bithiophene gave the corresponding π-conjugated polymers, poly(2-decylbenzimidazole-4,7-diyl-thiophene-2,5-diyl) 1b, poly(2-decylbenzimidazole-4,7-diyl-bithiophene-2,5-diyl) 1c and poly(N-methyl-2-decylbenzimidazole-4,7-diyl-thiophene-2,5-diyl) 2b, in 98-99% yields. The polymers 1b and 2b were fully soluble in CF₃COOH, and partially soluble in DMF (about 60 and 40% for 1b and 2b, respectively) and NMP (about 70 and 40%, respectively). The NMP soluble part of 1b and DMF soluble part of 2b gave values of 0.36 and 0.24 dl g⁻¹ in NMP and DMF, respectively. The DMF soluble part of 1b, 1c and 2b showed absorption peaks at about 458, 465 and 388 nm, respectively, in DMF. In an alkaline medium the absorption peaks of 1b and 1c are shifted to a longer wavelength by 92-101 nm; the observed shifts in the acidic medium and alkaline medium were much larger than those observed with usual benzimidazoles with low molecular weights. Packing structures of 1b, 1c and 2b are discussed based on their XRD patterns.     

Lithium secondary cells using LiX (X=ClO4, BF4) as electrolyte and poly(2,5-pyrrolylene) and poly(2,5-thienylene) as materials for positive electrodes

Repeated charge-discharge cycles of lithium secondary cells using poly(2,5-pyrrolylene) and poly(2,5-thienylene) on carbon fibre plates as the materials for positive electrodes have been tested. When the Li|LiBF₄|poly(2,5-pyrrolylene) secondary cell is charged and discharged at 0.1 mA cm^–2, it gives 91% current efficiency and 70% energy efficiency with an average discharging voltage of 2.75 V at the 9th charge-discharge cycle. This secondary cell has a theoretical energy density of 135 kW kg^–1 based on the energy stored and the weights of poly(2,5-pyrrolylene) and the active materials. The Li|LiClO₄|poly(2,5-thienylene) secondary cells show somewhat lower current efficiency and energy efficiency at the 9th charge-discharge cycle. The lithium cells using the polymers are rechargeable more than 50 times, but after about 50 cycles considerable lowering of the current efficiency and energy efficiency of the cells is observed, presumably due to degradation of the polymer.     

Optical‐limiting properties of poly(arylene ethynylenes) containing thiophene ring

Poly(arylene ethynylenes) containing thiophene ring were synthesized in good yield. In synthesis, pyridine was added to accelerate reaction owing to its phase transfer effect on CuI. The optical‐limiting properties of the prepared polymers were investigated with a Q‐switched Nd : YAG laser at 532 nm with 10‐ns pulse width. The experiments showed that the order of the optical‐limiting response of the polymers is poly(3‐hexyl‐2,5‐thienyleneethylene) (P3) > poly(2,5‐dihexyloxy‐1,4‐benzyleneethylene‐3‐hexyl‐2,5‐thienyleneethylene) (P2) > poly(9‐hexyl‐3,6‐carbazoleethylene‐3‐hexyl‐2,5‐thienyleneethylene) (P1). It can be understood well by the comparison of their conjugation length and D‐A structure. In addition, the results indicated that introducing the electron‐rich aromatic ring into the polymer backbone to enhance the D‐A structure would be an effective way to improve its optical‐limiting property. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 131–135, 2004     

The effect of annealing on tensile properties of injection molded biopolyesters based on 2,5-furandicarboxylic acid

In this study, we investigate four polyesters based on 2,5-furandicarboxylic acid and different diols including 1,2-ethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, and 1,6-hexylene glycol. Poly(ethylene 2,5-furanoate), poly(propylene 2,5-furanoate), poly(butylene 2,5-furanoate), and poly(hexylene 2,5-furanoate) (PHF) were characterized by thermogravimetric analysis, X-ray diffraction, differential scanning calorimeter, and tensile tests. In addition, the influence of annealing polyesters on their thermal and mechanical properties was investigated. For these reasons samples for the tensile test were prepared by injection molding. The tensile properties of injection molded samples were compared with samples that were additionally annealed after injection molding. All studied polyesters after heating treatment showed multiple melting behavior. The increase in the degree of crystallinity significantly influenced also the mechanical properties of the samples. It was found that the length of the aliphatic chain and degree of crystallinity plays a major role in the final properties of furan-based polyesters.     

N-（2-乙酰苯基）-2，5-二甲基吡咯的合成及其在卷烟加香中的应用研究

以邻氨基苯乙酮和2,5-己二酮为原料,通过Paal-Knorr反应合成了一种新型的N-取代吡咯衍生物N-（2-乙酰苯基）-2,5-二甲基吡咯。通过IR、^1H NMR、^13 CNMR、HRMS等波谱方法对产物结构进行了确证,并研究N-（2-乙酰苯基）-2,5-二甲基吡咯的热稳定性以及在300℃、600℃和900℃的热裂解行为。结果表明,温度对合成物质的热裂解产物种类和含量有较大影响．裂解产物主要包括邻氨基苯乙酮、吡啶衍生物、醇等,其中含有多种致香物质,能够有效改善卷烟吸味,增强烟香。