1,2-二[4-(2-溴乙氧基)-1-萘氧基]乙烷的结构及其卡宾前体的合成

以1,4-萘醌为原料采用Schlenk技术合成了非预期产物1,2-二[4-(2-溴乙氧基)-1-萘氧基]乙烷,利用1H NMR、13C NMR,尤其是借助DEPT和HSQC谱对其进行了结构确证.该化合物与1-甲基咪唑反应,得到一个新型卡宾前体1,2-双[4-(1-甲基-3-咪唑乙氧基)-1-萘氧基]乙烷六氟合磷酸盐,并利用1H NMR和ESI-MS进行了结构表征,进一步确证了1,2-二[4-(2-溴乙氧基)-1-萘氧基]乙烷的结构.     

基于RAFT聚合的蜂窝状有序多孔膜的制备及表征

以苯乙烯为单体,S,S′-(a, a′-二甲基-a″-乙酸)三硫代碳酸酯(BDAAT)为链转移剂,偶氮二异丁腈(AIBN)为引发剂,进行苯乙烯(St)的可逆加成——断裂链转移(RAFT)自由基聚合,同时以传统的自由基本体聚合方法制备聚苯乙烯(PS)。然后以两种方法制备的PS和聚乙二醇(PEG)为成膜物质,通过水滴模板法在高湿氮气下制备了微观多孔膜。探讨了聚苯乙烯多孔膜的形成机理,研究了聚合方式、聚合物溶液质量分数及溶剂的挥发性等对微观多孔膜结构的影响。研究结果表明,多孔薄膜的形貌受线性聚合物的末端基团以及亲水性物质等综合因素的影响,膜孔径随聚合物溶液质量分数的增大而减小。     

Synthesis and characterization of soluble aromatic azopolyamides containing sulfone and ether units

A series of new polyamides 3a–d containing aryl-azo, ether and sulfone groups in the main chain were synthesized from bis[4-(4-aminophenoxy)phenyl sulfone] 1 and several azo aromatic diacyl chlorides 2a–d by the low temperature solution polycondensation technique. FTIR spectroscopy, nuclear magnetic resonance (NMR) and elemental analyses confirmed the structure of these polymers. Owing to the aryl and amide groups in the main chain, these polymers exhibit photochromic properties as well as excellent thermal stabilities. The transition temperatures (T _g) are between 242 and 265 °C, and the char yields at 800 °C in nitrogen atmosphere were above 39%. Based on incorporation of flexible ether linkages and polar sulfone groups, the polyamides show desirable solubility in organic solvents such as DMAc, N,N-dimethylformamide (DMF), N-methyl-2-pyrroidinone (NMP) and dimethylsulfoxide (DMSO). And it is exemplified that polyamide containing 2 and 2′ substitutes performed better solubility. Funded by the National Natural Science Foundation of China (No. 50572081)     

Co-precipitation/hydrothermal synthesis of BiFeO<Subscript>3</Subscript> powder

A coprecipitation/hydrothermal route was utilized to fabricate pure phase BiFeO3 powders using FeCl3·6H2O and Bi（NO3）3·5H2O as starting materials, ammonia as precipitant and NaOH as mineralizer. The synthesized powders were characterized by XRD, SEM and DSC-TG analysis. In the process, single-phase BiFeO3 powders could be obtained at a hydrothermal reaction temperature of 180 ℃, with NaOH of 0.15 mol/L, in contrast to 200 ℃ and 4 mol/L for conventional hydrothermal route. Meanwhile, the micro-morphology of synthesized BiFeO3 powders changed with different reaction temperatures and concentrations of NaOH. The N6el temperature, Curie temperature and decomposition temperature of the synthesized BiFeO3 powders were detected to be 301 ℃, 828 ℃ and 964 ℃, respectively. The hydrothermal reactions mechanism to fabricate BiFeO3 powders were discussed based on the in-situ transformation process.     

Synthesis, characterization and protonation study of novel poly(thioether imide)s based on aromatic heterocyclic diimide

Novel poly(thioether imide)s were synthesized by 2,5-dimercapto-1,3,4-thiadiazole, and aromatic heterocyclic chlorodiimids through nucleophilic substitution reaction as alkali catalysts were presented. The poly(thioether imide)s exhibited good thermal property. The glass transition temperatures of polymers were around 373 ℃, and 10% weight loss temperatures were in the range of 450-500 ℃ in nitrogen/air atmosphere. Meanwhile, the chloroform dilute solutions of these polymers could show strong UV-vis absorption peaks at about 289 nm. After being protonated by inorganic acids (HCl), the new shoulder absorption peaks were observed at 350 nm. The PL absorption bands of polymer solutions were in the region of 350-550 nm, which showed the green-yellow fluorescence.     

1-苯基偶氮-2-萘酚和1-(2-硝基苯基偶氮)-2-萘酚的合成及光谱研究

以苯胺和邻硝基苯胺为原料,分别与2-萘酚发生重氮偶氮反应制得两个偶氮化合物(1：1-苯基偶氮-2-萘酚和2：1-(2-硝基苯基偶氮)-2-萘酚),用红外光谱表征其结构,并通过紫外光谱对化合物的光谱性质进行了研究。实验结果表明两个化合物均具有较大的摩尔吸光系数(1：ε_478nm = 1.49 × 10⁴ L/mol·cm;2：ε_329nm = 1.32 × 10⁴ L/mol·cm),在溶液pH小于10时紫外光谱基本不变,在强碱性范围内紫外谱图有变化,表现出一定的酸碱变色性。     

Synthesis and characterization of photosensitive poly(imide sulfonates) for fuel cell application

The novel sulfonated polyimide membranes were successfully synthesized by thermal imidization with monomers of 4,4’-(hexafluoroisopropylidene)diphthalic anhydride (6FDA), 4,4’-diamino-diphenyl ether-2,2’-disulfonic acid (SODA) and 3,3’-diaminochalcone (3DAC). Photosensitive chalcone moiety was introduced to the main chain of copolymers, and the photocrosslinking of resulting copolymer in aqueous electrolyte was attempted. A series of sulfonated copolyimide precursors containing chalcone functional groups in the main chain were prepared with different sulfonation degrees by controlling the molar ratio of SODA, 6FDA and 3DAC. The polymer membranes were prepared from these sulfonated aromatic precursors by solution casting and subsequent thermal imidization. The crosslinking with UV irradiation was attempted in the presence or absence of distilled water. The characterizations of the resulting membrane such as the ion-exchange capacity, water absorption and ionic conductivity were performed with respect to the copolymer compositions and the photocrosslinking conditions.     

新型含非共轭单元的光伏材料的合成及表征

基于高性能半导体聚合物给体聚［（2,6-（4,8-双（5-（2-乙基己基）-噻吩-2-基）-苯并［1,2-b:4,5-b’］二噻吩））-alt-（5,5-（1’,3’-二-2-噻吩基）-5’,7’-双（2-乙基己基）苯并［1’,2’-c:4’,5’-c’］二噻吩-4,8-二酮）］（PBDB-T）,通过Stile偶联聚合反应,首次合成了一种含非共轭单元的新型聚合物给体材料聚［（2,6-（4,8-双（5-（2-乙基己基）-噻吩-2-基）-苯并［1,2-b:4,5-b’］二噻吩））-（5,5-（1’,3’-二-2-噻吩基）-5’,7’-双（2-乙基己基）苯并［1’,2’-c:4’,5’-c’］二噻吩-4,8-二酮）-1,3-双（2-噻吩基）丙烷］（PDBS-5）,并将其应用于有机太阳能电池。紫外-可见光谱表明:相比于PBDB-T,非共轭单元的引入降低了PDBS-5吸收光谱中堆积峰的吸收强度,表明分子间π-π堆积减弱;循环伏安测试表明非共轭单元的引入降低了聚合物的能级。基于PDBS-5:IT-4F共混膜制备出能量转换效率达到7.42%的有机太阳能电池。研究结果表明含非共轭单元的聚合物PDBS-5是有潜力的有机太阳能电池给体材料。     

Synthesis and characterization of 2-cetyl-3-20 keto acid(N-ethyl perfluorinated octyl sulfonamide) N-ethyl ester

2-Cetyl-3-20 keto acid(N-ethyl perfluorinated octyl sulfonamide) N- ethyl ester was synthesized by the reaction of N-ethyl-N-hydroxyethyl perfluorinated octyl sulfonamide and alky ketene dimer. The experimental results show that the yield of products can be 89% when the molar ratio of perfluorinated octyl sulfonamide to ketene dimer is 1:1.1 and the reaction lasts about four hours at 80 °C. The structure of the product was characterized by FTIR and ¹HNMR. The product can dissolve in polar solvents such as NMP, DMAC, THF, DMSO, CHCl₃, and 10% weight-loss temperature measured by TGA is 202 °C. Funded by the National High-Tech Foundation(No. 2003 AA305920)     

4,4′-双(苯并噁唑-2-基)二苯乙烯的合成

以对氯甲基苯甲酸、亚磷酸三乙酯、对醛基苯甲酸甲酯、邻氨基苯酚为原料,经酯化、缩合、环化三步反应合成了荧光增白剂双苯并唑二苯乙烯(OB-1),三步反应的总收率接近80%。用元素分析、红外光谱以及在DMF中的紫外吸收光谱对化合物的结构进行了表征,经HPLC测定,产品纯度大于99%。     

基于二氨基苯基卟啉的新型聚酰亚胺的合成与表征

卟啉类化合物的结构特征使其在很多领域受到广泛的关注,现在通常在卟啉上做修饰以获得更优的性能。以氨基苯基取代的卟啉化合物作为二胺单体和均苯四甲酸二酐为二酐单体,以苯甲酸为溶剂,通过反应合成粗产品新型的聚酰亚胺材料,用丙酮和氯仿洗涤得到纯产品,并进一步合成了Zn-卟啉聚酰亚胺。采用傅里叶红外吸收光谱、紫外-可见吸收光谱对产物进行了结构表征,对主要的紫外光谱、红外光谱吸收带进行了经验归属,以及原料与产物的对比分析,初步确定了合成产物的结构。结果表明,聚合产物是以卟啉骨架结构为主要聚合单元的聚酰亚胺类共聚物。     

丙烯酸十八酯的聚合反应动力学

用溶液聚合法合成聚丙烯酸十八酯,主要探讨了引发剂,单体,温度及溶剂对聚合反应速率的影响。由实验得到以下主要结论：丙烯酸十八酯在进行溶液聚合反应时,反应速率与单体浓度的一次方成正比,与引发剂的浓度的0．5次方成正比,聚合反应常数的指前因子Aa=123．4,活化能Ea=29.72kJ/mol,在实验条件下,溶剂结构对丙烯酸十八酯的聚合反应速率没有显的影响,聚合反应过程中,没有加速聚合现象;在聚合反应过程中,四咱溶剂链转移常数的次序为：四氯化碳＞三氯甲烷＞二氯甲烷＞甲苯。     

基于二氨基苯基卟啉的新型聚酰亚胺的合成与表征

卟啉类化合物的结构特征使其在很多领域受到广泛的关注,现在通常在卟啉上做修饰以获得更优的性能。以氨基苯基取代的卟啉化合物作为二胺单体和均苯四甲酸二酐为二酐单体,以苯甲酸为溶剂,通过反应合成粗产品新型的聚酰亚胺材料,用丙酮和氯仿洗涤得到纯产品,并进一步合成了Zn-卟啉聚酰亚胺。采用傅里叶红外吸收光谱、紫外-可见吸收光谱对产物进行了结构表征,对主要的紫外光谱、红外光谱吸收带进行了经验归属,以及原料与产物的对比分析,初步确定了合成产物的结构。结果表明,聚合产物是以卟啉骨架结构为主要聚合单元的聚酰亚胺类共聚物。     

Effect of water soluble PVA on the microstructure characteristics of C-S-H formed in Na<Subscript>2</Subscript>SiO<Subscript>3</Subscript>-Ca(NO<Subscript>3</Subscript>)<Subscript>2</Subscript> solution system

The structure characteristics of hydrated calcium silicate synthesized by solution reaction method with the existing of water soluble polymer polyvinyl alcohol(PVA)are investigated.Using Na 2 SO 3 and Ca(NO 3 ) 2 as the main raw materials,in the condition of 2%(in weight)addition of PVA and the water to solid ratio of 20,hydrated calcium silicate samples(Ca/Si=1.0 and 1.5)were prepared with 60℃water bath.IR,BET,XRD and SEM methods were used to study the microstructure of the hydration products.The results s...     

固相反应合成4,4′-硫代双(5-甲基-2-叔丁基苯酚)低聚物抗氧剂

以４,４′－硫代双（５－甲基－２－叔丁基苯酚）为原料,氯化铁作氧化偶联剂,在碳酸钠的存在下应用超声波辐射进行固相反应合成了４,４′－硫代双（５－甲基－２－叔丁基苯酚）低聚物抗氧剂（ＰＴＢＰ）,收率为９８．５％。ＰＴＢＰ合成条件为：４,４′－硫代双（５－甲基－２－叔丁基苯酚）：三氯化铁：碳酸钠（摩尔比）＝１：２：１,超声波频率３３ｋＨｚ,功率１５０Ｗ,反应时间３ｈ,反应温度２５～５０℃。以核磁共振谱（１３Ｃ－ＮＭＲ）、场解吸质谱（ＦＤ／ＭＳ）和元素分析对低聚物结构进行了表征。该方法无反应溶剂,设备空间利用率高,副产物少,产品颜色浅且无需精制     

3（5）-取代-1H-吡唑甲酸及其铜配合物合成与表征

以四种不同的酮类化合物及草酸二乙酯为原料,设计合成了四种3（5）-取代-1H-吡唑甲酸化合物,通过IR及^1H NMR对所合成的化合物结构进行了表征．化合物3a与金属铜离子配位,得到一个双核铜配合物晶体,该晶体属三斜晶系,空间群为P-1,晶胞参数为a=7．082（8）A,b=9．156（10）A,c=25．86（3）A,a=97．088（19）°,β=92．024（18）°,γ=112．649（13）°,V=1529（3）A3,Z=4,Dc=1．597g/cm^3,配合物的晶体结构进一步确证了所合成化合物结构的准确性．     

Effect of catalyst on structure of （PEO）8LiClO4-SiO2 composite polymer electrolyte films

（PEO）8LiClO4-SiO2 composite polymer electrolytes（CPEs） were prepared by in-situ reaction, in which ethyl-orthosilicate （TEOS） was catalyzed by HCl and NH3·H2O, respectively. The ionic conductivity, the contact angle and the morphology of inorganic particles in the CPEs were investigated by AC impedance spectra, contact angle method and TEM. The conductivities of acid-catalyzed CPE and alkali-catalyzed CPE are 2.2×10^-5 and 1.1×10^-5 S/cm respectively at 30 ℃. The results imply that the catalyst plays an important role in the structure of in-situ preparation of SiO2, and influences the surface energy and conductivity of CPE films directly. Meanwhile, the ionic conductivity is related to the surface energy.     

新型8-氨基喹啉衍生物的合成及其光电性质

以8-氨基喹啉为合成子,采用一锅法的合成方法,制备一种新型偶氮类化合物—1,2-偶氮-8-二喹啉。运用红外光谱、核磁共振谱表征该化合物的分子结构;并利用紫外-可见光谱和循环伏安法来探究它的光电性质,结果表明浓度为2×10-3mol/L时,(0.053,0.0102 V)是一对可逆的氧化还原峰。     

肼基吡啶类化合物合成

以氯代吡啶、水合肼等为原料,通过亲核取代反应制备一系列卤代肼基吡啶,其结构由1H NMR, 13C NMR进行表征。考察在相同反应条件下,不同氯代吡啶的转化率。指出合成3-氯-5-三氟甲基-2-肼基吡啶收率低的原因是产生了大量副产物5, 6-二氯-3-肼基吡啶。       

聚亚胺醇(醌)前驱体的合成、表征与机理分析

由傅-克酰基化反应合成了1,4-双-(4′-溴苯酰基)苯(1)。以(1)和苯胺为单体,通过钯催化的胺化反应合成了1,4-双-(4′-氨基苯酰基)苯(2),其中叔丁醇钠(NaOt-Bu)为基体,1.1′-联萘-2.2′-二苯膦(BINAP)为配体。以(2)和锂化苯为底物,通过亲核加成反应得到1,4-双-[苯基-(4′-苯氨基)醇基]苯(3),此反应通过锂化苯对(2)中羰基的攻击实现。对(3)进行消除反应得到1,4-双-[(4-苄叉基-环己基-2,5-二烯苄基)苯(4)的粗产物,由氯仿萃取得到紫色溶液,通过水洗,蒸发,真空干燥制得紫色粉末精制品(4)。