含功能性季铵盐三苯胺聚合物的合成与电致变色和非易失性记忆性能

通过4-(4-氨基苯氧基)吡啶与4,4'-二溴二苯醚或1,4-二溴苯的偶合反应(Buchwald-Hartwig),得到聚[(4-(吡啶-4-氧基)-p-苯氧基]三苯胺或聚[4-(吡啶-4-氧基)]三苯胺,再与3-(氯甲基)-5-[4-(三氟甲基)苯基]-1,2,4-噁二唑进行季铵化反应,得到含功能性季铵盐三苯胺聚合物:聚[N-对苯氧基-N-[4-O-[2-对三氟甲基苯基-(4-氯化吡啶盐)噁二唑]基]三苯胺(PTP3FQ)和聚[N-[4-O-[2-对三氟甲基苯基-(4-氯化吡啶盐)噁二唑]基]三苯胺(PP3FQ).用核磁氢谱和红外光谱表征了PTP3FQ和PP3FQ的结构,用热失重和循环伏安法测定了PTP3FQ和PP3FQ的热性能和电化学性能.结果表明,在不外加电解质情况下,PTP3FQ和PP3FQ利用自身的季铵盐离子表现出良好的电致变色性能;将PTP3FQ和PP3FQ制成Al/聚合物/ITO结构的记忆器件,由于噁二唑基团与三苯胺形成电荷转移络合物,使记忆器件表现出非易失性可擦写(Flash)存储特性,开关比高达10~3.     

含取代噁唑结构的新型吡唑肟衍生物的合成与生物活性

为了发现具有良好生物活性的吡唑肟化合物,以唑螨酯为先导化合物,在吡唑肟中引入取代噁唑结构,设计并制备了20个未见文献报道的新型吡唑肟衍生物,利用1H NMR,13C NMR和元素分析确证了目标产物的结构.生物活性测试结果显示,部分目标化合物在500和100μg/mL浓度下对粘虫或蚜虫表现出优良的杀虫活性,其中5-(3-氟苯氧基)-1,3-二甲基-1H-吡唑-4-甲酰基-O-{[5-(4-氯苯基)噁唑-2-基]甲基}肟(9j)、5-(4-氟苯氧基)-1,3-二甲基-1H-吡唑-4-甲酰基-O-{[5-(4-氯苯基)噁唑-2-基]甲基}肟(9k)、5-(4-叔丁基苯氧基)-1,3-二甲基-1H-吡唑-4-甲酰基-O-{[5-(4-氯苯基)噁唑-2-基]甲基}肟(9r)和5-(4-甲氧基苯氧基)-1,3-二甲基-1H-吡唑-4-甲酰基-O-{[5-(4-氯苯基)噁唑-2-基]甲基}肟(9s)在浓度为100μg/mL时对粘虫的防治效果均达100%,5-(4-溴苯氧基)-1,3-二甲基-1H-吡唑-4-甲酰基-O-{[5-(4-氟苯基)噁唑-2-基]甲基}肟(9g)和9s在浓度为100μg/mL时对蚜虫的杀灭活性均为100%.此外,化合物9s在500μg/mL时对朱砂叶螨的防治效果为70%.     

N-(2-(5-(3-溴-1-(3-氯吡啶-2-基)-1H-吡唑-5-基)-1,3,4-噁二唑-2-基)-4-氯-6-甲基苯基)酰胺类新化合物的合成及生物活性

以N-吡啶基吡唑甲酸和2-氨基-3-甲基苯甲酸为起始原料,经由亲核加成、环化和酰化等多步反应合成了一系列结构新颖的N-(2-(5-(3-溴-1-(3-氯吡啶-2-基)-1H-吡唑-5-基)-1,3,4-噁二唑-2-基)-4-氯-6-甲基苯基)酰胺类化合物.测试了所合成化合物的杀虫及抑菌活性,结果表明,新化合物大多化合物在200 mg·L^-1浓度下对东方粘虫(Mythimna separataWalker)具有一定的杀虫活性,尤其是N-(2-(5-(3-溴-1-(3-氯吡啶-2-基)-1H-吡唑-5-基)-1,3,4-噁二唑-2-基)-4-氯-6-甲基苯基)乙酰胺(8a)和N-(2-(5-(3-溴-1-(3-氯吡啶-2-基)-1H-吡唑-5-基)-1,3,4-噁二唑-2-基)-4-氯-6-甲基苯基)-3-氯-2,2-二甲基丙酰胺(8e)致死率可达70%;部分化合物在50 mg·L^-1浓度下对油菜菌核病菌的抑菌活性相对较好(54.5%~63.6%),优于triadimefon和chlorantraniliprole;部分化合物如N-(2-(5-(3-溴-1-(3-氯吡啶-2-基)-1H-吡唑-5-基)-1,3,4-噁二唑-2-基)-4-氯-6-甲基苯基)-3,3-二甲基丁酰胺80和N-(2-(5-(3-溴-1-(3-氯吡啶-2-基)-1H-吡唑-5-基)-1,3,4-噁二唑-2-基)-4-氯-6-甲基苯基)-4-氟苯甲酰胺(8h)对苹果轮纹病菌具有中等抑菌活性.值得注意的是,化合物8e的杀粘虫活性和对油菜菌核病菌的抑菌活性都较为突出,可用作新农药创制研究的新型参考结构.     

1-[3’-(4″-甲氧基苯基)-5’-甲基异噁唑-4’-甲酰基]-4-芳基氨基硫脲及其衍生物的合成

以3,5-二取代异噁唑-4-甲酰肼为基本原料制备关键中间体1-(3-对甲氧基苯基-5-甲基异噁唑-4-基)-4-芳基氨基硫脲(3a～3c);3在不同条件下经关环反应制得含有3,5-二取代异噁唑的2-芳氨基噻二唑(4a～4c),2-芳氨基噁二唑(5a～5c)和3-[3’-(4″-甲氧基苯基)-5’-甲基-异噁唑-4’-基)-4-芳基-1,2,4-三唑-5-硫酮(6a～6c);6与碘甲(乙)烷反应合成了4-芳基-5-[3’-(4″-甲氧基苯基)-5’-甲基异噁唑-4’-基]-3-甲(乙)硫基-1,2,4-三唑(7a～8c),其结构经1H NMR,IR,MS和元素分析表征,其中4,5,7和8未见文献报道。     

1-[3′-(4"-甲氧基苯基)-5′-甲基异噁唑-4′-甲酰基]-4-芳基氨基硫脲及其衍生物的合成

以3,5-二取代异噁唑-4-甲酰肼为基本原料制备关键中间体1-(3-对甲氧基苯基-5-甲基异噁唑-4-基)-4-芳基氨基硫脲(3a～3c);3在不同条件下经关环反应制得含有3,5-二取代异噁唑的2-芳氨基噻二唑(4a～4c),2-芳氨基噁二唑(5a～5c)和3-[3′-(4"-甲氧基苯基)-5′-甲基-异噁唑4′-基)-4-芳基-1,2,4-三唑-5-硫酮(6a～6c);6与碘甲(乙)烷反应合成了4-芳基-5-[3′-(4″-甲氧基苯基)-5′-甲基异噁唑-4′-基]-3-甲(乙)硫基-1,2,4-三唑(7a～8c),其结构经1H NMR,IR,MS和元素分析表征,其中4,5,7和8未见文献报道.     

对称4-枝和8-枝噁二唑衍生物的合成与荧光性质

采用Wittig-Horner和Heck反应合成了3个对称多枝[1,3,4]-噁二唑衍生物2,5-双{4-{4-[N,N-二(4-溴苯基)-氨基] 苯乙烯基}苯基}-1,3,4-噁二唑(BrPASPO), 2,5-双{4-{4-{N,N-二{4-{4-[5-(4-叔丁基苯基)-1,3,4-噁二唑基-2-]苯乙烯基}苯基}氨基}苯乙烯基}苯基}-1,3,4-噁二唑(TPASPO)和2,5-双{4-{4-{N,N-二{4-{3,5-二[5-(4-叔丁基苯基)-1,3,4-噁二唑基-2]-苯乙烯基}苯基}氨基}苯乙烯基}苯基}-1,3,4-噁二唑(OPASPO). 目标化合物的结构经过红外光谱、核磁共振氢谱、质谱和熔点确认. 在CH2Cl2溶液中三者的最大吸收波长分别在403 (BrPASPO), 408 (TPASPO)和409 nm (OPASPO), 荧光发射峰分别为495 (BrPASPO), 509 (TPASPO)和506 nm (OPASPO). 化合物TPASPO和OPASPO在CH2Cl2溶液中的荧光量子产率分别为0.47和0.45. 8枝化合物的荧光寿命高于4枝化合物. 对称多枝化合物具有很强的分子内电荷转移能力和荧光发射能力.     

2-(ω-联苯基多亚甲基)-5-联苯基噁唑-1,3和2-(ω-联苯基多亚甲基)-5-联苯基噁二唑-1,3,4的合成

继2,6-二取代苯并二噁唑、2,5-二取代噁唑和2,5-二取代噁二唑及1,4-二(苯并噁唑-1,3基-2)苯等系列化合物合成及光性能研究后,又合成了双荧光发色团化合物2-(ω-联苯基多亚甲基)-5-联苯基噁唑-1,3和2-(ω-联苯基多亚甲基)-5-联苯基噁二唑-1,3,4共七种化合物。     

2,4和8-支噁二唑衍生物的三光子吸收和三光子上转换荧光

用飞秒Ti:sapphire激光测定了3个对称噁二唑衍生物4-{N,N-双[4-(4-[5-(4-叔丁基苯基)-1,3,4-噁二唑-2]苯乙烯基)苯基]氨基}苯甲醛(Bis-oxa)、2,5-双{4-[2-N,N-双(4-{4-[5-(4-叔丁基苯基)-1,3,4-噁二唑-2]苯乙烯基}苯基)氨基苯乙烯基]苯基}-1,3,4-噁二唑(Quadri-oxa)和2,5-双(4-{2-N,N-双[({3,5-二[5-(4-叔丁基苯基)-1,3,4-噁二唑-2]苯基}乙烯基)苯基]氨基苯乙烯基}苯基)-1,3,4-噁二唑(Octu-oxa)的三光子吸收谱和三光子荧光光谱. 在1260 nm飞秒激光激发下, 2,4和8-支噁二唑衍生物的三光子吸收系数分别为5.0×10^-5, 10.0×10^-5和10.0×10^-5 cm³/GW², 三光子频率上转换荧光发射波长分别为533, 544和551 nm. 研究了多支化合物线性吸收和透过、单光子荧光及量子产率、荧光寿命、多光子荧光光谱和三光子吸收系数谱. 对称多支噁二唑衍生物具有很强的三光子吸收和上转换荧光性质.     

新型含异噁唑环的苯腙基吡唑酮与芳偶氮基吡唑酮衍生物的合成

以乙酰乙酸乙酯为起始原料,经四步反应制备了关键中间体3-甲基-5-苯基异嗯唑甲酰肼(2);2分别与取代苯腙基乙酰乙酸乙酯和取代苯腙基乙酰丙酮反应合成了一系列新型的1.(3′-甲基-5′-苯基-异噁唑4′-甲酰基)-3-甲基4-苯腙基吡唑酮和1-(3′-甲基-5′-苯基-异噁唑-4′-甲酰基)-3,5-二甲基4-芳偶氮基...     

新型含异噁唑环1,3,4-噁二唑啉衍生物的合成

以N-羟基-4-甲氧基苯甲醛肟氯化物为原料,经两步反应制得3-对甲氧基苯基-5-甲基-异噁唑-4-甲酰肼(3);3依次经缩合和环合反应合成了一系列新型的2-芳基3-乙酰基-5-(3-对甲氧基苯基-5-甲基-异噁唑-4-基)-Δ4-1,3,4-噁二唑啉衍生物,其结构经~1H NMR,13C NMR,IR,MS(EI)和元素分析表征。     

Synthesis and electropolymerization studies of non-aggregated (4-{3-[3-(dimethylamino,diethylamino)phenoxy]propoxy}phenyl)propanoxy substituted silicon naphthalocyanines

In this study, 3-(4-{3-[3-(dimethylamino)phenoxy]propoxy}phenyl)propan-1-ol, 3-(4-{3-[3-(diethylamino)phenoxy]propoxy}phenyl)propan-1-ol and axially disubstituted silicon naphthalocyanines (SiNc) bearing electropolymerizable bis-[(4-{3-[3-(dimethylamino)phenoxy]propoxy}phenyl)propanoxy] and bis-[(4-{3-[3-(diethylamino)phenoxy]propoxy}phenyl)propanoxy] units were synthesized for the first time. Aggregation behavior of SiNcs was examined in different solvents and concentrations in DMSO. In all solvents and concentrations, SiNcs were non-aggregated. Also, electrochemical studies of SiNcs were investigated by cyclic and square wave voltammetry. While SiNcs gave only naphthalocyanine-based reduction process during the cathodic potential scans, they were electropolymerized on the working electrode during the anodic potential scan because of the oxidative electropolymerization of (4-{3-[3-(dimethylamino)phenoxy]propoxy}phenyl)propanoxy and (4-{3-[3-(diethylamino)phenoxy]propoxy}phenyl)propanoxy groups on the substituents of the complexes.     

New polypyromellitimide films based on cyclotriphosphazene and bisaspartimide derived diamines

Three new thermally stable polypyromellitimide films were made by the thermal cyclodehydration of the corresponding polyamic acids obtained by the polymerization of pyromellitic dianhydride with 4,4′-bis{N²-[4-(4-aminobenzyl)phenyl]aspartimido} diphenylmethane, 4,4′-bis{N²-[4-(4-aminophenoxy)phenyl]aspartimido} diphenylether, and bis(4-aminophenoxy)tetrakis (4-phthalamic acid phenoxy)cyclotriphosphazene. The bis(4-aminophenoxy)tetrakis (4-phthalamic acid phenoxy)cyclotriphosphazene was obtained from hexakis(4-aminophenoxy)cyclotriphosphazene involving its reaction with phthalic anhydride. The structure of these materials and precursors were characterized by using Fourier-transform-infrared (FT–IR) and proton nuclear magnetic resonance spectroscopy. The thermal stabilities of the films were evaluated by the thermogravimetric analysis, showing char yields at 800°C ranging from 68% to 58% in a nitrogen atmosphere and 24% in air atmosphere.     

可自交联超支化聚醚醚酮的合成与热性能研究

近15年来,由于超支化聚合物所具有的三维椭球状结构,良好的溶解性,大量末端官能团等独特的物理、化学特性及其在涂料、添加剂、药物载体、基因载体、大分子建筑“砌块”、超分子科学等领域的潜在应用,已成为高分子研究领域的一个热点．超支化聚合物在光通讯及微电子等领域的应用也已引起人们广泛而高度的重视．聚合物具有良好的热稳定性及溶解性是作为微电子和光学集成线路所必需的．本文以含有大侧基的“功能性”A：单体2．（4-苯氧基苯基）．1,4．苯二酚（POP）与B单体1,3,5-三[（4．（4．氟苯酰基）苯氧基]苯进行缩聚反应,得到全芳结构超支化聚醚醚酮（HPOP-PEEK）．     

2,2'-联吡啶参与的分子梭合成与1H NMR研究

2-{2-[4-苯基-二(4-特丁基苯基)甲基]苯氧基}乙氧乙醇磺酸酯(1)与4,4'-联吡啶在乙腈中回流36 h, 随后通过阴离子交换得到N-{2-{2-[4-苯基-二(4-特丁基苯基)甲基]苯氧基}乙氧乙基}-4,4'-联吡啶六氟磷酸盐(3), 产率为93.4%. 3与4,4'-二(溴甲基)-2,2'-联吡啶在乙腈中、70 ℃下反应72 h, 生成哑铃型化合物5, 产率为45%. 5与冠醚BPP34C10在55 ℃下搅拌5 d, 得到分子梭6和7, 产率分别为42.3%和27.3%. ¹H NMR数据表明, 富电子冠醚BPP34C10与哑铃型组分上贫电子4,4'-联吡啶的非键作用使4,4'-联吡啶上氢的化学位移向高场有较大移动.     

Structural development of free or coordinated 4'-(4-pyridyl)-2,2':6',2'-terpyridine ligands through N-alkylation: new strategies for metallamacrocycle formation

A series of N-alkylated derivatives of [Ru(pytpy)(2)]2+ (pytpy=4'-(4-pyridyl)-2,2':6',2'-terpyridine) has been synthesised and characterised. These include both model and functionalised complexes that complement previously reported iron(II) analogues. Reaction of [Ru(pytpy)(2)]2+ with bis[4-(bromomethyl)phenyl]methane leads to the formation of a [2+2] ruthenamacrocycle. Related ferramacrocycles could not be accessed by this route, and instead were prepared in two steps by first reacting bis[4-(bromomethyl)phenyl]methane or 4,4'-bis(bromomethyl)biphenyl with two equivalents of pytpy, and then treating the resulting bis(N-alkylated) product with iron(II) salts.     

Thermal decomposition characteristics of Alder-ene adduct of diallyl bisphenol A novolac with bismaleimide: effect of stoichiometry, novolac molar mass and bismaleimide structure

The addition-cured blends of diallyl bisphenol A formaldehyde resin (ABPF) with various bismaleimides (BMIs) were evaluated for thermal stability and degradation behavior by thermogravimetric analysis (TGA). TGA of the blend of ABPF and 2,2-bis 4-[(4-maleimido phenoxy) phenyl] propane (BMIP) with varying maleimide to allylphenol stoichiometry indicated that the thermal stability of the system was only marginally improved by the increase in BMI stoichiometry in the blend. The effect of BMI structure on thermal stability was studied using four different BMIs, viz. bis (4-maleimido phenyl) methane (BMIM), bis (4-maleimido phenyl) ether (BMIE), bis (4-maleimido phenyl) sulfone (BMIS) and BMIP. TGA showed a two stage decomposition pattern for BMIS system and a single stage for all the other three. The thermograms of BMIM and BMIE were identical and superior to that of BMIS; the latter showing a relatively poor performance at lower temperatures. Compared to the BMI-adduct of monomeric diallyl bisphenol A (DABA), the polymeric analog viz. ABPF system exhibited better thermal stability. Non-isothermal kinetic analyses of the different systems showed the decomposition occurring in at least two kinetic steps. The computed activation energy exhibited a direct correlation to the relative thermal stability of the systems.     

Synthesis and properties of polyimides derived from bis-(Aminophenoxy) containing naphthalene, [Phenyl] propane and [Methyl] cyclohexane segment and 4, 4′-carbonyldiphthalic anhydride

ABSTRACT

Three wholly, semi aromatic and aliphatic-aromatic polyimides containing bis(phenoxy) naphthalene, bis[(phenoxy) phenyl] propane and bis(phenoxy-methyl) cyclohexane segments by the two-step procedure from 2, 7-bis(4-aminophenoxy) naphthalene (BAPON), 2, 2-bis[4-(4-aminophenoxy)phenyl]propane (BAPOP), 1, 4-bis (4-aminophenoxy methyl) cyclohexane (BAPMC) as a diamine and 4,4′-carbonyldiphthalic anhydride (CDPA) were prepared. The first step of this procedure including ring-opening polyaddition in a polar solvent to give poly(amic-acid)s, second step containing cyclodehydration reaction to form polyimides. Synthesized monomer and polyimides were characterized by FT-IR, ¹H NMR spectroscopy and elemental analyses (CHN) that obtained results gave the most powerful evidence. The polyimide synthesized from BAPON was characterized as semi-crystalline, whereas the other polyimides showed amorphous patterns by the x-ray diffraction studies. The inherent viscosity was ranging between 0.87–1.01 dL/g. Tensile strength, initial moduli, and elongation at break of the polyimide films ranged from 88–117 MPa, 1.98–2.32 GPa, and 5–8%, respectively. Thermogravimetric analysis in nitrogen atmosphere shows that these polymers having good stability, so 10% weight will be lost in the range of 500–630°C. The point of polyimide with BAPMC segment, is “adding of good thermal stability and processability” lower moisture absorption and dielectric constant (0.75% and 2.90).     

新型氯取代含杂萘联苯结构可溶性聚芳酰胺的合成、表征和性能

以类双酚单体4-(3-氯-4-羟基-苯基)-2H-二氮杂萘-1-酮(DHPZ-OC)和对氯苯腈为原料进行亲核取代反应合成二腈化合物4-[3-氯-4-(4-氰基苯氧基)苯基]-2-(4-氰基苯基)二氮杂萘-1-酮(),然后在碱性(KOH)条件下进行水解制得了一种新型的含氯取代杂萘联苯结构的芳香二酸,4-[3-氯-4-(4-羧基苯氧基)苯基]-2-(4-羧基苯基)二氮杂萘-1-酮().用新二酸与各种芳香二胺进行直接缩合聚合制得了一系列新型氯取代含杂萘联苯结构的聚芳酰胺,特性粘度可达1.23dL/g.用FTIR和¹HNMR研究了新型二酸单体及聚合物的结构.该类聚芳酰胺均可溶解于NMP,DMAc和DMSO等极性有机溶剂中,并且可浇铸成透明韧性膜,其玻璃化转变温度在291～332℃之间,10%的热失重温度在460℃以上.     

Calix[6]arene derivatives selectively functionalized at alternate sites on the smaller rim with 2-phenylpyridine and 2-fluorenylpyridine substituents to provide deep cavities

The synthesis is described of calix[6]arene derivatives 4, 9, and 14 functionalized at alternate sites on the smaller rim with 4'-(pyrid-2' '-yl)phenylmethoxy, (6'-phenylpyrid-3'-ylmethoxy), and {6'-[2-(9,9-di-n-hexylfluorenyl)]pyrid-3'-ylmethoxy} substituents, respectively. They were obtained by 3-fold reactions of 2-[4-(bromomethyl)phenyl]pyridine (3), 5-(bromomethyl)-2-phenylpyridine (8), and 5-(bromomethyl)-2-(9,9-di-n-hexylfluorenyl)pyridine (13) with the 1,3,5-trimethylether of the t-Bu-calix[6]arene in the presence of sodium hydride in THF in 56-75% yields. Detailed analysis of the 1H NMR spectra (including variable-temperature data for 4) has established that 4, 9, and 14 exist predominantly in the C3v cone conformation with minor Cs isomers also observed. The X-ray crystal structure of 4 reveals two molecules of similar cone conformation, with all three 4'-(pyrid-2' '-yl)phenylmethoxy substituents stretched in the axial direction. Molecule I has a dimeric capsule structure with (pyrid-2' '-yl)phenylmethoxy substituents of one molecule interpenetrating those of its inversion equivalent to form a deep enclosed intermolecular cavity, which contains a CH2Cl2 guest molecule. Molecule II forms no such pair: the intramolecular cavity is filled with solvent molecules.     

2-(p-氯苯)-5,8-二氢螺咪唑并〔2,1-b〕苯并〔d〕噻唑7(6H),1′-环己烷的合成及晶体结构

合成了2－（p-氯苯）-5，8-二氢螺咪唑并[2，1-b]苯并[d]噻唑7（6H），1’-环乙烷5，并测定了其晶体结构。晶体分子式晶体属单科晶系，空间群为结构的偏离因子分子结构中有一个大的平面部分，是由噻唑五员环（A）和咪唑五员环（B）构成。