Synthesis and Characterization of Polyesterimides Containing Ether Linkages

Abstract

Three novel dicarboxylic acids, bis-4,4′-[N-4(4′-hydroxycarbonyl phenyleneoxy) phthalimido] diphenyl sulfone, bis-4,4′-[N-4(4′-hydroxycarbonyl phenyleneoxy) phthalimido] diphenyl methane, and bis-4,4′-[N-4(4′-hydroxycarbonyl phenyleneoxy) phthalimido] diphenyl ether, were synthesized, and several polyesterimides were prepared from diacid chlorides and bisphenols by solution polycondensation. The polymers were obtained in 65–88% yield and had inherent viscosities in the 0.18 to 0.64 dL/g range. The polymers were characterized by IR, elemental analysis, x-ray, TGA, DSC, and solubility tests. All the polymers were readily soluble in polar aprotic solvents and had a 10% weight loss temperature above 375°C in nitrogen.     

Synthesis and Characterization of Organosoluble Polyimides Containing Pyridyl Moiety with Ether Linkages

Two novel diamine monomers, bis(4‐amino‐3,5‐dimethylphenyl)‐3‐pyridyl methane and bis(4‐aminophenoxy‐3,5‐dimethylphenyl)‐3‐pyridyl methane were synthesized. A series of pyridine containing aromatic polyimides derived from the diamines were synthesized through a typical two‐step polymerization method. Most of the polymers show good solubility in NMP, DMAc, DMF, DMSO and CHCl₃ at room temperature. These polyimides exhibit T_g in the range of 249–317°C and 10% wt loss (T₁₀) takes place in the range of 474–564°C in N₂ and 469–558°C in air. The polymers have tensile strength in the range of 88–96 MPa, elongation at break in the range of 8.5–12.5% and tensile modulus in the range of 1.5–2.1 GPa. These polyimides also have low dielectric constant (3.26–3.64 at 1 KHz and 3.24–3.61 at 10 KHz) and low moisture absorption (0.42–0.89%).     

含叔丁基、醚键和双酚A单元可溶性聚酰亚胺的合成与表征

通过分子设计合成了一种含叔丁基、醚键和双酚A单元的二胺单体2,2-二(3'-叔丁基-4'-氨基二苯醚-4-基)丙烷(4),然后将其与4种商品化的芳香二酐单体:联苯四羧酸二酐(BPDA)、二苯醚四酸二酐(OPDA)、二苯六氟异丙基四酸二酐(6FDA)和均苯四酸二酐(PMDA)经高温一步法制备了一系列新型聚酰亚胺(PI)树脂,并对它们的结构与性能进行了研究.结果表明,该系列PI在NMP、DMF、DMAc、THF和CHCl3等普通有机溶剂中具有良好的溶解性;玻璃化转变温度Tg(DSC)在265~302℃之间,5%热失重温度(N2氛围)在519℃以上;在400~760 nm可见光波长范围内,具有优异的光学透明性,透光率约等于或大于90%;PI的数均分子量(Mn,GPC)在1.90×10~4~3.90×10~4范围内,分子量分布(PDI)介于2.63~4.63之间,X-射线衍射(XRD)结果表明所得PI为无定形聚合物,吸水率低于0.5%.叔丁基、醚键和双酚A单元同时引入具有协同效应,可提高PI的溶解性和透明性,并保持PI原有良好的热稳定性、机械性能和较低的吸水率.     

Synthesis and Characterization of Poly（ether amide）s Containing Bisphthalazinone and Ether Linkages

A novel aromatic diacid, 4, 4′-bis[2-(4-carboxyphenyl)phthalazin- 1-one-4-yl]-bisphenyl ether III, containing bisphthalazinone and ether linkages was prepared from nucleophilic substitution of p-chlorobenzonitrile with the bisphenol-like monomer I, followed by alkaline hydrolysis of the intermediate dinitrile II. A series of poly(ether amide)s containing bisphthalazinone and ether linkages derived from diacid III and aromatic diamines were synthesized by one-step solution condensation polymerization using triphenyl phosphite and pyridine as condensing agents. Moreover, the properties of poly(ether amide)s including thermal stability,solubility and crystallinity were also studied.     

Synthesis and Characterization of Macrocycles Containing 1,3,4-Oxadiazole

The design of molecules with delocalized π-electronic structures which are useful as organic conductor and light-emitting diodes(LEDs) has attracted much attention.^[1-2] We have synthesized some conjugated Schiff base macrocycles containing 1,3,4-oxadiazole(such as compound 1) and after being doped with I₂,they showed electrical conductivity in the region of semiconductor.^[3] To continue this work and understand the relationship between molecular structure and solid state properties, we designed other conjugated schiff base macrocycle containing 1,3,4-oxadiazole.     

含均三嗪环氮杂环蕃合成与表征

环蕃具有空腔结构,从而显示出许多独特的性质,有很大的应用前景.为了做进一步的研究,用三聚氯氰、苯酚,甲醇钠、1,6-己二胺、4,4'-二氨基-二苯甲烷为原料,经多步取代合成了几种新的氮杂环蕃,并用1HNMR,IR,MALDI-TOF-MS和元素分析对其结构进行了表征.同时对实验中所用的溶剂、缚酸剂以及反应浓度都进行了实验探索,得到了反应的最佳条件.     

Synthesis and Characterization of Solid Supports Containing silicon

Combinatorial chemistry has been a new field of chemistry since 1990's.^[1][2] More than 90% of researchers play their emphases on the studies of the solid supports such as P-(CH₂)_n-N and P-(CH₂)_n-O(n=1,2,3), but only a couple researchers play their emphases on the studies of the P-(CH₂)_n-Si(n=1,2,3). Because of the characteristic of the Si-Ar bond, we devise a series of the solid supports containing Si-Ar bond.These solid supports containing silicon were synthesized in two methods. At the same time,we also synthesized the monomer of the solid supports containing silicon or tin. The structures of these compounds were characterized by IR, elemental analysis.The synthetic routes of the solid supports containing silicon are shown in scheme 1 and the synthetic routes of the monomer of the solid supports containing silicon or tin are shown in scheme 2.     

含咔唑生色团的聚磷腈的合成与表征

通过后重氮偶合方法制备了一种含咔唑双功能生色团的聚磷腈光折变高分子,并用1H-NMR3、1P-NMRI、R、UV-vis、GPC以及DSC、TG等测试手段对聚合物进行了分析和表征。1H-NMR、IR、UV-vis谱图表明对硝基偶氮苯基团连接在咔唑环上。31P-NMR谱图上的单峰说明聚二氯磷腈分子链上的氯已经全部被咔唑基团取代,而且后功能化反应条件没有破坏磷腈主链结构。GPC测得聚磷腈的Mw=1.28×104。热分析结果显示聚磷腈的Tg=20℃,并在300℃开始分解。     

含偶氮苯生色团的聚合物纳米微球的制备与表征

用质子化的4-乙烯基吡啶-丙烯腈无规共聚物(P4VP+-r-AN)与偶氮苯染料酸性间胺黄(MY)在水溶液中通过静电力作用制备了一种新型的侧链偶氮复合物(P4VP-r-AN/MY). 采用FTIR, UV-Vis, DSC, TEM和HRTEM-EDS研究了溶剂对P4VP-r-AN/MY聚集形态的影响, 并初步探讨了P4VP-r-AN/MY聚集体的形成过程及转变机理. 结果表明, P4VP-r-AN/MY在水溶液中聚集形成尺寸为10~250 nm的球形聚集体; 在DMF中, 球形聚集体解聚, 形成较为均匀的薄膜结构; 而向P4VP-r-AN/MY的N,N′-二甲基甲酰胺(DMF)中逐渐增加水的含量, P4VP-r-AN/MY又会重新聚集, 当含水量达到质量分数为62.5%时, P4VP-r-AN/MY聚集形成尺寸为30~200 nm的空心纳米球. 溶剂的组成(水和DMF的质量比)对P4VP-r-AN/MY聚集体形态起着至关重要的作用.     

Synthesis and Characterization of Polymers Containing Rare Earth Metals

Europium and terbium salts of methacrylic acid (MA) and octanoic acid (OCA) were prepared by a method similar to that described in the literature. Either Eu(MA)₃ or Tb(MA)₃ with three double bonds (C?C) was used as a crosslinker containing rare earth metal ions, but the octanoic acid salts were used as additives. The salts were dissolved in methacrylic acid (<20%) and then copolymerized with methyl methacrylate (>80%) using AIBN (0.2 wt%) as initiator. The two types of polymers, one containing Eu(MA)₃ or Tb(MA)₃ and the other with Eu(OCA)₃ or Tb(OCA)₃, were synthesized by bulk copolymerization in molds made of two glass plates and characterized. The fluorescence spectroscopy of these polymers under ultraviolet/visible excitation light was investigated. The fluorescence excitation and emission spectra of the polymers showed the characteristic spectra of the free Eu³⁺ or Tb³⁺. The fluorescence intensity of the rare earth metal ions increased with increasing rare earth metal content. Fluorescence measurements for Eu(MA)₃, Tb(MA)₃, and Eu(OCA)₃ polymers do not display fluorescence quenching behavior within the range of the rare earth metal content used in our experiments. But for Tb(OCA)₃ polymers, this phenomenon was observed, illustrating that ionic aggregates exist in Tb(OCA)₃ polymeric systems.     

含金属钌配合物的可溶性三元聚酰亚胺的合成与表征

通过改变与6FDA共缩聚的两种二胺单体的比例,在分子主链中引入具有庞大侧基的9,9-二苯基芴单元,然后和金属钌配合物进行配位,得剑了三个含金属钌配合物的三元聚酰哑胺BFPI-1-Ru,BFPI-2-Ru和BFPI-3-Ru.用元素分析、GPC、FT-IR、TG和UV-Vis等对其分子量、结构及性质进行了表征.结果表明,随9,9-二苯基芴单元含量的增加,含金属聚合物在低沸点溶剂CHCl_3和THF中的溶解性提高.所合成的含金属聚酰亚胺具有良好的热稳定性,在350～800nm较宽的紫外可见光区有良好的光吸收性质.     

Synthesis and Characterization of Biphenylene‐Containing Diazaacenes

We describe the efficient synthesis of substituted benzo[3,4]cyclobuta[1,2‐b]phenazine, benzo[3,4]cyclobuta[1,2]benzo[1,2‐i]phenazine, and benzo[3,4]cyclobuta[1,2‐b]naphtho[2,3‐i]phenazine by a condensation reaction of aromatic diamines with the stable biphenylene‐2,3‐dione.     

Synthesis and Characterization of Na And Mg Containing Carbonatefluorapatites

Abstract

The apatites were precipitated in an aqueous NH₄OH-NH₄NO₃ solution with pH 9–10 at temperatures 20°C and 80°C. The synthesized materials were studied by chemical and thermal analyses (TG/DTG/DTA, TG/ETIR-EGA), IR-spectroscopy, XRD-powder analysis and specific area measurements.     

含硫脲基不对称双席夫碱的合成与表征

通过二氨基硫脲与酮或不同的醛进行分步反应,合成了3种未见报道的不对称双席夫碱。其结构经IR,MS和元素分析确定。     

过氧铌杂多配合物位置异构体的合成、表征及催化性能

合成了6种钨硅杂多配合物异构体α、β_i-M₃H₂[SiW₁₁(NbO₂)O₃₉]·H₂O(M=Me₄N⁺(TMA),Bu₄N⁺(TBA),Et₄N⁺(TEA);β_i=β₁,β₂,β₃)。IR光谱、UV光谱、极谱、I^--S₂O₃^2-滴定证明合成的杂多配合物中有NbO₂基存在, ¹⁸³W NMR光谱证明其阴离子具有Keggin结构,催化实验结果表明,合成的化合物对烯烃环氧化反应具有催化活性,且过氧杂多配合物的催化活性高于非过氧杂多配合物,β异构体的催化活性高于α。     

Synthesis and Electrochemical Characterization of Azomethine Containing N-Ethylcarbazole Group

Conjugated aromatic azomethines containing a carbazole group were synthesized. Their structures have been confirmed by IR, MS and UV spectrometries. When iodine was used as the dope to the conjugated compounds, the electrical conductivities （EC） of the doped conjugated compounds were increased by several orders of magnitude. The thermal stability of these two compounds investigated by TGA shows a good result, which guarantees the correct result of EC when the compounds are heated. As can be seen from the CV characterization of the electrochemical properties of these two compounds, the azomethine diamine and p-aminophenyl-9-ethylcarbazolyl azomethine possess electrochemical activity, which arises from the heteroatom of molecules.     

Synthesis and Characterization of Nitrogen and Sulfur Containing 1,4-Naphthoquinones

Abstract

New N,S-disubstituted naphthoquinones were synthesized by reactions of S- and N-nucleophiles with 2,3-dichloro-1,4-naphthoquinone. 2-(Hexadecylthio)-3-(phenylamino)-naphthalene-1,4-dione 5a was synthesized by reaction of 2-chloro-3-(phenylamino)-naphthalene-1,4-dione 3a with hexadecanethiol 4a. The structures of the new synthesized naphthoquinone derivatives were determined by micro analyses and spectroscopic methods (FT-IR, ¹H NMR, ¹³C NMR, MS, and UV/Vis.). Photo- and electrochemical properties of selected compounds were investigated by using fluorescence spectroscopy and the cyclovoltammetry method.     

Novel Phosphoranes Containing Urea Derivatives: Synthesis and Characterization

N-Acetyl-N′-methyl urea or ethyl urea in the presence of an acetylenic ester and a desired phosphine functioned as a NH-acid and added to the triple bond in a chemoselective reaction. One of the obtained products underwent lactonization to the corresponding imidazolidine containing ylide moiety when heated in the presence of a base such as triethyl amine.     

A Convenient and Efficient Synthesis of Novel Cyclic Phospholipid Analogues Containing Thio(Seleno) Phosphate-Phosphonate Linkages

Some novel cyclic phospholipid analogues containing the thio(seleno) phosphate-phosphonate linkages have been synthesized in good yields by a convenient one-pot procedure utilizing tris(diethylamino)phosphine activated by iodine as the phosphorylating and ring-closing reagent.