乙二醇单乙醚醋酸酯合成用固体催化剂的筛选及催化作用分析

采用自建动态酯化反应实验装置，通过色谱分析测定了不同催化剂上乙二醇单乙醚醋酸酯合成反应的转化率－时间关系曲线。根据多种催化剂的活性及寿命，筛选出一种较为理想的锆基催化剂。该催化剂在实验条件下，反应２ｈ，转化率达９７％，对目标产生的选择性为１００％。     

聚芳醚亚砜的合成与表征

以二苯醚和二氯亚砜为主要单体 ,在无水AlCl3/CH2 ClCH2 Cl/NMP催化剂溶剂体系中进行低温溶液共聚 ,合成聚芳醚亚砜 (PPOS) ,研究了AlCl3/NMP用量及单体摩尔比对聚合反应的影响 .用IR、DSC、TG和X ray等对PPOS进行结构和性能的分析与表征 ,研究结果表明 :PPOS属无定形聚合物 ,具有较高的玻璃化转变温度 (Tg) ,软化温度在 2 6 0℃左右 ,在加热过程中出现二个热分解温度     

含磷聚醚醚酮酮砜的合成与表征

聚芳醚酮(PAEK)具有优良的热性能、机械性能、电绝缘性能及耐化学药品性,在航空航天、电子电器、核能工业以及民用高技术领域有着广泛的应用[1].聚芳醚酮熔融温度高且难溶于一般有机溶剂,不易加工.为改善聚芳醚酮的溶解性和加工性,可采取在主链中引入大的侧基、柔性基团、扭曲的非平面结构和采用共聚等方法[2～5].     

一种可溶性含呫吨结构的聚醚醚酮酮的合成与表征

以呫吨酮为起始原料,经二氯亚砜作用得到9,9-二氯呫吨中间体,继而与苯酚发生取代反应,探索了"一锅、二步"法制备含呫吨结构的双酚单体———9,9-二(4-羟基苯基)呫吨(BHPX)的新方法.在氮气保护下,在K2CO3存在下,以环丁砜为溶剂,将其与1,3-二(4-氟苯甲酰基)苯进行亲核缩聚反应,制得了一种高分子量的(数均分子量为45000,多分散性指数为1.9)新型含呫吨结构的Cardo型聚醚醚酮酮(PEEKK-X),并用FTIR,DSC,TG及WAXD等方法对其进行了分析表征.结果表明,所制得的聚合物(PEEKK-X)为无定形结构,其玻璃化转变温度(Tg)为215℃;在氮气气氛中5%的热失重温度(Td)为558℃,700℃时的残炭率为67%;在常温下易溶于非质子极性溶剂(如NMP、DMF和DMAc)和极性较弱的溶剂如CHCl3中.该聚合物可通过溶液浇铸成膜,所得到的薄膜韧性好,透明且耐折,其拉伸强度为81.5 MPa,杨氏膜量为2.48 GPa,断裂伸长率为16.8%.     

冠醚部花青的合成及其光电化学性能

部花青类化合物是一种光敏材料,由于它的结构比较稳定,吸收光谱范围可以调节以及容易做成薄膜电极等优点,用部花青染料做光伏器件的研究引起了人们的注视.Ghosh报道了用青类化合物做成高效率Schottky太阳能电池,光电转换效率达到1%.     

磺酰脲类除草剂的合成及其除草活性

磺酰脲类除草剂具有用量低,活性高、选择性好、毒性小的优点。为开发和应用此类除草剂,我们合成了在氮原子上连正丁基的8个新的衍生物,并进行了室内药效测定。     

一种耐高温憎水聚芳醚的合成与性能初步研究

以双酚芴单体和全氟联苯为原料,通过亲核取代反应,在较低温度(120℃)下直接聚合,得到了一种高分子量的含芴部分含氟的聚芳醚,并用1H-NMR进行表征.合成的聚合物具有好的热稳定性,玻璃化温度达到271℃,5%的热失重为420℃.这些聚合物能溶于四氢呋喃、二氯甲烷、氯仿和DMAC等常见的有机溶剂,通过溶液浇注的方法制备出光滑、柔韧的膜,并利用表面接触角(CA)对膜材料的表面性能进行了表征.用氯仿制备膜的接触角为102°,而用四氢呋喃制备膜的接触角为107°,接触角接近聚四氟乙烯(112°),具有较好的憎水性.     

一种耐高温氟化聚二氮杂萘酮芳醚憎水材料的合成及性能

由五氟苯肼和2-(4-羟基苯甲酰)苯甲酸制备了AB-型双官能团单体4-(4-羟基苯基)-2-五氟苯基-二氮杂萘酮,以苯做带水剂,在K2CO3的催化下温和的反应条件下通过自身亲核缩聚反应合成了结构规整的氟化聚二氮杂萘酮芳醚材料.用傅里叶衰减全反射红外光谱(FTIR ATR)、氢谱(1H-NMR)、氟谱(19F-NMR)对材料的结构进行了表征.该聚合物的玻璃化转变温度Tg为316℃,Td,5 wt％为491℃,具有良好的热性能;该聚合物薄膜样品测试结果表明该材料具有高的力学性能和绝缘性,拉伸强度超过了60 MPa,表面电阻率为1.8×1015Ω/m2,体积电阻率为5.6×1012Ω/m3;该聚合物在DMAc,DMF,DMSO,NMP,1,1,2,2-四氯乙烷,四氢呋喃,氯仿,吡啶和环丁砜中有良好的溶解性,可加工得到光滑、硬韧的膜;利用表面接触角测定仪考察了不同溶剂体系所得膜材料的表面性能,用DMAc制备膜的接触角为93.3°,用氯仿制备膜的接触角为92.5°,用THF制备膜的接触角为127.1°,接触角大于聚四氟乙烯(112°),且所有考察溶剂中所得膜的接触角都大于90°,具有较好的憎水性.     

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）．     

对偶氮苯基苯偶氮氨基苯甲酰聚氧乙烯醚的合成及性质

报道了一种新型大分子对偶氮苯基苯偶氮氨基苯甲酰聚氧乙烯醚 (PE·PATB)的合成及性质 ,并与相应的小分子试剂对偶氮苯基苯偶氮氨基苯甲酸 (PATB)比较。结果表明 ,PATB进一步缩合为PE·PATB后 ,性能明显改善 ,表现为在水和乙醇中溶解度明显增大 ,光度测定金属离子的灵敏度明显提高 ,特别是在表面活性剂析相萃取中 ,改变了原灵敏度高但水溶性差的小分子试剂及其金属络合物难以被萃取的不足 ,而且也不像水溶性的小分子 (如对甲酰基苯偶氮变色酸 )和高分子试剂 (如聚乙烯醇缩对甲酰基苯偶氮变色酸 )等易受无机盐和表面活性剂浓度的影响 ,在室温下就有很高的萃取率 ,可用于微量甚至痕量组分的分离富集和测定 ,拓宽了表面活性剂析相萃取分离方法的应用范围。     

新型含环氧端基聚芳醚酮的合成及表征

以 4,4′ 二氟二苯酮和 4 (4 羟基苯基 ) 2 ,3 二氮杂萘 1 酮经亲核取代逐步聚合制得含二氮杂萘酮结构的聚芳醚酮低聚物 ,再与环氧氯丙烷反应制得了所需分子量的含环氧端基的聚芳醚酮 (E PPEK) .用FT IR和1H NMR表征了分子链结构 ,并测定了聚合物的玻璃化转变温度Tg 和溶解性 .     

SYNTHESIS OF ALKYL AND ARYL 1-PROPENYL ETHER MONOMERS: A NEW APPROACH

A new, convenient synthesis of alkyl and aryl 1-propenyl ether monomers in good to excellent yields has been developed. Alkyl and aryl allyl ethers can be smoothly isomerized to the desired 1-propenyl ethers by refluxing in a basic ethanolic solution containing pentacarbonyliron as a catalyst. A simplified two-step, one-pot procedure has also been developed which consists of combining an alcohol with allyl bromide in the presence of base and then adding pentacarbonyliron to isomerize the in-situ generated allyl ether to directly give the 1-propenyl ether. Good yields of alkyl 1-propenyl ethers were obtained using this process. Factors affecting the isomerization reaction were investigated and a mechanism was proposed.     

N-1-取代苯并三唑的简易快速合成及生物活性

本文应用相转移催化和微波辐射合成１０个Ｎ－１－取代苯并三唑;Ｎ－１－苄基、－乙氧羰基亚甲基、－芳基、－乙酰基、２个一羧亚甲氧烷基苯并三唑及４个二（苯并三唑基）烷烃,其中有７个为新化合物,这种简易快速方法具有产率高、反应时间短、操作方便、低能耗和无环境污染的优点。初步测试它们的生物活性,大多数化合物具有较好的抗菌活性。     

THE SYNTHESIS OF A NEW TYPE OF DISINFECTANT RESIN AND ITS ANTIBACTERIAL ACTIVITY

Polymer supported alkyl dimethyl benzyl ammonium chloride resin disinfectant used for the disinfection of drinking water has been synthesized,and its antibacterial activities have been determined,compared with the commercially used triiodine disinfectant resin.The resin disinfectant was generated successfully when use the combination of surface active agents and ultrosonic.     

SYNTHESIS AND CHARACTERISTICS OF POLY(ARYLENE ETHER DIKETONE)S

Poly(arylene ether diketone)s were prepared by the aromatic nucleophilicdisplacement reaction of 4,4'-difluorobenzil with different bisphenols in the presence of an-hydrous potassium carbonate in diphenylsulfone at elevated temperature. The polymersobtained had inherent viscosity of 0.51 ～ 0.63 dL/g, and exhibited glass transition temper-ature ranging from 136 ～217℃ mainly depending on the bisphenols used in the polymersynthesis. Thermogravimetry of these polymers showed excellent thermal stability, indi-cating that 10% weight losses of the polymers were observed in the range above 428℃ and438℃ in air and nitrogen, respectively. The mechanical properties of these polymers werealso described and the permeability of five polymers for H_2, O_2 and N_2 was determined at30℃.     

可紫外光交联氟代聚芳醚的合成及性能研究

以丙酮酸、苯甲醚为原料合成了1,1-双(4-甲氧基苯基)(BMPE)乙烯单体,并通过去甲基反应得到了含可交联基团的二酚单体1,1-双(4-羟基苯基)乙烯(BHPE),并且用核磁共振、飞行质谱及元素分析表征了单体的结构,DSC测试了单体的熔点.并将BHPE与全氟联苯(DFBP)在氟化钾和氢化钙的催化作用低温下进行缩聚反应,得到了一种可紫外辐照交联的氟代聚芳醚.通过核磁共振证明了所合成的单体以及聚合物的结构,凝胶渗透色谱(GPC)测定了聚合物的分子量.傅立叶变换红外光谱分析了聚合物紫外辐照下的交联反应.所合成的氟代聚芳醚在室温下可溶于氯仿、四氢呋喃等有机溶剂,紫外交联后不溶于任何有机溶剂.且合成的聚合物具有良好的热稳定性能(玻璃化转变温度为160℃,交联后的5%热失重为465℃).     

以聚醚链相连的萘甲酸酯-氨基吖啶体系的合成及分子内能量传递研究

本文分别用聚三乙二醇及聚四乙二醇柔性链将α-萘甲酸与9-氨基吖啶连接起来,合成了新型二元发色团分子体系,发现在两个体系中,选择性激发α-萘甲酸酯,都可以发生从α-萘甲酸酯到9-氨基吖啶的高效率的单重态-单重态能量转移,并讨论了溶剂极性对能量传递效率的影响。     

SYNTHESIS AND CRYSTALLIZATION BEHAVIOR OF POLY(ETHER ETHER KETONE ETHER KETONE)(PEEKEK)*

In this paper, the synthesis and crystallization behavior of poly(ether ether ketone ether ketone) (PEEKEK) arereported. PEEKEK was prepared from 4,4'-bis(p-fluorobenzoyl) diphenyl ether (4,4'-FBDE) and hydroquinone along thenucleophilic substitution route. The thermal properties were investigated by using DSC and TGA. The crystallizationbehavior of PEEKEK under several conditions, i.e., crystallization from the molten state (melt crystallization), crystallizationfrom a quenched sample (cold crystallization) and crystallization induced by exposing glassy sample to methylene chloride(solvent-induced crystallization) has also been investigated. The results show that crystallization of PEEKEK could beinduced by the above methods, and no polymorphism was found. The diflierences in the crystallization of PEEKEK inducedby the above methods are seen in their degree of crystallinity.     

SYNTHESIS OF POLYCATECHOL WITH ELECTROCHEMICAL ACTIVITY AND ITS PROPERTIES

The electrochemical polymerization of catechol on platinum has been carried out using repeated potential cyclingbetween-0.2 and 1.1 V (versus SCE). The electrolytic solution consisted of 0.2 mol dm~(-3) catechol, 0.5 mol dm~(-3) NaCl and0.1 mol dm~(-3) Na_2HPO_4 with pH 8.72. Catechol can not be polymerized at pH≥10.12. Polycatechol has an electrochemicalactivity at pH≤4. The anodic and cathodic peak potentials of polycatechol shift towards more negative values as the pH ofthe solution increases from 1 to 4. The electrochemical activity of polycatechol hardly changes in this pH region, but itdecreases slowly with time. This is caused by oxygen in air, which leads to an irreversible oxidation of polycatechol. Thisproperty is favorable for protecting metals from corrosion. Raman and FTIR spectra of polycatechol and catechol are quitedifferent. AFM images of polycatechol films provide evidence that the image of the oxidized state of polycatechol ismarkedly different from that of the reduced one. This difference is caused by doping and dedoping of polycatechol.