含二苯联噁二唑大环多胺及其配合物的合成

用2,5-双-(间甲酰基苯基)-1,3,4-噁二唑和相应的二胺,经[2 2]缩合环化反应,合成了三个含二苯联噁二唑的新型大环多胺4、5和7以及5的钡络合物。     

含苯侧基杂环聚芳酰胺酰亚胺的合成与性能

聚酰胺酰亚胺 (ＰＡＩ)是一类已商业化的耐热高分子材料 ,具有与聚酰亚胺类似的耐热性能 ,但是改善了聚酰亚胺的溶解性、可加工性能 ,因此进一步开发综合性能优异、加工性能好的聚芳酰胺酰亚胺近年来成为研究热点之一[1～ 3 ] .ＰＡＩ的经典制备方法为 :( 1 )偏苯三酸酰氯与芳香二胺的聚合反应 ;( 2 )含酰亚胺环的偏苯酸和异氰酸酯反应 .近年来聚酰胺酰亚胺又开发了以下途径制备 :( 1 )含亚胺环的二酸与芳香二胺一步缩聚反应 ;( 2 )含亚胺环的芳香二卤代物与二胺的催化羰基化反应等[4～ 6] .本研究组近期合成了一种新型芳香二胺 ,并合成了耐…     

含二苯联恶二唑大环多胺及其配合物的合成

用2,5-双-(间甲酰基苯基)-1,3,4-恶二唑和相应的二胺，经[2+2]缩合环化反应，合成了三个含二苯联恶二唑的新型大环多胺4、5和7以及5的钡络合物。     

四苯(基)苯基多乙烯基硅油的合成及结构测定

<正> 多乙烯基硅油是高温硫化硅橡胶的集中交联剂,当无耐热填料时,所得硫化胶的耐热性不高。为了使多乙烯基硅油既具有集中交联作用,又赋予耐热性,本文采用Diels-AIder反应合成了含有四苯(基)苯基的多乙烯基硅油。前文曾合成多种多苯(基)苯基有机硅化合物,但实验在封管内进行,诸多不便,投量也甚少,为此,改用高沸点溶剂(α-氯萘),在常压下反应,得到了高产率的四苯(基)苯基多乙烯基硅油:     

羧酸衍生物取代甲基苯基聚硅烷制备杂取代聚硅烷

以甲基苯基聚硅烷　(PhSiMe　) n为原料 ,在无水AlCl3 存在下 ,通过与酰氯、酸酐及酯的取代反应合成了氯代聚硅烷及一系列共聚物 .在乙酰氯的作用下 ,　(PhSiMe　) n上的苯基能够被近乎完全的取代而生成氯代聚硅烷 .一元酸酐 (乙酸酐和丙酸酐 )在用酰氧基部分取代聚硅烷上苯基的同时 ,进行得更多的还是Cl取代 .而顺丁烯二酸酐、邻苯二甲酸酐和乙酸乙酯则只进行不完全的Cl取代 ,根据分子活性的不同得到取代比率各不相同的共聚物 .初步分析了各反应的过程 ,讨论了影响反应的因素 ,同时对于各产物的荧光和紫外特性也进行了分析和讨论     

钯催化二溴代化合物自偶联环化合成二苯并[a,e]环辛四烯

由于独特的结构和广泛的应用,多取代环辛四烯及其苯并稠环衍生物的合成方法研究具有重要意义.本文报道了一种钯催化烯基溴化物与芳基溴化物的偶联反应.利用此钯催化的环化自偶联反应,以中等至较好的收率高选择性地从双溴代芳基或烯基化合物合成了多种二苯并[a,e]环辛四烯衍生物.     

矩形多环芳烃的合成

本文用3,4-二苯基-2,5-二(3,5-二溴苯基)环戊二烯酮(4a)与二苯乙炔(5a)通过Diels-Alder环加成反应得到1,2,4,5-四苯基-3,6-二(3,5-二溴苯基)苯(6a)。化合物6a通过经典的Suzuki偶联反应得到1,2,4,5-四苯基-3,6-二(3,5-二(4-十二烷基噻吩))苯基苯(8a),再利用Fe Cl3作为氧化剂发生Scholl氧化脱氢关环反应,得到目标化合物1a。采用类似合成方法,得到目标化合物1b。化合物的结构均通过1H NMR和MALDI-TOF MS表征,并对其光谱特征、热性能及电学性能进行了初步研究。     

多苯基三联苯有机硅化合物的合成及其对聚合物耐热性影响的研究

本文通过Diels-Alder反应合成了1,4-双(2′,3′,6′-三苯基,4′-四甲基乙烯基二硅氧基苯基)苯(简称Ⅰ)和1,4-双(2′,3′,6′-三苯基,4′-三乙氧基硅基苯基)苯(Si称Ⅱ)两种新的多苯基三联苯有机硅单体,产率均为80％左右,并作了下列耐热性研究,其结果:(1)把化合物(Ⅰ)作为硅橡胶的热稳定剂,所得硅弹性体在300℃×150小时老化后,具有较好的耐热性和机械性能;(2)化合物(Ⅱ)可以做室温胶的交联剂,所得胶片在300℃×48小时老化,仍保持好的弹性。     

过渡金属催化下N-取代苯基-苯并噻噁唑酮-3-甲酰胺的合成及其生物活性

为了寻找新的含苯并噻(噁)唑稠杂环农药先导化合物,利用(6-氯)-苯并噻(噁)唑酮与取代苯基异氰酸酯发生偶合反应,合成了15个N-取代苯基-苯并噻(噁)唑酮-3-甲酰胺化合物3,并利用1H NMR,IR,MS及元素分析对其结构进行了表征.初步生物活性试验结果表明,在试验浓度下部分目标化合物具有一定的杀菌和杀虫活性.考察了部分过渡金属催化剂对该偶合反应的催化效果,结果表明在钯催化、温和条件下即可较高产率得到产物.     

4,4'-(多苯基三联苯)双(有机硅烷)的合成

本文研究了以4,4'-双(三苯基环戊二烯酮基)苯为双烯体,含乙烯基或苯乙炔基有机硅烷为双亲烯体,通过成环反应合成了六个新的4,4'-(多苯基三联苯)双(有机硅烷),产率60%～85%,并用元素分析,IR和'HNM表征了它们的结构。     

PREPARATION AND CATALYTIC BEHAVIOUR OF POLYMER-BOUND METALLOPORPHYRIN IN HYDROGENATION OF OLEFIN

The meso- tetraarylporphyrin has been anchored to styrene- divinylbenzenecopolymers by reaction of meso- tetra (4-hydroxylphenyl ) porphyrin with chloromethylatedresin under mild condition. A number of polymer transition metal complexes have beenprepared with the polymer ligand and metal salts. The polymeric ligand and its complexeshave been characterized by electronic spectra, and vibrational spectra. Cyclohexene can behydrogenated with the polymeric porphyrin palladium complex(P-THPPPd) as catalyst,and its catalytic activity was influenced by the polarity of solvents, the contents of water inethanol or reaction temperature. However, its catalytic activity was lower for nitro groups,carbonyl groups and olefins with steric hindrance substituents, and showed no activity foraromatic rings under these conditions.     

醋酸乙烯与活性聚丁二烯基锂反应机理的探讨

以萘锂为引发剂,抽余油为溶剂,探讨了醋酸乙烯与活性聚丁二烯基锂之间的反应机理。研究结果表明,醋酸乙烯加至活性聚丁二烯溶液中后,主要发生了偶联反应。同时,还向高分子链中引入了羟基。     

STUDY ON SIDE REACTION IN THE SYNTHESIS OF HYPERCROSSLINKED POLYMERS

The systematical study about side reactions have revealed the formation mechanism of oxygen-containing groups of hypercrosslinked polymers. Surface chemistry and functionality of the polymers are characterized by Fourier-transform infrared spectroscopy （FT-IR）, solid state nuclear magnetic resonance （NMR） and contact angle. The results showed that the ether groups were from chloromethylated reaction, and the alcohol groups arose from partial hydrolysis of chloromethyl groups during the post-crosslinking reaction, and the carbonyl functionality was formed by further oxidation of the alcohol groups. Catalyst and solvent used in the postcrosslinking reaction would greatly influence the surface chemistry of the polymer.     

PHOTOCHEMISTRY OF cis-POLYISOPRENE AND ITS SINGLET OXYGEN ADDUCT

Abstract— Reaction of singlet oxygen (¹Δ_g, ¹O₂) with cis -polyisoprene yields an allylic hydroperoxide with an olefinic double bond shifted in the polymer chain. The photochemical decomposition of the resultant hydro-peroxide and the subsequent polymer chain scission kinetics have been studied in the absence of oxygen. Quantum yields of hydroperoxide decomposition range from 3.1 to 8.4 in cyclohexane, depending on the initial amount of hydroperoxide in the polymer. On the other hand, the quantum yields for polymer chain scission are low, and vary with the frequency of the incident light. The ratio for number of polymer scissions per number of hydroperoxy groups decomposed is of the order of 10^-2. The polymer chain degradation is sensitized by the addition of ketones. Based on these data, a reaction mechanism for the overall photodegradation of the cis -polyisoprene initiated by singlet oxygen is proposed.     

SYNTHESIS AND CHARACTERIZATION OF POLYMERS BEARINGAZOBENZENE AND CARBAZOLE GROUPS VIA POST-AZO-COUPLING REACTION

A series of polymers bearing azobenzene and carbazole groups for photorefractive purpose were prepared viapost-azo-coupling reaction.The successful reaction was identified by spectroscopic analysis and gel permeationchromatography.This approach is more facile compared with the direct polymerization of corresponding functionalmonomer.The polymers prepared have weight average molecular weight of higher than 1.5×10~4 and are easily soluble incommon organic solvents like chloroform and tetrahydrofuran,polymer films with high optical quality could be easilyfabricated through solution casting.Glass transition temperature (T_(?)) of the polymers ranges from 60℃to 182℃,dependingon the alkylene spacer length between the functional side group and the polymer backbone,and the polymers are relativelystable under 300℃.     

蒸馏沉淀聚合法制备窄分散聚二乙烯基苯-co-丙烯腈功能聚合物微球

采用蒸馏沉淀聚合法,利用过氧化苯甲酰(BPO)为引发剂,在不加任何稳定剂和不搅拌的情况下,丙烯腈(AN)和二乙烯基苯(DVB)为共聚单体制备了不同交联度的微米和亚微米窄分散聚合物微球,考查了共聚单体对球体的影响,并用扫描电镜(SEM)和红外光谱对微球进行了表征.     

含偶氮苯基侧基聚硅氧烷的合成及光致变色性

含偶氮苯基侧基聚硅氧烷的合成及光致变色性张其震，张静智，王艳（山东大学化学系济南２５０１００）（山东大学环境科学中心济南２５０１００）关键词聚硅氧烷，光致变色，光异构化，量子产率将光致变色性和液晶性化合物结合可得到新的多功能高分子材料，Ｒｉｎｇｅｄｏ...     

氟化氢与涂有聚合物膜下二氧化硅的反应研究

ＨＦ与ＳｉＯ２的反应是一种亲核取代反应，但高温下此反应不能发生．当涂覆在ＳｉＯ２表面的聚合物膜中含有某些特殊的有机化合物或超强酸时，可以促进该反应的发生，这些化合物被称为诱蚀剂．诱蚀剂分三类：（１）三级胺与ＨＦ形成季铵盐得到浓度很高的氟阴离子使该反应很容易发生；（２）强的偶极非质子官能团化合物与ＨＦ中的氢形成氢键使氟的亲核活性增加，有助于该反应发生；（３）超强酸因其质子对ＳｉＯ２骨架中氧的牢固结合能力活化了反应的离去基团，对ＨＦ与ＳｉＯ２的亲核反应起到催化作用．聚合物膜对添加在其中的小分子诱蚀剂起到阻止逃逸的栅栏作用，而本身带有诱蚀官能团的聚合物可以同时充当成膜物及诱蚀剂的作用．通过光化学反应可以选择性地实现聚合物膜下ＨＦ与ＳｉＯ２的刻蚀反应．     

化学接枝改进ZnO-有机硅纳米复合材料的光学性能

采用N-(三甲氧基硅丙基)-4-叠氮-2,3,5,6-四氟苯甲酰胺(PFPA-silane)改性纳米氧化锌,并将PFPA-silane接枝在有机硅聚合物链上.接枝反应改变了纳米复合物的折光指数,并使ZnO纳米粒子与有机硅基体的折光指数更加匹配.这减少了纳米氧化锌粒子对光的散射作用,增加了纳米ZnO-有机硅纳米复合物的透明性.所制备的复合物通过接枝改性后透光率最多可提高50%.研究结果表明无机物和聚合物的折光指数的匹配程度可以通过偶联剂与聚合物基体的反应来进行调控.     

POSTGRAFTING OF HYPERBRANCHED DENDRITIC POLYMER FROM TERMINAL AMINO GROUPS OF POLYMER CHAINS GRAFTED ONTO SILICA SURFACE

This paper describes postgrafting of hyperbranched dendritic polyamidoamine initiated from terminal amino groups of polymer chains grafted onto ultrafine silica surface in order to modify the silica surface. Surface grafting of polymer having terminal amino groups as initiator sites was performed by a reaction of terminal diamine-type polyoxyethylene with epoxy groups previously introduced onto the surface by 3-glycidoxypropyltri-methoxysilane treatment. The postgrafting reaction of dendritic polyamidoamine from the terminal amino groups was achieved by repeating the Michael addition of methyl acrylate to amino groups followed by amidation of the resulting ester moieties with ethylenediamine or hexamethylenediamine. Both the amount of amino groups and the percentage of postgrafting of the resulting polyamidoamine increased with an increase in the number of generations: the amino group content increased from 0.40 mmol/g to 2.68 mmol/g, and the percentage of postgrafting reached 61.0% after the 12th generation by using ethylenediamine in amidation. These values, however, were considerably smaller than the theoretical values. This indicates that the postgrafted polyamidoamine was a hyperbranched polymer but not a precise dendrimer. Ethylenediamine as a reactant in amidation was more effective than hexamethylenediamine, and a low content of initial amino groups was also preferred to a large amount of them probably because of steric hindrance in the propagation of hyperbranched dendritic polyamidoamine. The average particle size of hyperbranched dendritic polyamido-amine-postgrafted silica measured by light scattering photometry increased with an increase in the number of generations of the resulting polyamidoamine.