INVESTIGATIONS ON VINYLENE CARBONATE Ⅰ. PREPARATION AND PROPERTIES OF POLY-(VINYLENEC ARBONATE)

Bulk polymerization of vinylene carbonate using t-butylperoxypivalate at 40℃gave colourless, high molecular weight poly(vinylene carbonate) (PVCA). Solutions of PVCA in acetone and DMF are not stable at 25℃and this degradation was studied. From measurements in DMF with unfractionated PVCA a Mark-Houwink equation was obtained:     

生物可降解磷酸酯-碳酸酯共聚物的合成及性能研究

通过光气，二氯磷酸酯和双酚Ａ反应，合成六种磷酸酯 碳酸酯共聚物，用ＩＲ、１Ｈ ＮＭＲ及元素分析表征了共聚物，测量了Ｍｎ和热学性质．初步研究了在ｐＨ７４磷酸盐缓冲溶液中，核糖核酸酶或碱性磷酸酶存在下的体外降解性能及其对抗肿瘤药物５ Ｆｕ的释放性能．     

苯丙炔酸低聚物的合成及性能

极性-共轭双取代乙炔-苯丙炔酸在Pd(PPh3)2Cl2催化下直接通过易位催化机理聚合为低聚物.单体苯丙炔酸由两步制得,先通过液溴和肉桂酸的加成反应得到二溴代苯丙酸,然后消去两分子溴化氢得到单体.通过红外光谱(IR)、核磁共振(NMR)对单体及低聚物的结构进行了表征.凝胶渗透色谱(GPC)结果显示,聚合反应以甲苯作溶剂,75℃下效果最好,产率中等.这种共轭低聚物可以溶于四氢呋喃(THF)等极性溶剂,TGA结果表明低聚物热稳定性高.紫外可见吸收光谱(UV-Vis)显示,由于聚合后共轭主链大大增长,苯丙炔酸低聚物骨架上电子的跃迁使得低聚物的四氢呋喃溶液在波长高于310 nm光谱的区域中有吸收.荧光光谱(FS)显示,低聚物的四氢呋喃溶液在342 nm激发光下发蓝光,420 nm处有特征荧光发射峰.     

新型催化剂下碳酸丙烯酯合成条件的优化

新型催化剂下碳酸丙烯酯合成条件的优化唐占忠＊（辽阳石油化纤公司研究院辽阳１１１００３）关键词碳酸丙烯酯环氧丙烷二氧化碳催化反应均匀设计中图分类号Ｏ６２４．５前言碳酸丙烯酯（下简称ＰＣ）是一种高沸点有机溶剂，在纺织、高分子合成、气体分离及电化学等领域有...     

苯酚氧化羰化合成碳酸二苯酯的新型PdCl2-Co(Pyca)2催化体系

研究了新型的Ｐｄ－Ｃｏ催化体系催化氧化碳化苯酚合成碳酸二苯酯。当ｎ（ＰｄＣｌ２）：ｎ「Ｃｏ（Ⅱ）」：ｎ（四丁基化铵）：ｎ（苯醌）＝１：１：１０：２５,Ｔ＝１２０,Ｐ＝２．５ＭＰａ（Ｐｃｏ／Ｐｏ２＝４：１）,反应时间８ｈ,ＰｄＣｌ２－Ｃｏ（Ｐｙｃａ）２比ＰｄＣｌ２－Ｃｏ（ＯＡｃ）２的催化活性高。当使用ＰｄＣｌ２－Ｃｏ（Ｐｙｃａ）２催化剂时,ＤＰＣ的产率为６．０３％。最佳的反应温度是１２０℃,ＤＰＣ的产率随着体系的总压增加而增大,当压力升到３．５ＭＰａ时,ＤＰＣ产率为８．５３％。     

IMMOBILIZATION OF GLUCOSE OXIDASE AND CELLULASE BY CHITOSAN— POLYACRYLIC ACID COMPLEX

This study is concerned with chitosan-polyacrylic acid complex as a carrier to immobilize glucose oxidase (GOD)and cellulase. The optimum emperature of the immobilized GOD (IG) was determined to be 60℃which is higher than that of the native GOD about 40℃. The optimum temperature of the immobilized cellulase (IC) was determined to be about 30℃higher than that of native cellulase. Both of the optimum pH of IG and IC shifted one pH unit to acid. Immobilized enzyme may be used in more wide pH range. Their storage life are much longer compared with their native states. Both of them can be reused at least 12 times.     

聚甲基丙烯酸-聚乙烯吡啶复合物固定纤维素酶的研究

<正> 作为植物细胞壁主要成份的纤维素,占植物总重的一半,是地球上最丰富的有机物,是对人类有用而且潜力很大的自然资源。将这些廉价易得的纤维素利用纤维素酶转变成葡萄糖,不仅在食品工业上有现实意义,而且对未来化学工业的发展有着不可估量的影响。但由于酶在水溶液中不稳定,反应后难以分离和回收,只能使用一次,成本较高,使其应用受到一定的限制,固定酶的发展正好弥补了上述不足。     

SYNTHESIS AND PROPERTIES OF POLYACETYLENES CONTAINING CARBAZOLE AND AMINO ACID MOIETIES

 Novel 9-proparylcarbazole monomers containing amino acid moieties, 2-N-(tert-butoxycarbonyl)-L-alanine-9-proparylcarbazole ester (1), 2-N-(tert-butoxycarbonyl)-L-O-cyclohexyl-L-glutamic acid-9-proparylcarbazole ester (2) and 2-N-(tert-butoxycarbonyl)-L-phenylalanine-9-proparylcarbazole ester (3) were synthesized and polymerized with (nbd)Rh+[η⁶-C₆H₅B–(C₆H₅)₃] to give the corresponding polymers with number-average molecular weights ranging from 7050 to 10500 in 70%-86% yields. The polymers were completely soluble in toluene, CHCl₃, CH₂Cl₂, THF and DMSO, but insoluble in hexane, diethyl ether and MeOH. The specific rotation studies revealed that poly(1)-(3) do not took predominantly one-handed helical structures in the solvents although they possess chiral groups. The polymers emitted fluorescence in 0.40%–2.35% quantum yields. The cyclic voltammograms of the polymers indicated that the polymers exhibited electrochemical properties.     

十一碳烯氧甲基苯并冠醚的合成与团载化及固载化产物的催化硅氢化性能

十一碳烯氧甲基一缩二乙二醇、二缩三乙二醇分别与１，２－β（β－羟乙氧基）苯双对甲苯磺酸酯在氢化钠存在下关环缩合，得到９－十一碳烯氧甲基－２，３－苯并１５－冠－５与９－十一碳烯氧甲基－２，３－苯并１８－冠－６．二者与三乙氧基硅烷反应产物以二氧化硅固载化，得到具有十一烯氧甲基连接基团的二氧化硅固载苯并冠醚．它们可与铂形成配合物．铂配合物对烯烃与三乙氧基硅烷的硅氢加成反应具有极好的催化效能     

新型含胆酸功能基生物降解性水凝胶的合成与表征

合成了N-胆酰胺己基-甲基丙烯酰胺(CAHA)单体,将其与聚乳酸-聚乙二醇-聚乳酸双丙烯酸酯(APLEG)共聚制成了一种新型含胆酸功能基生物降解性水凝胶(CAHY).用红外(FT-IR)、核磁(H1NMR)、质谱(MS)、扫描电镜(SEM)、热重分析(TG)和示差热分析(DSC)研究了其结构与性能.结果表明:随着共聚物中胆酸单体(CAHA)比例的增大,干态CAHY水凝胶熔融温度及熔融焓变增大,热失重逐渐减小(300℃时总的热失重小于6%),而其孔状网络结构致密性增大,孔径变小(290μm～8μm).制得的CAHY水凝胶吸水溶胀率可达1300%～1700%.     

配位负载金属卟啉的合成及催化氧化环已烷的性能研究

合成了三种与咪唑配体键合的新型载体，并通过其与四苯基卟啉铁和卟啉锰配位得到了改性的负载金属卟啉催化剂。讨论了它们在催化氧化环己烷反应中的稳定性、活性等，结果表明配位负载方式明显提高了金属卟啉的稳定性，其中硅胶配位负载锰卟啉还具有较高的活性。     

不对称变色酸双偶氮氟胂型新显色剂的合成及其与钍的显色反应研究

合成了8种不对称变色酸双偶氮氟胂型新显色剂，并研究了它们与钍的显色反应，建立了最佳反应体系。试验发现由于引入了吸电子性极强的氟取代基，反应体系的酸度、选择性及灵敏度大为提高，是一组很好的测钍显色剂。     

SYNTHESIS, STRUCTURE AND PROPERTIES OF INTERPENETRATING SULFONIC ACID RESINS WITH HIGH CAPACITY

Two series of interpenetrating sulfonic acid resins (ISAR), 10×n and n×10, were prepared by means of the wet method, and the physicochemical, thermodynamic and kinetic properties of the ISAR were measured. The results show: 10×n resins exhibit better properties than n×10 ones, mainly in higher apparent degree of crosslinking and larger conformational entropy effect, among which, 10×1 resin exhibits the best thermodynamic and kinetic properties. In the DTA graphs of n×10 resins, there are two T_g and two T_(ox), but in those of 10×n, only one T_g and one T_(ox). This result well supports the conclusion that 10×n resins have much better interpenetrating structural aspects.     

界面缩聚法制备间苯二甲酰双酚酸酯聚芳酯

以四丁基氯化铵为相转移催化剂,双酚酸甲酯或双酚酸乙酯与间苯二甲酰氯界面缩聚,合成得到了侧链含酯基的聚芳酯.在吡啶、三乙胺、碳酸氢钠、氢氧化钠中选择合适的催化剂,既可以发生聚合反应又不会使双酚酸酯的酯基发生水解.聚合反应在7种溶剂中进行,通过探讨聚合反应机理以解释溶剂对聚合反应产率以及聚合物特性黏数的影响.以二氯甲烷为溶剂,在优化的聚合条件下较高产率地得到了高特性黏数的聚合物.DSC及TGA分析表明,间苯二甲酰双酚酸酯类聚芳酯具有比间苯二甲酰双酚酸好的热稳定性,热分解温度可从200℃提高到300℃.     

IMMOBILIZATION OF Saccharomyces Cerevisiae USING POLY（ACRYLAMIDE） GEL FOR ASYMMETRIC SYNTHESIS OF R（-）-MANDELIC ACID

In this paper, the poly(acrylamide) hydrogel used to immobilize saccharomyces cerevisiae for asymmetric synthesis of R(-)-mandelic acid was prepared with free radical ploymerization in deionized water at room temperature under nitrogen atmosphere. The influence of the composition of hydrogel, loading amount of cells and culture conditions on the asymmetric synthesis was investigated. Results show that PAAm hydrogel is a feasible carrier for immobilization of cells which is a potential alternative method to prepare enantiomerically pure R(-)-mandelic acid.     

IMMOBILIZATION OF Saccharomyces Cerevisiae USING POLY(ACRYLAMIDE)GEL FOR ASYMMETRIC SYNTHESIS OF R(-)-MANDELIC ACID

1. INTRODUCTIONPoly(acrylamide) hydrogel (PAAm gel), which is able to swell, but cannot be dissolved in the aqueous environment, is a three-dimension network with repeating hydrophilic units -CONH2. Since PAAm gel has a good biocompatibility as well as a high mechanical strength, and can be easily separated from reaction medium, PAAm gel has often been employed to immobilize enzymes and cells so as to catalyze various of chemical and biochemical reactions [1,2]. So far, biosynthesis …     

SYNTHESIS OF ALKYL- AND ARYLPHOSPHONIC ACID MONOESTERS BY DIRECT ESTERIFICATION OF DIBASIC PHOSPHONIC ACIDS IN THE PRESENCE OF AN ARSONIC ACID CATALYST

Partial hydrolysis of a diester, hydrolysis of the monochloro monoester, or alcoholysis of a phosphonic acid anhydride generally is used to prepare monoesters of alkyl- and arylphosphonic acids. Limited cases have been reported for the esterification of a dibasic phosphonic acid to yield the monoester, and none of these methods are as simple as the analogous method for preparing carboxylic acid esters, in which the carboxylic acid is esterified with an alcohol in the presence of an acid catalyst. Described is a method for preparing monoesters of alkyl- and arylphosphonic acids by direct esterification with an alcohol in the presence of a catalytic amount of phenylarsonic acid. The water formed during the reaction is removed azeotropically. For example, methylphosphonic acid was esterified in good yield to give its isopropyl, butyl, cyclohexyl, bornyl, and octadecyl monoesters. Similarly prepared are the ethyl, butyl, hexyl, and 2-(ethylthio)ethyl monoesters of phenylphosphonic acid, as well as 2-isopropoxyethyl hydrogen ethylphosphonate and 2-methoxyethyl hydrogen benzylphosphonate.     

硫化态K—Mo合成低碳醇催化剂的制备条件和载体效应研究

用浸渍法制备以KCl为助剂的ZrO_2、γ-Al_2O_3和SiO_2负载硫化态钼基催化剂,研究了钼和助剂钾两种组分浸渍顺序、助剂含量、载体差别以及浸渍溶液的酸碱性对催化剂上CO加氢合成低碳混合醇性能的影响。ZrO_2按先钼后钾、γ-Al_2O_3和SiO_2则按相反的顺序浸渍两种组分、且K/Mo原子比分别为0.5,0.8和1.0制备催化剂,其合成醇活性最佳。由于载体性质的差异,K-Mo/SiO_2、特别是K-Mo/ZrO_2的合成醇活性强烈依赖于钾助剂含量。而K-Mo/SiO_2在较宽的钾含量范围内,其活性差别不明显。适当选择较高碱性的浸渍溶液制备K-Mo/γ-Al_2O_3催化剂,有利于醇活性的提高。     

四氢呋喃开环均聚以及四氢呋喃和环硫氯丙烷共聚新催化体系

研究发现无水稀土氯化物 ５０％发烟硫酸体系是四氢呋喃（ＴＨＦ）均聚和四氢呋喃与环硫氯丙烷（ＣＭＴ）共聚合的优良新催化体系．考察了ＴＨＦ均聚反应特征，在合适条件下，ＴＨＦ聚合以６５％转化率制得粘均分子量达１０，０００～１５，０００的白色聚四氢呋喃（ＰＴＨＦ）固体．端羟基分析法测得聚合物的分子链两端均为羟基．考察了影响ＴＨＦ ＣＭＴ共聚合反应诸因素，如聚合温度和时间、两单体的比例等，制得数均分子量为１，０００左右的淡黄色粘性固体共聚物．     

SYNTHESIS AND THERMAL PROPERTIES OF A NEW CHOLIC ACIDCONTAINING COPOLYMER

A new copolymer was synthesized by free radical polymerization in solution from methyl 3α-methylacryloyl-7α, 12α-dihydroxy-5β-cholan-24-oate (MACAME) and maleic anhydride (MAN). The copolymer was characterized by FT-IR and functional group analysis. The reactivity ratios of the two monomers were estimated [r_1 = 11.6 (MACAME), r_2 = 0.01(MAN)] by conducting a series of copolymerizations with a variety of monomer feed compositions and analyzing thecopolymer composition. Thermogravimetric and differential scanning calorimetric analyses of the samples indicate that thecopolymer possesses good thermal stability. The temperature at which the copolymer samples experienced a 10% weight loss(T_(WL)) is over 287℃, and the T_g ranged from 174 to 185℃ for the copolymers.