光敏感遥爪聚合物——聚4-乙烯基吡啶的制备及其溶液性质

以香豆素二硫化物(C-S-S-C)/三丁基膦(Bu₃P)/H₂O复合体系为链转移剂, 偶氮二异丁腈(AIBN)为引发剂, 4-乙烯基吡啶为单体制备了末端含有疏水性香豆素光响应基元的光敏感遥爪聚合物(聚4-乙烯基吡啶(C-P4VP)). 用傅里叶变换红外(FTIR)光谱、凝胶渗透色谱(GPC)、氢核磁共振(¹H-NMR)等对该聚合物进行了结构表征. 研究显示该遥爪聚合物可在不同pH值(pH=3-6)的酸性水溶液中自组装成胶束, 且随体系酸值的降低, 聚合物胶束结构由松散变为紧密, 同时香豆素端基的光二聚反应程度呈现先下降后上升的趋势.     

高选择性透过SO_2气体分离膜研究 Ⅰ.丙基乙烯基亚砜改性聚乙烯醇功能高分子的合成

本文研究聚乙烯醇与丙基乙烯基亚砜经Michael加成反应合成含亚砜基的改性聚乙烯醇功能高分子.用IR、~1H-NMR、X-射线衍射等鉴定反应产物.结果表明,随着亚砜基含量的增加聚合物的结晶性降低,而在冷水,DMSO,CH_3OH,C_2H_5OH和CH_2Cl_2中的溶解性提高.     

烷基锂引发的丁二烯阴离子聚合的理论研究进展

一、前言从本世纪初开始的丁二烯聚合,在高分子科学和工业的发展中占有重要地位。自1956年M.Szwarc提出了活性聚合物的概念以来,阴离子聚合作为高分子化学的一个重要部份不断发展,丁二烯阴离子聚合也进入了一个新的阶段,诸如SBS、中乙烯基聚丁二烯、遥爪     

聚烯烃低聚物转化为双端正离子活性链及其遥爪三嵌段物的合成

非“活性”的端羧聚丁二烯及端羧聚丁腈胶通过THF开环聚合转变为双端正离子活性链。用液氨或二乙胺终止反应制得伯胺或叔胺端基遥爪聚丁二醇-聚烯烃-聚丁二醇三嵌段低聚物。     

四氢呋喃正离子聚合转为烯类单体负离子嵌段共聚合的研究

本文以癸二酰氯-高氯酸银催化剂在低温引发四氢呋喃正离子聚合,用伯胺终止,制得带有双端仲胺基的聚四氢呋喃遥爪聚合物(PTHF-NHR,R为苄基、正丁基、苯基)。当R为苯基时,PTHF-NHR与萘钠的金属化反应接近完全。以PTHF-NHR的胺钠盐引发烯类单体(甲基丙烯酸甲酯、苯乙烯、丙烯腈)负离子嵌段共聚合。当R为苯基、单体为甲基丙烯酸甲酯时,室温反应可得到转化率为100％的ABA型嵌段共聚物,为热塑性弹性体,其抗张强度为157kg/cm~2,扯断伸长率为700％。     

光敏感遥爪聚合物C-PDMAEMA的合成及其性能研究

以香豆素二硫化物(C-S-S-C)/三丁基膦复合体系为链转移剂、甲基丙烯酸-N,N-二甲氨基乙酯(DMAEMA)为单体、偶氮二异丁腈(AIBN)为引发剂制备了末端为香豆素光响应基元的双亲性遥爪聚合物(C-PDMAEMA). 用FTIR, GPC, ¹H NMR等对该聚合物进行了结构表征. 研究表明该遥爪聚合物可直接在水中形成纳米聚集体|且其香豆素端基可在365 和254 nm交替光照下进行可逆光二聚反应. 同时纳米粒度跟踪(Malvern Zetasizer Nano-ZS)、透射电镜(TEM)跟踪结果表明, 随香豆素端基光二聚反应的进行, 聚合物纳米聚集体的粒径逐渐增大|反之, 随着光解二聚反应的进行, 该纳米聚集体的粒径逐渐减小.     

遥爪型液体聚合物及其多相共聚物的合成与表征——Ⅲ.遥爪型三组份四臂星形共聚物的合成及其动态力学性能

本文在前报所合成的端羧基乙烯基四氢呋喃-环氧丙烷液体共聚醚的基础上,利用其端羧基同双官能团环氧反应,生成端环氧基三嵌段共聚物。然后再利用端乙烯基与烯类单体反应,制备了遥爪型三组份四臂星形共聚物。通过动态力学性能的测试,观察了一些因素对阻尼性能的影响。     

高选择性透过二氧化硫气体分离膜的研究(Ⅲ)──乙烯基亚砜与聚乙烯醇的Michael加成反应及其结构表征

本文合成了4种烷基乙烯基亚砜。研究了其与聚乙烯醇在碱催化下的Michael加成反应,制备了不同亚砜含量的聚合物。研究了其溶解性能,用IR及¹HNMR法对聚合物进行了表征。     

高选择性透过SO2气体分离膜研究 Ⅰ.丙基乙烯基亚砜改性聚乙烯醇功能高分子的合成

 本文研究聚乙烯醇与丙基乙烯基亚砜经Michael加成反应合成含亚砜基的改性聚乙烯醇功能高分子.用IR、¹H-NMR、X-射线衍射等鉴定反应产物.结果表明,随着亚砜基含量的增加聚合物的结晶性降低,而在冷水,DMSO,CH₃OH,C₂H₅OH和CH₂Cl₂中的溶解性提高.     

基于半刚性的4-羧基苯乙酸和富氮共配体组装的Zn(Ⅱ)/Cd(Ⅱ)配位聚合物的合成、结构和性质（英文）

采用溶剂热法合成了一系列Zn(Ⅱ)/Cd(Ⅱ)配位聚合物:{[Zn(cbaa)(bpmp)_(0.5)(H_2O)]·2H_2O}n(1)、[Zn(cbaa)(bip)]_n(2)、[Cd(cbaa)(Hizb)]_n(3)和[Cd_2(cbaa)_2(itmb)(H_2O)]_n(4)(H_2cbaa=4-羧基苯乙酸;bpmp=1,4-二(4-吡啶甲基)哌嗪;bip=3,5-双(1-咪唑基)吡啶;Hizb=2-(4-咪唑-1-基苯基)-1H-苯并咪唑;itmb=1-(咪唑-1-基)-4-(1,2,4-三唑-1-基甲基)苯)。X射线单晶衍射结果表明,半刚性的4-羧基苯乙酸和富氮辅助配体构筑形成了4个多样化拓扑结构的配位聚合物。化合物1和2是Zn(Ⅱ)配位聚合物:1是由2个Zn-羧酸盐链之间通过富氮配体桥连形成的一维梯形结构,而2是由Zn-羧酸盐链之间通过富氮配体拓展形成的二维单层结构;化合物3和4是Cd(Ⅱ)配位聚合物:3是由Cd-O无机链之间通过羧酸配体的桥连拓展形成的二维单层结构,富氮配体作为伸出层平面的悬臂仅仅起到结构修饰作用,而4则形成了Cd-羧酸盐空旷双层结构,富氮配体填充在层内空腔中,从而导致了致密双层结构的产生。另外,考察了4个化合物的热稳定性和光致发光性能。     

Ene-sulfides as Reaction Partners of Organometallic Compounds

A comparison of the reactivity of ene-sulfides and en-ethers towards organometallic reagents reveals some remarkable differences. With the thio compounds metallation at the olefinic site next to the hetero atom dominates clearly over the alternative deprotonation of an allylic position. Only with propenyl phenyl sulfide both exchange modes were observed simultaneously, whereas with all higher homologues of it as well as vinyl phenyl sulfide the metal was exclusively attached to the olefinic α-carbon atom.     

Facile oxygenation of organic sulfides with H2O2 catalyzed by Mn-Me3TACN compounds

Two binuclear Mn-Me₃TACN (Me₃TACN is 1,4,7-N,N′,N″-trimethyl-1,4,7-triazacyclononane) compounds catalyze the oxygenation of organic sulfides utilizing H₂O₂ under ambient conditions. Both phenyl sulfide and ethyl phenyl sulfide were converted to the corresponding sulfones and chloroethyl phenyl sulfide proceeds to its elimination product of phenyl vinyl sulfone.     

Preparation of Diazo Phenyl Sulfides. Kinetics and Mechanism of the Diazo Coupling Reaction of p-Nitrobenzenediazo Phenyl Sulfide with β-Naphthol under Various Conditions

Aryldiazophenyl sulfides prepared from diazotised arylamines and thiophenol at controlled pH, are coupled with β-naphthol yielding the corresponding azo dye. A kinetic study of the diazo coupling reaction of p-nitrobenzenediazo phenyl sulfide with β-naphthol under various conditions revealed that the reaction is of first order kinetics with respect to the diazo phenyl sulfide, and that the rate of coupling measured colorimetrically is influenced by the hydrogen ion concentration and by the ionising power of the medium.     

Sulfur-containing vinyl monomers. XII. Charge transfer complexes of thioethylene derivatives with π-electron acceptors

The absorption spectra of charge-transfer (CT) complexes of thioethylene derivatives with p-chloranil (CA), tetracyanoethylene (TCNE), and 7,7,8,8,-tetracyanoquinodimethane (TCNQ) were measured in methylene chloride. Since the CT bands of alkyl vinyl sulfides having bulky substituents such as isopropyl, cyclohexyl and tert-butyl were similar to that of methyl vinyl sulfide, the complexing site of these sulfides to acceptor was assumed to be the vinyl group rather than the sulfur atom. In the case of the TCNE complex of phenyl vinyl sulfide, however, a new second CT band at 378 nm was observed, and the first CT band was also close to that of ethyl phenyl sulfide, indicating that the TCNE formed a complex with this vinyl sulfide mainly at its phenyl group. To investigate further the conformation of the complex, CT spectra of bis-, tris- and tetrakis (phenylthio) ethylenes were measured. These compounds showed markedly different CT bands, and the changes in these CT bands with the number of the phenylthio substituents appears to be attributable to the change in complexing site with the acceptors used.     

Graft Copolymerization of Methyl Methacrylate on Poly(phenyl Vinyl Sulfide)

Graft copolymer of poly(phenyl vinyl sulfide) and methyl methacrylate was obtained. The isolation of graft copolymer was carried out by the fractional precipitation method. The isolated polymer was confirmed to be a graft copolymer by IR spectra and T determinations. Graft copolymerizations of poly(phenyl vinyl sulfide) with vinyl acetate, acrylonitrile, acrylamide, and acrylic acid were also carried out, but the separation of graft copolymer in these cases was difficult, and satisfactory results could not be obtained.     

含硫化合物热解规律的研究

选择丁硫醚、叔丁硫醚、四氢噻吩、乙基苯基硫醚作为模型化合物,在模拟 催化裂化微反装置上考察了含硫化合物热解规律,在热解过程中,烷基含硫化合物转化程度与硫醚烃基结构、反应条件有关。异构含硫化合物比正构含硫化合物容易转化,反应温度升高,转化程度增大,转化产物主要为硫化氢和硫醇,只有少量四氢噻吩发生转化,反应温度升高论程度增加,大部分乙基苯基硫醚发生转化,生成苯硫酚和少量硫化氢;反应温度升高,转化程度增加。含硫化合物热解可能是通过自由基历程进行的。     

Living block copolymerization of phenyl vinyl sulfoxides and characterization of a stereogradient polymer

The polymerization of phenyl vinyl sulfoxide in blocks of increasing enantiomeric excess was carried out. Portions of the polymer were removed after each charge of monomer was consumed. The poly(phenyl vinyl sulfoxide)s were characterized by gel permeation chromatography and nuclear magnetic resonance spectroscopy. Reduction of the poly(phenyl vinyl sulfoxide)s to poly(phenyl vinyl sulfide)s permitted assignment of the polymer stereochemistry and verification that stereogradient polymers were formed.     

催化裂化过程中含硫化合物转化规律的研究

选择丁硫醚、叔丁硫醚、四氢噻吩和乙基苯基硫醚作为模化合物,在模拟固定床催化裂化微反装置上考察含硫化合物转化和分布规律,在催化裂化过程中,烷基硫醚可以完全转化,转化产物为硫化氢,反应条件对转化程度没有明显影响;环状含硫化合物的转化程度与反应条件、溶剂性质有关,转化产物主要为硫化氢和汪量噻吩,生产的噻吩可进一步发生烷基化反应,反应温度升高,溶剂供氢能力增强,硫化氢的收率增加;乙基苯基硫醚也可以完全转化,转化产物主要为硫化氢和苯硫酚,生成的苯硫酚可进一步发生烷基化反应,反应温度升高,溶剂供氢能力增强,硫化氢的收率增加。     

Cycloaddition-elimination reactions of 5-imino-1,2,4-dithiazolidin-3-ones with heterocumulenes

5-Benzylimino-1,2,4-dithiazolidin-3-one ( 2a ) reacts with heterocumulenes (isocyanates, isothiocyanates, ketenes) with elimination of carbonyl sulfide, yielding the heterocycles 6–8 . The thiadiazolidine 6a , obtained from 2a and phenyl isocyanate, underwent similar reactions but under milder conditions, indicating that phenyl isocyanate is a better leaving group than carbonyl sulfide.     

Unexpected catalyzed C=C bond cleavage by molecular oxygen promoted by a thiyl radical.

Olefin oxidation with molecular oxygen, promoted by a transition metal catalyst and a thiophenol, involved C=C bond cleavage into the corresponding carbonyl derivatives. This new reaction proceeds under one atmosphere of oxygen, at room temperature, in the presence of an excess of thiophenol and a catalyst such as MnL(2) 3a or VClL(2) 3c. It was applied to aromatic and aliphatic olefins, as well as to functionalized or unfunctionalized acyclic compounds, providing the corresponding ketones and aldehydes in up to 98% yield. The synthetic interest of this catalytic oxidation was illustrated by a one-step preparation of the fragrance (-)-4-acetyl-1-methylcyclohexene 7e in 73% isolated yield. The C=C bond cleavage probably results from a catalyzed decomposition of the beta-hydroperoxysulfide intermediate 12 that is formed by the radical addition of thiophenol to the olefin in the presence of oxygen. Although an excess of the thiophenol was used, it was transformed into the disulfide which could then be reduced without purification in 83% overall yield, thereby allowing for recycling. In addition, the C=C bond cleavage under oxygen could be promoted by catalytic quantities of the thiyl radical, generated by photolysis of the disulfide; thus, in the presence of 0.1 equiv of bis(4-chlorophenyl) disulfide 4b and 5% of the manganese complex 3a, trans-methylstilbene 1b gave, under radiation, benzaldehyde 6a and acetophenone 7a in up to 95% yield. This new reaction offers an alternative to the classical C=C bond cleavage procedures, and further developments in the fields of bioinorganic and environmental chemistry are likely.