芳杂环腈及其聚合物XV. 不同结构芳香族腈的聚合及其聚合物结构的测定

本文研究了十二种不同取代基的芳香族腈在Lewis酸-金属体系催化下的聚合反应。结果表明, 取代基的吸电子能力越强, 聚合反应速率越快。其速率常数与Hammett方程中的取代基特性常数σ值呈线性关系, 此外, 对聚合物的结构也进行了测定。     

芳杂环腈及其聚合物 ⅩⅤ.不同结构芳香族腈的聚合及其聚合物结构的测定

本文研究了十二种不同取代基的芳香族腈在Lewis酸-金属体系催化下的聚合反应。结果表明,取代基的吸电子能力越强,聚合反应速率越快。其速率常数与Hammett方程中的取代基特性常数σ值呈线性关系。此外,对聚合物的结构也进行了测定。     

芳杂环二腈及其聚合物VII含喹啉环二腈异构体的合成及分离

氰基邻苯二胺1与对-溴苯基乙二醛2反应,可得到喹啉衍生物3和4,由此可进一步制得含喹啉环的二腈5和6.3和4以及6均互为异构体.合成化合物5后,进一步确定了3,4和6的结构.     

芳杂环二腈及其聚合物——Ⅻ.二(对氰基苯基)醚和二(对氰基苯基)砜的聚合反应动力学

<正> 我们曾研究了4,4'-联苯二甲腈(I)在联苯二甲腈氯化锌配合物催化下的聚合反应动力学,结果表明,该聚合反应是二级反应,聚合反应速度与氰基和配合物的浓度各成一次方比例,可用下式表示:     

取代茚基的茂金属Ti、Zr化合物的合成及其催化乙烯聚合活性

茂金属化合物;烯烃聚合;取代茚基的茂金属Ti、Zr化合物的合成及其催化乙烯聚合活性     

聚合色素的研究Ⅸ.侧链悬挂偶氮型染料的聚合膦腈酸多氟烷基酯的合成和性能

首次将偶氮染料和聚合膦腈酸多氟烷基取代酯相结合，合成了一类具有阻燃、疏水憎油等特性的功能聚合物。研究了合成色素的润湿性和热性能，结果表明：所合成的色素具有期望的应用特性。此外，对合成反应的机理和聚合色素的红外光谱特性也进行了初步的讨论。     

聚合色素的研究：Ⅸ.侧链悬挂偶氮型染料的聚合膦腈酸多氟烷基 …

首次将偶氮染料和聚合膦腈酸多氟烷基取代酯相结合，合成了一类具有阻燃、疏水憎油等特殊的功能聚合物。研究了合成色素的润湿性和热性能，结果表明：所合成的色素具有期望的应用特性。此外，对合成反应的机理和聚合色素的红外光谱特性也进行了初步的讨论。     

芳杂环二腈及其聚合物Ⅲ.若干含苯并噻唑环的芳香族二腈的合成

合成了下列五种含苯并噻唑环的芳香族二腈也合成了三个与此有关的单腈化合物.在合成这些化合物中,不少中间物也是新化合物.所有这些化合物的氰基红外吸收峰皆在2232cm^-1左右.     

柄型金属有机化合物（Ⅴ）——锗桥连茚基及取代茚基锆合物的合成及催化烯烃聚合

锗桥连茚及取代茚配体相继与丁基锂及ZrCl4作用，生成锗桥连茚基及取代茚基锆化合物Me2Ge(2-R^1-4-R^2-Ind)2ZrCl2[R^1=R^2=H(1);R^1=Me,R^2=H(2);R^1=Me,R^2=Ph(3)]。化合物1－3均为内消旋和外消旋异异构体的混合物，通过多次重结晶得到化合物1和2的纯外消旋异构体及化合物3的内消旋异构体。由元素分析和^1H NMR谱表征了化合物的分子结构。研究了在甲基铝氧烷（MAO）的助催化下，化合物1－3对乙烯和丙烯聚合的催化性能。由锗桥连茚基化合物1－3得到的聚乙烯的分子量分布比一般茂金属催化剂略宽，内消旋和外消旋异构体的混合物（3）由于两个催化活性中心不等同而使得到的聚乙烯的分子量分布相当宽。外消旋异构体1和2催化丙烯聚合得到高等规聚丙烯。     

Nd(OR)3-nCln-AlEt3催化体系对丁二烯的聚合 II.聚合物微观结构和催化剂诱导效应指数的关系

With a new series of binary catalyst Nd(OR)3-nCln-AlEt3 prepared in our laboratory, the effect to catalyst composition on the microstructure of polybutadiene was studied in detail. A linear relationship is found between the variation of the microstructure of the polymer obtained and the iductive effect index (I) which reprepresents the magnitude of the displacement of paired valence electrons on transition metal-halogen bond (MT-X) of the catalyst. This linear relationship also holds in dealing with the data published in the literature.     

Nd(OR)3-nCln-AlEt3催化体系对丁二烯的聚合 I.聚合的一般规律

Homopolymerization of butadiene has been carried out with a new series of binary catalyst system Nd(OR)3-nCln-AlEt3 and the catalytic activity as well as the microstructure of the resulting polymer have been studied. The results indicate that the stereospecificity of the polybutadiene obtained with these beinary catalyst system (when n=2) is similar to that prepared with thernary system Nd(OR)3-Al2Et3Cl3-AlEt3, yet the catalytic activity of the former is somewhat higher. Hence, it is possible that the present simpler binary system is more preferable to be applied than the ternary. System in butadiene polymerization.     

一类新型的双β-氨基醇的合成及催化硼烷对芳酮的不对称还原反应

以L-半胱氨酸盐酸盐出发，经与二卤代烷偶联，成酯和格氏反应制得三种双手性β-氨基醇，1,2-双[R-2-氨基-3-羟基-3,3-二苯基丙硫基]乙烷(4a)，1,3-双[R-2-氨基-3-羟基-3,3-二苯基丙硫基]丙烷(4b)，1,4-双[R-2-氨基-3-羟基-3,3-二苯基丙硫基]丁烷(4c)。将此类双手性β-氨基醇与硼烷在THF溶液中反应，in situ制备双手性恶唑硼烷催化硼烷对芳酮的不对称还原，产物苯乙醇的光学收率达72.8%、α-溴代苯乙醇的光学收率达91.4%。     

有机钼, 钨化合物研究IV:新的环烯开环聚合催化体系及聚合物性质的初步研究

本文报道以M(CO)6和CHnX4-n(M-Mo,W;n=1,0;X=Cl,Br)这类体系在光照下对环烯的开环聚合催化作用. 发现该体系能有效地对2,3-二氢吡喃, 环戊烯和环己烯开环聚合, 对α-蒎烯也具有一定的开环聚合催化作用. 研究了光照条件, 催化剂用量,聚合温度和时间, 以及其它条件对聚合反应的影响. 并对此催化体系开环聚合的催化机理进行了初步讨论.     

导电高分子薄膜修饰电极的研究I. 聚吡咯薄膜电极的电化学合成及行为

利用在水溶液中的电化学聚合制备了聚吡咯烷、薄膜修饰电极. 讨论了对电化聚合的影响因素及薄膜修饰电极在不同电解质中的伏安特性, 从X-射线光电子能谱推测, 在吡咯的电化聚合过程中氧的参加引起在聚吡咯烷膜的结构中有羰基和羟基的生成.     

Preparation of ortho-substituted aryldifluorophosphines, 2-XC6H4PF2 (X = MeO or Me2N), and some of their derivatives. X-ray crystal structure determination of (2-MeOC6H4P)4 and of the platinum complex,Cl2Pt(2-MeOC6H4PF2)2

The preparation of the ortho-substituted aryldifluorophosphines 2-MeOC₆H₄PF₂ and 2-Me₂NC₆H₄PF₂ by chlorine-fluorine exchange from the corresponding dichlorophosphines using sodium fluoride in acetonitrile in the presence of a crown ether is described. The ortho-substituted aryldichlorophosphines 2-MeOC₆H₄PCl₂ and 2-Me₂NC₆H₄PCl₂ were prepared from the respective bis(N,N-dimethylamino) phosphines by cleavage of the PN bonds with hydrogen chloride. The reaction of 4-fluoroanisole and 2-methoxy-phenyllithium with phosphorus trichloride did not yield the expected chlorophosphines, i.e. 2-MeO-5-F-C₆H₃PCl₂ and 2-MeOC₆H₄PCl₂, but led to formation of 4-fluorophenyldichlorophosphite in the former, and to tris(2-methoxyphenyl)phosphine in the latter case. The difluorophosphine 2-MeOC₆H₄PF₂ was found to undergo a spontaneous oxidation-reduction reaction with formation of the tetrafluorophosphorane 2-MeOC₆H₄PF₄, and the cyclotetraphosphine (2-MeOC₆H₄P)₄. A single-crystal X-ray structure determination of the latter indicated the presence of a strongly puckered four-membered ring with PP bond lengths ranging between 222 and 223 pm, and endocyclic bond angles of 84°. Vicinal MeOC₆H₄ groups were found arranged trans to each other. Dichloroplatinum(II) complexes were prepared, involving the two new fluorophosphines, 2-XC₆H₄PF₂ (X = MeO or Me₂N), as ligands. In neither case was any evidence found for coordination between platinum and oxygen or nitrogen, and the fluorophosphines were found to function solely as phosphorus donors. The absence of interaction between platinum and the oxygen atom in the ortho position of the ligand 2-MeOC₆H₄PF₂ was confirmed in a single-crystal X-ray determination of the complex Cl₂(2-MeOC₆H₄PF₂)₂Pt. The compound was found to exist as a planar, cis-coordinated species with PtCl bond lengths between 232 and 234 pm, and a PtP bond length of 218 pm. All compounds were characterized by NMR spectroscopy (¹H, ³¹P and ¹⁹F, where applicable).