铁体系催化丁二烯聚合的研究——Ⅴ.ESR、NMR和IR研究聚合机理

本文用ESR、¹H-NMR及IR研究了Fe(phen)Cl₃-(i-C₄H₉)₃Al体系催化丁二烯聚合的机理。ESR谱表明,聚合活性中心上的铁为Fe(Ⅱ)。同时观察到自由基的信号,为其还原历程提供了证据。体系中不存在丁二烯时有很宽的ESR信号(ΔH_pp=900G)、加入丁二烯时可以观察到一窄信号(ΔH_pp=50G),二者有明显区别。提出了Fe(phen)Cl₃-(i-C₄H₉)₃Al体系催化丁二烯聚合的反应机理,两个体系的¹H-NMR和IR谱图的比较证实了这个机理。     

2D NMR Studies on the Structure of Urushiol of Chinese Lacquer

The urushiol diacetate was successfully separated by centrifugal rotation TLC on the silica gel coated with silver nitrate.The structure and configuration of key component of.urushiol (64.6%) were determined successfully by using 1H and 13C conventional method,DEPT technique,homo- and heteronuclear chemical shift correlation 2D-NMR,2D-J NMR,hftteronuclear relayed coherencetransfer 2D-NMR,and relaxation time T1 investigation.The as-signment of resonances for 1H and C were confirmed.There is plentyof evidence which shows that the key component of urushiol is3-(8'Z,11'E,13'Z-pentadecatrienyl)catechol.The results show that RELAY 2D-NMR new technique can be successfully applied to determining the structure of complicated unknown compounds.     

The characteristics of lanthanide coordination catalysts and the cis-polydienes prepared therewith

The stereoregularity of polydienes is almost the same in regard to the individual elements of the lanthanide series, whereas the activity of the Ln catalysts in diene polymerization varies from one to the other within the series. The latter may be attributed to the difference in the number of electrons that occupy the 4f orbitals. It has been proved that the polymerization of dienes with Ln catalysts under certain conditions proceeds by a “living polymer” mechanism. With regard to the polymerization of butadiene, the most active catalyst is a Nd³⁺species a new binary system of NdCl₃-3ROH + AlR₃ has been discovered. The cis- 1,4 content in polybutadiene is about 97% and the 1,2 content, less than 1%. For the polymerization of isoprene with a Nd³⁺ catalyst system, the effects of ligand and alkyl groups in AIR₃ on cis-1,4 content (ca. 95%) in polyisoprene can be neglected. For the copolymerization of butadiene and isoprene, the cis-1,4 contents of these two monomeric units in the copolymer are greater than 95% the reactivity ratios r₁ and r₂ are determined. and the T_g's of the copolymers of various compositions deviate slightly from the calculated values for random copolymers. A linear relationship exists between the yield strength from the stress-strain curve of Ln-polvbutadiene and its [n] This relationship is verified by Ln-polyisoprene and natural rubber but different slopes are obtained     

聚合物异核交叉弛豫及二维NOE谱

Kover和Batta首次采用选择性质子π脉冲来测定~(13)C自旋-晶格弛豫速率并与常规反转回复法测定的自旋-晶格弛豫速率相比较求出了交叉弛豫速率,并以此来计算异核间的距离,但他们的计算方法仅适用于满足极端窄化条件的刚性球状分子。二维异核NOE谱(HOESY)是1983年才发展起来的二维NMR技术,它可用来研究异核间的交叉弛豫作用及研究分子间相互作用。Kover和Batta在此方面作了许多     

THE APPLICATIONS OF NUCLEAR SPIN RELAXATION TO POLYMER DYNAMICS AND INTERMOLECULAR INTERACTIONS

The correlation functions of the side - groups and side ?chains of polymers are obtained for nuclear spin relaxation if the segmental motion of the polymers is described by VJGM model, these functions are derived from unequal two ?side and three -site jump internal rotation, diffusion internal rotation, restricted internal rotation and multiple internal rotation. The corresponding spectral density functions are also given, and these functions are used to interpret the nuclear spin relaxation data of the side-groups of some polymers. The average spectral density functions of side-groups are derived under the magic angle spinning, the correlation times and diffusion coefficients of the side-groups of crosslinked poly (methyl methacry-latcs) and solid poly(vinylbutyral) are obtained by using these average spectral density functions. The multiphase structures of nylon 6, poly (ethylenc glycol) and its complexes are investigated with cross ?polarization and magic angle spinning techniques.Three methods using     

在CP/MAS条件下交联聚甲基丙烯酸甲酯中α-甲基的~(13)C自旋-晶格弛豫(英文)

根据不同的跃迁运动和自由扩散运动模型导出了魔角旋转条件下的平均谱密度函数。从CP/MAS谱计算了样品中交联剂DVB的含量。依据实验测得的T_1值计算了一系列用DVB交联的聚甲基丙烯酸甲酯中x-甲基的转动相关时间以及扩散系数。结果表明:(1)随交联剂DVB含量的增加,相关时间增加,而扩散系数下降;(2)x-甲基的转动活化能与交联剂DVB无关,并且小于从介电和力学松弛所得的值。     

有部分峰重叠时NOESY谱的全弛豫矩阵分析

采取用理论计算的NOESY峰强度代替NOESY谱中重叠的对角峰或交叉峰强度,用理论计算值和实验数据相结合的方法解决峰强度矩阵的完整化问题,用全弛豫矩阵分析法定量分析了谱中有部分峰重叠的天然有机化合物冬凌草乙素的相敏NOESY谱,计算出冬凌草乙素分子中各质子间的交叉弛豫速率,根据1/r_ij⁶∝σ_ij计算出相应的质子间距离,结果表明:用全弛豫矩阵分析法计算出的质子间距与分子力学计算得到的质子间距离完全一致。该方法能够用于谱中有部分峰重叠的天然有机化合物的NOESY谱的定量处理,可以为核磁共振方法确定分子在溶液中的三维空间结构提供可靠的结构参数     

COLOC-S脉冲序列在天然有机化合物结构分析中的应用

本文用远程异核化学位移相关谱(COLOC-S脉冲序列)和异核化学位移相关谱研究了香茶菜属二萜类化合物冬凌草甲素和香茶菜醛的化学结构,并对这两个化合物的¹³C和¹HNMR谱线进行了归属。     

STUDY OF THE MOLECULAR MOTION IN POLYEPICHLOROHYDRIN BY HIGH RESOLUTION NMR

The molecular motion in polyepichlorohydrin (PEPCH), in solution and bulk, was studied by high resolution NMR by means of line width, spin-lattice relaxation time T_1 and nuclear Overhauser effect NOE. The results show that the VJGM model can describe the main chain motion of PEPCH in solution perfectly. In bulk state, the relationship between the line width and the temperature is consistent with WLF equation, but that between the high frequency molecular motion correlation time (in T_1 scale ) and temperature is consistent with Arrhenius equation. The motion parameters of PEPCH in both states were calculated. The internal rotation motion of side—CH_2Cl group was analyzed by using equal three-site jump and diffusion internal rotation model in both states.