【作者】 殷霞；

【导师】 章伟光；

【作者基本信息】 华南师范大学 ， 高分子化学与物理， 2004， 硕士

【摘要】 1．本论文系统地综述了国内外稀土与ⅡB族金属含硫有机配体配合物的研究进展，对该类配合物的合成方法、结构表征与分析测试方法做了综述，概述了国内外橡胶硫化促进剂的研究现状。 2．ⅡB族金属二苄基二硫代氨基甲酸配合物[Cd（DBTC）₂]₂与[Zn（DBTC）₂]₂（4，4’-bipy）的合成、晶体结构表征、红外光谱和热重分析。室温条件下，在乙醇与水的混合溶剂中合成得到以上两种配合物，并培养得到了适合X射线单晶衍射分析的晶体。通过对配合物[Cd（DBTC）₂]₂与[Zn（DBTC）₂]₂（4，4’-bipy）的X射线单晶衍射分析，结果显示，配合物[Cd（DBTC）₂]₂为呈中心对称结构二聚体。分子中有两个双齿配位的S原子（S1和S1^a），起到桥联作用；分子中存在一个Cd₂S₂配位四元环。每个Cd（Ⅱ）离子处于由5个配位硫原子组成的四方锥的中央，配位数为5。该配合物属于单斜晶系，空间群为P2_1／n，分子式为C₃₀H₂₈CdN₂S₄，分子量M=657.18，a=1.11098（4）nm，b=1.56325（5）nm，c=1.66695（6）nm，α=γ=90°，β=97.9220（10）°，Z=4，V=2.86743（17）nm³，Z=4，R1[I＞2σ（I）]=0.044，wR2（all reflections）=0.099。配合物[Zn（DBTC）₂]₂（4，4’-bipy）的分子是中心对称的双核结构。每个晶胞单元中有2个分子，每个二硫代氨基甲酸配体与锌离子都是以双齿螯合配位。锌离子是5配位的，处于由4个S原子和1个N原子（NS₄）组成的三角双锥的中心，具有三角双锥的几何构型。2个Zn（Ⅱ）离子通过1个4，4’-联吡啶桥联，形成二聚体。该配合物属于三斜晶系，空间群为P-1，分子式为C₇₀H₆₄N₆S₈Zn₂，分子量M=1376.5，a=1.06878（7），b=1.26278（8），c=1.32586（8）；α=93.090（1）°，β=104.488（1）°，γ=108.270（1）°，Z=1（dimer），R1[I＞2σ（I）]=0.046，wR2（all reflections）=0.119。 3．二苄基二硫代氨基甲酸钕的合成条件优化。对配体二硫代氨基甲酸钠的制备条件进行了改进和优化。文中主要讨论了：（1）反应物的配比对配体产率的影响；（2）反应时间对配体产率的影响。综合考虑产物的产量与纯度，最后确定了反应物的最佳配比。 4．讨论了二苄基二硫代氨基甲酸镉配合物在天然橡胶中的硫化促进性能。以[Cd（DBTC）₂]₂促进的胶料具有典型的平硫化曲线，硫化平坦性好，硫化速率高，体现了二硫代氨基甲酸配合物的“短焦烧、快硫化”的特点。加入[Cd（DBTC）₂]₂得到的硫化胶，与传统硫化促进剂—NOBS、CZ／TMTD—相比，抗撕裂性能和拉华南师范大学硕士学位论文伸强度增强，其它力学性能相近。 5.对稀土配合物在橡胶中的硫化促进性能进行了配方改进实验。结果表明，随着促进剂份量的增大，硫化胶的定伸强度和硬度增大;拉伸强度和扯断伸长率先增加，在2.5份达到最大值，然后降低;撕裂强度也是先增加后降低，但最大值出现在用量为2.0份。在同等份量硫磺下，硫化胶的交联密度随着促进剂份量增大而增大，定伸强度和硬度随交联密度的增加而增加，拉伸强度和撕裂强度均在某个交联密度下达到最大值。综合考虑各种性能，最后确定了稀土促进剂的最佳用量。更多还原

【Abstract】 1. In this thesis, the studies on complexes of IIB and rare earth metals with organic ligands containing sulphur atoms have been reviewed. Synthetic methods, structural characterization and analytic methods of these complexes are discussed in detail. At the same time, the application of vulcanization acceleration for these complexes has been described.2. Two new metal complexes, which were shown as [Cd(DBTC)2]2 (1) [Zn(DBTC)2]2(bipy) (2) (where DBTC = N,N-dibenzyl dithiocarbamate; bipy = 4,4’-bipyridine), were synthesized in mixture of ethanol and water at room temperature and characterized by IR spectra, TGA analysis and X-ray crystallographic analysis. The complex (1) is centrosymmetric dinuclear structure. There are two tridentate dithiocarbamate ligands which bridge via one sulfur atom each to two cadmium atoms leading to the formation of a Cd2S2 core. Each cadmium atom is coordinated to five sulphur atoms from three ligands and it results in the formation of a tetragonal pyramidal geometry. Crystal data were listed as following: C30H28CdN2S4 M = 657.18, monoclinic, space group of P21/n, a = 1.11098(4) nm, b = 1.56325(5) nm, c = 1.66695(5) nm, p = 97.9220(10), V = 2.86743(17) nm3, Z = 4, Rl [I>2( I)] =0.044, wR2 (all reflections) = 0.099. The complex (2) shows centrosymmetric dinuclear structure. Zn(II) ions, which is five-coordinated to sulphur atoms from two bidentate dithiocarbamate ligands and one nitrogen atom from bipy, has a trigonal bipyramidal geometry. In each cell, two identical Zn(II) units are linked by bipy to form a dimer. It is triclinic, space group of P-l, with Z= 1. Its lattice parameters: C70 H64 N6 S8 Zn2, M = 1376.5, a = 1.06878(7) nm, b = 1.26278(8) nm, c = 1.32586(8) nm; a = 93.090(1), β = 104.488(1), γ = 108.270(1). Rl [I>2( I)] = 0.046, wR2 (all reflections) = 0.119.3. Very crucial synthetic conditions for preparing the ligand Na(DBTC), such as the mole radio of reactants and reaction time, et al, have been discussed in this thesis. In view of the product’s yield and purity, the optimal synthesis conditions are obtained. Then, the complex [Nd(DBTC)3(HMPA)2] was synthesized by changing the syntheticconditions.4. Vulcanizing properties of the Cd(II) complex [Cd(DBTC)2]2 as vulcanizing accelerator in natural rubber were studied. Compared with traditional accelerators NOBS and CZ/TMTD etc, the results show that the cross-linked rubber accelerated by the complex [Cd(DBTC)2]2 has more excellent physical mechanical properties on tensile strength and tear strength than that by the others.5. Additive capacity of the Nd(III) complex [Nd(DBTC)3(HMPA)2] in natural rubber have been studied. With the dosage of the complex increase, modulus and Shore hardness of cross-linked rubber increase. Their tensile strength and elongation at break increase with the content of the accelerant in the beginning, and the optimal properties are obtained at 2.5 percent, and it would decrease with the increase of the content. It has also been similarly changed on tear strength and the optimal conditional appears at 2.0 percent.With fixing the dosage of sulphur, the crosslink density changes with the increase of the accelerator, and same changes on the modulus and Shore hardness have been taken place with crosslink density, but tensile strength and tear strength would come to head with certain crosslink density. The optimal content of [Nd(DBTC)3(HMPA)2] as an accelerator on the natural rubber would be determined on the basis of considering various properties.更多还原