锡偶联无规溶聚丁苯橡胶13C NMR研究(Ⅰ)烷碳区谱峰归属

研究了锡偶联溶聚丁苯橡胶烷碳区¹³C NMR谱图,借助DEPT谱区分CH和CH₂,利用文献值和经验计算公式,对实验中观察到的24个谱峰进行了归属.     

无规丁苯共聚物的核磁共振波谱——二单元序列结构的定量计算

在前文谱带指认的基础上,用¹³C-NMR谱的脂肪碳部分计算了无规丁苯共聚物中十六种二单元的组成.由它们推出的四种结构单元的组成与从氢谱得到的结果相符.在本聚合体系下,二单元的序列长度和四种结构单元的平均持续比表明,苯乙烯单元(S)易形成短嵌段聚合物,1,2-丁二烯单元(v)显示出易与其它三种单体单元结合的趋势,反式1,4-丁二烯单元(t)和顺式1,4-丁二烯单元(c)除形成本身的嵌段聚合物以外,也易形成交替式结构.结果表明,¹³C-NMR是研究丁苯共聚物微观结构的有力工具.     

1,3-和1,4-环己亚硝酸二酯电子轰击解离的结构效应（英文）

烷基亚硝酸二酯是一种重要的亚硝化剂,也是大气中NOx污染物的来源之一,近年来引起了人们的广泛关注.烷基亚硝酸二酯中两个ONO官能团对分子反应活性的影响以及在化学反应中的作用尚不清楚.本文用电子碰撞电离质谱研究了 1,3-环己亚硝酸二酯和1,4-环己亚硝酸二酯的解离过程.实验结果发现两种结构异构体的分解产物不同:除了亚硝酸酯的特征碎片NO~+(m/z=30)外,对于1,3-异构体,碎片离子m/z=43和71的丰度最高;而对于1,4-异构体,电子碰撞电离质谱谱图中解离产物m/z=29、57、85和97的强度较大.对中性分子、分子离子以及中间产物的结构和电荷计算结果显示,1,3-环己亚硝酸二酯的分解清楚地显示出两步解离机制,即母体阳离子M~+首先失去一个NO,然后中间离子(M-NO)~+通过两个αC-βC键的断裂打开六元碳环;对于1,4-环己亚硝酸二酯,除了两步分解机制之外,还可以直接从母体阳离子M~+发生βC-βC键的裂解.研究结果有助于理解在大气反应及亚硝化合成反应中烷基亚硝酸二酯的分子结构对反应历程的影响.     

1H-NMR谱表征2G/TMEDA体系丁戊橡胶的微观结构

用400MHz高分辨率核磁共振氢谱首先对2G/TMEDA体系下均聚的丁二烯和异戊二烯橡胶进行了微观结构的分析,进而对不同调节体系下共聚的丁戊橡胶的微观结构进行了研究,建立了不同调节体系下的丁戊橡胶的微观结构的分析方法,解决了丁戊橡胶复杂的微观结构的定性定量分析问题.     

P_6团簇结构与稳定性的理论研究

采用量子化学HF,B3LYP和MP2方法,选用6-31G*,6-311G*,cc-pVDZ和cc-pVTZ基组,对P6团簇的8种异构体进行了优化,并对它们的几何构型、稳定性、电子结构和振动频率进行了讨论,比较P6团簇各种异构体的稳定性以及导电性.研究表明:根据异构体的相对能量,P6异构体最稳定的构型c具有C2v对称性,而最不稳定的构型h具有D3h对称性,不同方法和基组所得到的稳定性大小基本一致,并且得到结构g的导电性最好.     

4,5—二氧—2—硫—1,3,2,4—二氮二磷杂环戊烷衍生物的^31PNMR谱

~(31)PNMR谱表明,在4,5-二氧-2-硫-1,3,2,4-二氮二磷杂环戊烷类型化合物中,存在着顺式和反式两种异构体.顺式异构体化学位移出现在高场,~2J_(pp)偶全合常数较大;而反式异构体化学位移在低场,~2J_(pp)偶合常数较小.用Van der Waals排斥力和Pπ-dπ反馈理论解释了以上现象,并讨论了其他取代基R、X对~(31)P—NMR化学位移的影响.     

一个含苯并咪唑环的酰氨基硫脲NMR研究

该文合成了一个新的在医药方面具有潜在应用价值的含苯并咪唑环的酰氨基硫脲化合物,即4-(4-甲氧基苯基)-1-[2-(4-硝基苯氧基甲基)-苯并咪唑-1-基\]甲酰基氨基硫脲,并利用元素分析、IR和NMR对其结构进行了表征. 通过NOESY谱确定了其两种异构体(A和B)的构型,并利用2D NMR技术对它们的¹H NMR 和¹³C NMR谱进行了全归属,给出了相应的偶合常数和两种异构体的含量.     

^lH-NMR谱表征2G／TMEDA体系丁戊橡胶的微观结构

用400MHz高分辨率核磁共振氢谱首先对2G／TMEDA体系下均聚的丁二烯和异戊二烯橡胶进行了微观结构的分析,进而对不同调节体系下共聚的丁戊橡胶的微观结构进行了研究,建立了不同调节体系下的丁戊橡胶的微观结构的分析方法,解决了丁戊橡胶复杂的微观结构的定性定量分析问题。     

一种含末端炔喹啉酮类化合物的波谱学研究

通过Cu(I)催化有机叠氮化物和端基炔之间的1,3-偶极Huisgen环加成反应,又称“点击化学”, 可快速、高效合成专一的1,4-二取代-1,2,3-三唑产物. 为得到含有末端炔的喹啉酮衍生物,以7,8-二氢-2,5(1H,6H)-二酮（1）为原料,通过烷基化反应将端基炔引入到化合物1中,合成了1-(2-炔丙基)-7,8-二氢喹啉-2,5(1H, 6H) 二酮（3）,并利用重结晶和硅胶柱分离两种化学手段,得到了该化合物的两种构型异构体. 采用DEPT、¹H NMR、¹³C NMR、¹H-¹H COSY、NOESY、HMQC多种NMR实验测试分析方法,对该化合物的构型异构体进行了验证和区分,并分别对其¹H NMR和¹³C NMR谱的信号进行了归属.     

模板对异构体选择性生长的动力学控制作用与化学气相沉积金刚石的生长机理

阐述了模板的动力学控制作用对大尺度有序结构特别是亚稳相的生长，对自由能相差很小的异构体的选择生长所具有的重要作用.汲取现有金刚石生长理论的合理思想，以模板概念为基础给出了对化学气相沉积(CVD)过程的动力学热力学综合描述：1)碳原子在碳氢化合物中的化学势高于固相碳，气相碳氢化合物的碳原子有可能落到化学势较低的固态碳的各种异构体.2)气相碳通过表面反应实现向固相碳的转化.3)表面的模板作用是控制气相碳原子转换方式的主要动力学因素，不同的表面(石墨各种取向的表面及金刚石不同取向的表面)选择了落入其上的碳原子的结构方式及能量状态.4)因此,衬底的不同区域可发生几种不同的独立的表面反应过程,这些反应对应于不同表面的生长.5）而这些表面反应的方向性及速度受表面临域热力学因素的影响，反应的方向性决定了某种晶面是生长或刻蚀，在特定的温度、压强及各种气体分压下可以实现金刚石的生长和石墨的刻蚀.6)衬底局域晶格结构及键价结构和衬底表面气相的温度、压强及各种气体分压等热力学条件共同决定了成核的临界条件.7）与外界有能量和物质交换的等离子体系统，以及气相中发生的一系列化学反应，仅起到了维持某种固相表面生长所需要的非平衡热力学条件和化学条件的作用.金刚石和石墨表面具有的模板动力学控制作用，在特定热力学条件下主导自身外延层的生长方式；异质衬底的某些局域微观结构可以作为新相生长成核的局域模板；不同材料、不同的处理方法、及不同的化学环境下的衬底具有不同的局域微观结构，从而决定了多晶薄膜的取向优势. 关键词： 模板 异构体 选择性生长 金刚石薄膜     

Effect of glycidyl methacrylateas compatibilizeron physico-chemical properties of gamma irradiated composites ofethylene propylene diene monomer rubber / styrene butadiene rubber/ground tire rubber

ABSTRACT

Composites of ethylene propylene diene monomer rubber (EPDM)/ styrene butadiene rubber (SBR)/ground tire rubber (GTR)(50/50/20) phr (part per hundred parts of rubber, by weight)loaded with different contents of glycidylmethacrylate (GMA) 2–6?phr. were irradiatedfrom 50 to 250?kGy. The physicochemical properties were investigated.

Irradiation dose and GMA improved physicochemical properties, the optimum content of GMA is 6?phr at a low dose of irradiation. These results were confirmed by scanning electron microscopy (SEM).     

Structure and Properties of a cis-1,4-Polybutadiene/Organic Montmorillonite Nanocomposite Prepared via In Situ Polymerization

Cis-1,4-polybutadiene (cis-1,4-PB) is one of the most important synthetic rubbers, having superior performances such as wear resistance, cold resistance and high elasticity. However, its mechanical properties, including low tensile strength, tear resistance and thermal stability, limit its application in comparison to natural rubber and butadiene-styrene rubber that have excellent overall performances. Thus, the reinforcing of cis-1,4-PB is a necessity. The dispersion of clay in rubbers on the nanoscale can improve the mechanical, gas permeability and thermal properties of the resulting composites. In this paper, organic montmorillonite (OMMT) clay was dispersed into the cis-1,4-PB matrix via an in-situ polymerization method and the chemical structure, phase morphology, mechanical properties and thermal stability of the composite were investigated. The properties of the composite were analyzed by such techniques as X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM) and thermal gravimetric analysis (TGA). In the in-situ polymerization, a Ni-based catalyst system with the presence of OMMT showed high efficiency and 1,4-selectivity for the polymerization of butadiene. The OMMT could be dispersed in the polymeric matrix on the nanoscale during the polymerization. The interfusion of OMMT had little influence on the thermal stability and the chemical micro-structure of the cis-1,4-PB when the content of cis-1,4 units was more than 95%. The loss tangent of the composite was higher than that of cis-1,4-PB from ?110 to ?55°C, the temperature range examined, and the mechanical properties of the cis-1,4-PB/OMMT nanocomposite (NC) were improved upon the addition of OMMT.     

Study of the road surface properties that control the acoustic performance of a rubberised asphalt mixture

Simultaneously with the fact that vehicle industry has been able to lower the noise emission from driving vehicles, tire/pavement noise has become the most significant source of traffic noise. In order to reduce it, low noise surfaces are seen as a practical solution. One of these types of surfaces may be elaborated with bituminous mixtures with crumb tire rubber added to the binder in high content by a wet process. However, the generation mechanisms involved in the tire/pavement sound and the reasons of the noise attenuation achieved with these mixtures are not so clear. This study analyses the different generation mechanisms that take place in the tire/pavement sound generation in these crumb tire rubber pavements. The surface properties of the in-service pavement, which are most important in controlling the acoustic performance (texture, acoustic absorption and dynamic stiffness or mechanical impedance), have been measured for the characterization of a test track constructed with and without crumb tire rubber. After results correlation of these surface characteristics in a pavement with crumb tire rubber added by a wet process, it seems that the parameters of roughness and texture could have a relevant role in the global tire/pavement sound emission, whereas dynamic stiffness influence is relatively minor.     

Angular-distribution He(I) /Ne(I) /Ar(I) photoelectron spectra of unsaturated hydrocarbons

The energy dependence of the anisotropy parameters of the π- and selected σ-bands of ethylene, 1,3-butadiene, benzene, cyclohexene, norbornadiene, 1,3-and 1,4-cyclohexadiene has been determined in the low energy region. Whereas the behaviour of the σ-bands is much less uniform, all π-band β-values decrease with decreasing energy towards similar threshold values. Strong intra-band energy dependencies have been observed for both π and σ orbitals, while in the multiple π-orbital molecules there is a symmetry-specific contribution to the π β-values. Marked intensity variations are observed among the ethylene, butadiene and benzene bands, and the anisotropy-parameter-based assignment of symmetric character to the 1,4-cyclohexadiene first band is confirmed.     

Effect of the amounts of glycidyl methacrylate on the mechanical and dynamic properties of styrene–butadiene–glycidyl methacrylate terpolymer/silica composites

GMA-SBRs with GMA contents in the range of 0.06–0.71 wt.% were synthesized and used to evaluate the properties of the silica composites for fuel-efficient tires. The chemical structures of the GMA-SBRs were analyzed using Fourier transform infrared spectroscopy, ¹H nuclear magnetic resonance (¹H NMR), size exclusion chromatography (SEC), and differential scanning calorimetry (DSC). GMA-SBRs can enhance filler–rubber interaction through covalent bond formation between the silica filler and rubber molecules. After compounding, the cure characteristics and mechanical and dynamic properties of the GMA-SBR silica-filled composites were analyzed. The mechanical properties, including the Mooney viscosity, bound rubber, swelling ratio, and moduli, exhibited obvious differences with increasing GMA content. However, the optimum content of GMA in the GMA-SBR, in terms of dynamic properties such as the Payne effect which represents the change in dynamic modulus against the strain to determine the extent of filler flocculation and tan δ at 60 °C representing tire rolling resistance, was ~0.6 wt.%. These results are due to improved silica dispersion, resulting from increased covalent bond formation between GMA-SBR and the silica surface. This approach assists in the determination of functional group contents in functionalized emulsion styrene–butadiene rubber for fuel-efficient tires, leading to a decrease in vehicular greenhouse gas emission.     

Effects of Replacement of Part of the Silica Reinforcement with Hybrid Modified Microcrystalline Cellulose on the Properties of their Rubber Composites

Hybrid modified microcrystalline cellulose (HMCC), with SiO₂ nanoparticles being in-situ loaded on the surface of microcrystalline cellulose (MCC), was obtained through a sol-gel process of tetraethoxysilane (TEOS) by using ammonia as catalyst. HMCC was characterized by thermogravimetric analysis and scanning electron microscopy. The results showed that the spherical nano-SiO₂ particles had been loaded successfully on the surface of the MCC with a loading ratio of approximately 10%. Then the HMCC was used in high vinyl solution-polymerized styrene butadiene rubber (SSBR)/silica compounds to replace part of the silica, and its effects on the physio-mechanical and dynamic mechanical properties of the vulcanizates were investigated. The results showed that the HMCC samples had improved physio-mechanical properties and lower heat build-up than that of MCC ones. Dynamic mechanical analysis (DMA) showed that the tanδ value of the compounds decreased at 60°C while increased obviously at 0°C, which meant that the tires would have improved wet-skid resistance while maintaining low rolling resistance when HMCC was used in tire tread compounds. As observed from scanning electron microscopy (SEM) photos, the sizes of the HMCC were in-situ decreased from 20–90 µm to 0.5–10 µm during the processing of the rubber compounds. Compared with MCC, the interfacial adhesion between HMCC and rubber was also improved greatly.     

Rotational analysis of bands in the high-resolution infrared spectra of the three species of butadiene-1,4-d2; refinement of the assignments of the vibrational fundamentals

Samples of trans,trans and cis,cis forms of butadiene-1,4-d₂ have been synthesized and found to contain useful amounts of the cis,trans species as a contaminant. Assignments of fundamental frequencies for the three isotopomers of butadiene-1,4-d₂ have been extended and improved from investigations of their Raman spectra as well as their infrared (IR) spectra. High-resolution IR spectra have been recorded for the three isotopomers, and a rotational analysis has been completed for strong bands of each species. Ground state and some upper state rotational constants have been fit. Corresponding ground state moments of inertia compare favorably with equilibrium moments of inertia obtained from B3LYP/6-311++G** theory. Two ¹³C isotopomers are being prepared, and an improved structural analysis of butadiene will soon be available to assess how π-electron delocalization affects its structure.     

Electronic structure and fluorescence of the Mg(II) complex of 1,4-diazepinotribenzoporphyrazine

Spectral and luminescent properties of a new phthalocyanine analog, the magnesium complex of diphenyl substituted mono(1,4-diazepino)tribenzoporphyrazine, have been studied at 293 and 77 K. The results have been explained on the basis of quantum-chemical calculations for both this molecule and its simpler analogs with respect to 6H/1H-isomerism of the 1,4-diazepine ring. The small difference between the ground-state energies for the 6H and 1H isomers makes tautomerism between them possible. It is shown that the electronic transitions with intramolecular charge transfer from the diazepine fragment to the macrocycle have relatively low energy, especially for the 1H isomers. These states can be of considerable importance for photophysical and photochemical processes. A comparison of the theoretical and experimental electronic absorption spectra has confirmed that the diazepine ring in the substituted Mg-diazepinoporphyrazine is present in the 6H-form. It is established that substitution of one benzene ring by a diazepine fragment leads to quenching of fluorescence, decreasing its quantum yield to 27% (for Mg-phthalocyanine 76%). Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 76, No. 3, pp. 365–375, May–June, 2009.     

Comparative DFT study of the adsorption of 1,3-butadiene, 1-butene and 2-cis/trans-butenes on the Pt(1 1 1) and Pd(1 1 1) surfaces

The interaction of 1,3-butadiene, 1-butene and 2-cis/trans-butenes on the Pt(1 1 1) and Pd(1 1 1) surfaces has been studied with density functional theory methods (DFT). The same most stable adsorption modes have been found on both metal surfaces with similar adsorption energies. For 1,3-butadiene the 1,2,3,4-tetra-σ adsorption structure is shown to be the most stable one, in competition with a 1,4-metallacycle-type mode, which is only less stable by 10-12 kJ mol⁻¹. On Pt(1 1 1) these total energy calculations were combined with simulations of the vibrational spectra. This confirms that the 1,2,3,4-tetra-σ adsorption is the most probable adsorption structure, but cannot exclude the 1,4-metallacycle as a minority species. Although similar in type and energy, the adsorption on the Pd(1 1 1) surface shows a markedly different geometry, with a smaller molecular distortion upon adsorption. The most stable adsorption structure for the butene isomers is the di-σ-mode. Similarly to the case of the 1,3-butadiene, the adsorption geometry is closer to the gas phase one on Pd than on Pt, hence explaining the different spectroscopic results, without the previously assumed requirement of a different binding mode. Moreover the present study has shown that the different selectivity observed on Pt(1 1 1) and Pd(1 1 1) for the hydrogenation reaction of butadiene cannot be satisfactory explained by the single comparison of the relative stabilities of 1,3-butadiene and 1-butene on these metals.     

Effect of High Aspect Ratio Fillers on the Performance of Styrene-Butadiene Rubber

Among the many material performance properties of vulcanized elastomers for tire tread application, rolling resistance and wet traction are particularly important since both greatly impact fuel efficiency and traction of a vehicle. Rolling resistance and wet traction are generally negatively correlated, i.e., with the increase in rolling resistance of a tire, its wet traction decreases. Silica nanofillers are often used for achieving the desired balance of wet traction and rolling resistance. However, the high cost of silica limits its wide spread application. In this research we studied the effects of using fillers with different aspect ratios (calculated by dividing the long dimension of a filler by its short dimension) on the performance of vulcanized styrene butadiene rubber (SBR), a common rubber for tire tread application. Three high aspect ratio fillers were used: aragonite calcium carbonate, wollastonite and carbon nanofiber. For comparison purpose, spherical silica filler was also included. We found that the high aspect ratio fillers were efficient in improving the wet traction and rolling resistance as well as enhancing the mechanical energy dissipation of SBR. Among the three high aspect ratio fillers studied, wollastonite provided the best wet traction and rolling resistance balance due to its high aspect ratio and compatibility with the base rubber. The effects of fillers induced crosslinking on the dynamic performance were also discussed.