六亚甲基桥连的希夫碱及其锰（Ⅲ）络合物催化剂的红外光谱研究

研究了六亚甲基桥连的希夫碱及其锰（Ⅲ）络合物催化剂的红外光谱，对一些主要谱带进行了经验归属。配体的分子内氢键谱带出现在～３４３８ｃｍ－１（以ＬＨ为例），νＣ＝Ｎ谱带在～１６３０ｃｍ－１（以ＣＨ为例，下同），苯的特征谱带在～１５９８，～１４６９和～７５５ｃｍ－１，νＭｎ—Ｎ为主的复合振动在～３６９ｃｍ－１，δＭｎ—Ｎ为主的复合振动在～２４７ｃｍ－１，νＭｎ—Ｏ为主的复合振动在～３２９ｃｍ－１，δＭｎ—Ｏ为主的复合振动在～２７５ｃｍ－１，νＭｎ—Ｃｌ特征谱带在～３０３ｃｍ－１。与苯基锰（Ⅲ）卟啉络合物相比，νＭｎ—Ｎ特征谱带向高波数位移，νＭｎ—Ｃｌ特征谱带则向低波数有较大位移。     

α-呋喃酯的结构与红外光谱特征

总结和归属了α－呋喃甲酸酯α－呋喃甲醇酯和α－呋喃丙烯酸酯的主要红外吸收谱带和特征,讨论了其红外吸收频率随取代基结构而变化的规律。结果表明：α－呋喃环存在三个明显的吸收特征,α－呋喃丙烯酸酯中ＶＣ＝Ｃ约为１６４１ｃｍ＾－１,δ＝Ｃ－Ｈ面外变角振动频率为９７３ｃｍ＾－１,表明双键为反式构型。ＶＣ＝Ｏ约为１７１３ｃｍ＾－１,Ｃ－Ｏ－Ｃ键对称与伸缩振动在１３０５,１２６２和１１６５ｃｍ＾－１处产生三个强     

邻羧基苯基荧光酮与碲显色反应的研究及应用

在ｐＨ＝４．５ＨＡｃ－ＮａＡｃ缓冲介质中,ＣＴＭＡＢ存在下,邻羧基苯基荧光酮（ｏ－ＣＰＦ）和Ｔｅ（Ⅳ）生成４∶１稳定络合物,λｍａｘ＝５６０ｎｍ,ε＝１．２５×１０５Ｌ·ｍｏｌ－１·ｃｍ－１。Ｔｅ（Ⅳ）含量在０—１０μｇ／２５ｍＬ内符合比耳定律,方法用于烟尘中碲的测定,结果令人满意。     

4－羧基杂氮硅三环中羧基红外光谱的研究

１－甲基及１－乙烯基－４－羧基杂氮硅三环在１６４５～１６３５ｃｍ－１均有与４－羧基相联系的弱吸收。对１－氯烷基取代物在上述范围的红外光谱研究表明，此吸收应归属于氢键存在下羧基上Ｃ＝０的伸缩振动，这种氢键形成于４－羧基与另一杂氮硅三环的桥氧之间，给杂氮硅三环化合物的质子化机理提供了直接证据。     

4—羧基杂氮硅三环中羧基红外光谱的研究

１－甲基及１－乙烯基－４－羧基杂氮硅三环在１６４５～１６３５ｃｍ＾－１均有与４－羧基相联系的弱吸收。对１－氯烷基取代物在上述范围的红外光谱研究表明，此吸收应归属于氢键存在下羧基上Ｃ＝Ｏ的伸缩振动，这种氢键形成于４－羧基与另一杂氮硅三环的桥氧之间，给杂氮硅三环化合物的质子化机理提供了直接证据。     

含R2dtc配体和V=O基的金属簇红外光谱研究

本文报道两类含Ｒ２ｄｔｃ配体的金属簇的红外光谱特点及某些规律,含Ｒ２ｄｔｃ的立方簇合物在４００－５００ｃｍ＾－１有较宽而弱的吸收,可归结于Ｍ－μ３Ｓ振动。Ｍ－Ｓｄｔｃ在３３０－３８０ｃｍ＾－１,Ｃ－Ｎ振动在１４７０－１５１０ｃｍ＾－１。二甲基ｄｔｃ配体立方的ｖ（Ｃ－Ｎ）与ｖ（Ｃ＝Ｓ）比值他二烷基ｄｔｃ立方烷的相应振动分别蓝移和红移,可归结于甲基超共轭效应所致。「Ｖ２Ｃｕ２Ｓ４（Ｒ２ｄｔｃ）２（ＰｈＳ）２」＾２－和「ＶＣｕ４Ｓ４（Ｒ２ｄｔｃ）ｎ（ＰｈＳ）４－ｎ」＾３－（ｎ＝０,１,２）的Ｍ－μ３Ｓ振动分别出现在４８０和４６５ｃｍ＾－１,可作为区别两类化合物的一个指标。另一类含（Ｒ２ｄｔｃ）２Ｖ２Ｏ２（μ－Ｓ）２单元的金属簇中,Ｖ－Ｏ伸缩频率在８４４－９７０ｃｍ＾－１范围内,（Ｅｔ４Ｎ）「Ｖ２Ｓ２Ｏ３（Ｅｔ２ｄｔｃ     

Y_（1－x）Nd_xSr_2Cu_（2．7）Mo_（0．3）O_（7－δ）体系的拉曼和红外光谱研究

利用拉曼散射和红外吸收光谱研究了Ｙ１－ｘＮｄｘＳｒ２Ｃｕ２．７Ｍｏ０．３Ｏ７－δ（ｘ＝０，０．２，０．５，０．８，１．０）系列样品的声子振动性质。实验结果表明，对ｘ＝０的样品，在拉曼光谱中主要出现３２３，４４３，５２２和５７８ｃｍ－１几个特征峰，在中红外吸收光谱中出现５２２，５８０和６４６ｃｍ－１特征峰。随着样品中Ｎｄ组分的增加，３２３ｃｍ－１峰向低波数发生位移，而５２２和６４６ｃｍ－１峰则向高波数发生位移。本文对这些振动模进行了指认，并对其随不同样品组分的变化行为进行了讨论     

Al(Ⅲ)-CAS-OP-PVA体系分光光度法测定沸石分子筛中的铝

研究了在聚乙二醇辛基苯基醚（乳化剂ＯＰ）及聚乙烯醇（ＰＶＡ）存在下铝（Ⅲ）与铬天青Ｓ（ＣＡＳ）的显色反应。在ｐＨ５．３的ＨＡｃ－ＮａＡｃ缓冲介质中，题示体系最大吸收波长λｍａｘ＝６１２ｎｍ，对比度Δλ＝１０２ｎｍ，表观摩尔吸光系数ε６１２ｎｍ＝２．８４×１０４Ｌ·ｍｏｌ－１·ｃｍ－１。铝（Ⅲ）浓度在０－０．６０μｇ／ｍＬ范围内遵守比耳定律。本法已成功地用于沸石分子筛中铝含量的测定，结果良好。该法具有稳定性高、准确度好的特点。     

LaH2分子基态（C2V,A1）的势能函数

在ＱＣＩＳＤ水平上基于相对论紧致有效势（ＲＣＥＰ：Ｒｅｌａｔｉｖｉｓｔｉｃ Ｃｏｍｐａｃｔ Ｅｆｆｅｃｔｉｖｅ Ｐｏｔｅｎ－ｔｉａｌ）方法优化出ＬａＨ２分子的基态为Ｃ２ｖ（Ｘ＾２Ａ１）构型,其〈ＨＬａＨ－１２４４°、平衡核间距Ｒｅ＝２．１９４５Ａ和离子解能Ｄｅ＝５．５９９ｅＶ,并计算出谐振频率：ｖ１＝１２１６．５２１ｃｍ＾－１、ｖ２＝１０８７．４１７ｃｍ＾－１和ｖ３＝２１５６．９５７２ｃｍ＾－１。     

铜与2-羟基-3-羧基-5-磺酸基苯重氮氨基偶氮苯反应的分光光度法研究及应用

研究了铜与２－羟基－３－羧基－５－磺酸基苯重氮氨基偶氮苯（ＨＣＳＤＡＡ）的显色反应。在Ｔｒｉ－ｔｏｎＮ－１０１存在下和ｐＨ１０．４～１１．５的缓冲介质中，Ｃｕ２＋与ＨＣＳＤＡＡ形成１∶２的红色配合物，其最大吸收波长是５３０ｎｍ，对比度为１０２ｎｍ，表观摩尔吸光系数为１．３１×１０５Ｌ·ｍｏｌ－１·ｃｍ－１。铜在０～０．２４μｇ／ｍＬ范围内服从比尔定律。用于铅锌矿和花生中微量铜的测定，相对误差不大于３．７％，相对标准偏差不大于１．６％（ｎ＝６）。     

基于傅里叶红外光谱的钢渣代炭黑环保型复合橡胶的补强机理及性能研究

以铁水脱硫渣作为研究对象,利用铁水脱硫渣作为橡胶填料取代部分炭黑与丁苯橡胶进行复合,制备铁水脱硫渣/丁苯橡胶。利用多种方法测试铁水脱硫渣/丁苯橡胶的性能,采用傅里叶变换红外光谱仪测试硫化过程中不同阶段铁水脱硫渣的结构组成。结果表明：利用铁水脱硫渣部分替代炭黑,可达到补强效果与降低补强剂成本的目的。铁水脱硫渣/丁苯橡胶的正硫化时间(t₉₀)为25.08 min,其焦烧期为0~15 min、热硫化期15~25 min和硫化平坦期25~45 min。在焦烧期铁水脱硫渣可以提供碱环境,利于增加丁苯橡胶流动性;在热硫化期与硫化平坦期,铁水脱硫渣中Ca₂SiO₄能够持续加速发生水化反应生成C-S-H凝胶,达到对丁苯橡胶补强的效果。另外,铁水脱硫渣可以避免铁水脱硫渣/丁苯橡胶过硫化期的出现。     

Carbon Black–Filled Styrene Butadiene Rubber Masterbatch Based on Simple Mixing of Latex and Carbon Black Suspension: Preparation and Mechanical Properties

An improved process was developed for the production of carbon black (CB)–filled styrene butadiene rubber masterbatch (SBR-CB-MB) using a simple latex/CB mixing technology; the improvement comprised processing the CB as an emulsifier-free aqueous suspension by high-rate shearing. Tensile and tear strength, dynamic compression behaviors, the Payne effect, equilibrium swelling and bound rubber of the SBR-CB-MB and dry mixing CB filled SBR (SBR-CB-DM), covering a wide range of CB loading (45–70 phr), were investigated and compared. It was found that the tensile and tear strength, heat buildup and compression set, abrasion volume loss, and the Payne effect of the SBR-CB-MB were lower than those of the SBR-CB-DM, while the bound rubber content were higher, indicating good CB/rubber interaction in the SBR-CB-MB. SEM analysis showed that no free CB could be found on the surface or inside of the granular SBR-CB-MB particles, indicating good CB dispersion in the rubber matrix.     

基于X射线衍射法研究改性脱硫灰基生态橡胶的制备过程及机理

脱硫灰作为半干法脱硫技术主要副产品,其利用难度大且成本高,导致大量脱硫灰以直接堆放和填埋的方式处理,不但造成环境污染,而且浪费潜在资源。橡胶作为广泛应用的聚合物材料,在橡胶制备加工过程中需大量使用填料改善其力学性能、加工性能和填充增容。炭黑与白炭黑作为常用的橡胶填料,其不仅生产工艺繁杂,而且对能源和资源消耗量大,导致成本较高。面对上述问题,如何利用脱硫灰开发一种价格低廉的无机橡胶填料,既是固体废弃物高附加值利用又是资源可持续发展的重要途径之一,也是橡胶企业大幅降低填料成本提高经济效益的重要途径之一。由于脱硫灰属于无机材料,橡胶属于有机材料,为了更好的降低脱硫灰界面与橡胶界面(无机界面/有机界面)的不相容性,需要对脱硫灰进行化学改性处理。以该课题组前期取得的研究成果为基础,创新性以改性脱硫灰取代部分炭黑制备改性脱硫灰基生态橡胶。利用XRD对改性脱硫灰基生态橡胶制备过程各阶段的生产物质进行测试,即丁苯橡胶密炼胶制备阶段、改性脱硫灰基生态橡胶密炼胶制备阶段和改性脱硫灰基生态橡胶制备阶段,从微观层面揭示丁苯橡胶密炼胶制备过程、改性脱硫灰基生态橡胶密炼胶制备过程和改性脱硫灰基生态橡胶制备过程,阐明硫化过程中丁苯橡胶密炼胶与改性脱硫灰的结合机理。同时采用SEM对丁苯橡胶密炼胶与改性脱硫灰基生态橡胶密炼胶的微观形貌进行测试,以进一步佐证所获得的相关机理。结果表明:改性脱硫灰加入丁苯橡胶密炼胶后,改性脱硫灰基生态橡胶密炼胶的最大转矩F max大幅下降、最小转矩F L保持稳定、ΔF=F max-F L显著下降,同时焦烧时间t 10与正硫化时间t 90均缩短。硫化诱导期为0~387 s、硫化反应期为387~1586 s和硫化平坦期为1586~1800 s。在硫化诱导期形成非交联网络结构、硫化反应期前期形成基本交联网络结构、硫化反应期后期完善交联网络结构和硫化平坦期保持交联网络结构。以期为高附加值的脱硫灰资源化利用提供一定理论依据和技术支持。     

About the cure kinetics in natural rubber/styrene Butadiene rubber blends at 433 K

Vulcanized blends of elastomers are employed in several goods mainly to improve physical properties and reduce costs. One of the most used blends of this kind is that composed by natural rubber (NR) and styrene butadiene rubber (SBR). The cure kinetic of these blends depends mainly on the compound formulation and the cure temperature and time. The preparation method of the blends can influence the mechanical properties of the vulcanized compounds.     

苯乙烯的三维荧光特性及水污染应急处理

苯乙烯对人体健康和自然环境具有极大的危害,是国际卫生组织确认的致癌物。历年来,苯乙烯泄漏事故频繁发生,对饮用水安全造成了极大的隐患。对水中苯乙烯污染进行快速监测并采取切实有效的应急处理措施有助于保障饮用水的卫生安全。利用三维荧光光谱技术对苯乙烯的水溶液进行分析,发现在Ex255/Em305处有一个明显的荧光峰,荧光峰值与苯乙烯溶液浓度呈现良好的线性相关,相关系数r达到了0.995 7,其颜色随浓度增加而变深。苯乙烯中共有4个共轭π键,其中苯环具有大的共轭π键结构,乙烯基上同样具有一个共轭π键。同时,苯乙烯的分子结构中,碳原子处于同一个平面上,属于平面构型且具有一定的刚性,符合强荧光物质所具有的特征。因此通过三维荧光扫描结合苯乙烯的荧光特性,能快速测定水体中苯乙烯浓度及判断水体的污染程度。粉末活性炭可以有效地吸附去除水中的苯乙烯。当苯乙烯在源水中的浓度达到《生活饮用水卫生标准》规定的限值0.02 mg·L-1时,采用180目的粉末活性炭,投加量为15 mg·L-1时,苯乙烯浓度可降至0.001 mg·L-1,去除率达95.5%。     

Effect of Modified Nano-Silica on the Reinforcement of Styrene Butadiene Rubber Composites

The performance of styrene butadiene rubber (SBR) composites filled with nano-silica has been improved by surface modification of the nano-silica using silane coupling agents. The dispersion of nano-silica in SBR rubber and the bonding force of nano-silica with SBR were significantly improved, and the physical and mechanical properties of the vulcanized rubber were greatly improved. The results showed Si69 (bis-(γ- triethoxysilylpropyl)-tetrasulfide) was the best modifier among the six silane coupling agents used in the experiments, and its optimum amount was 12% (wt) of nano-silica.     

A Comparative Study of the Dynamic-Mechanical Properties of Styrene Butadiene Rubber/Epoxidized Natural Rubber Dual Filler Nanocomposites Cured by Sulfur or Electron Beam Irradiation

The properties of (50/50?wt%) styrene butadiene rubber/epoxidized (50%) natural rubber (SBR/ENR50) blends containing nanoclay (NC, 5 or 10phr) without and with carbon black (CB 20phr) cured by sulfur or by electron beam (EB) irradiation (50 and 100kGy), were compared. A sulfur cured compound containing 35phr CB was prepared as a reference sample. Dynamic mechanical thermal analysis (DMTA) indicated that the sulfur cured sample containing 10phr NC and 20phr CB and the 100kGy irradiated sample with 5phr NC and 20phr CB had higher crosslink density, storage modulus, and tensile strength, and less loss factor and loss modulus, compared to the reference sample. Scanning electron microscopy (SEM) images of cryo- fractured surfaces confirmed the DMA and crosslink density results. We suggest a light weight 100kGy irradiated sample containing the lowest amount of NC and 20phr CB with a uniform distribution of the –C–C– bonds crosslinks, for high thermal stability applications and also for passenger cars tire treads, for its ice grip and wet skid properties especially for icy and wet roads, with improvements of 23% and 20%, respectively as compared to the reference sample.     

浊度计快速测定苯乙烯单体中聚合物的研究

建立了用浊度计快速测定苯乙烯单体中聚合物的方法，样品用甲醇溶解后，以样品／正己烷溶液为空白，通过测定其浊度，确定聚合物的含量。消除了GB／T 12688．3-1990用光度法测定聚合物过程中空白基体的影响。在0-50mg／kg范围内线性关系良好，相关系数r=0．9991，检出限达到0．01mg／kg，方法简便、快速，完全能达到实际检测要求。     

NMR relaxation and NMR imaging of elastomers in the course of thermal aging

A complex aging regime occurs in the course of thermal aging of elastomers. Depending on the type and the content of the rubber filler materials, temperature, chemical environment (normally air), and time, a different aging process can be observed also by nuclear magnetic resonance (NMR) [1–6]. The methods used are the common spin-echo ¹H-NMR, including variable echo times and parameter-selective NMR-¹H-imaging (material properties imaging). The decay of the echo-magnetization is discussed on the basis of a single-chain model with a distribution of dipolar interactions. This model is based on the influence of a very fast, but anisotropic, local motion, as well as larger and slower motions, which are able to diminish the residual dipolar interaction. Carbon-black-filled natural rubber, as well as silica and carbon-black-filled E-SBR (emulsion-polymerized styrene butadiene rubber) and S-SBR (solution-polymerized SBR) are the systems under investigation, with the results showing some characteristic features of the course of aging observable by NMR.     

聚苯乙烯餐具中残留苯乙烯单体的顶空气相色谱法测定

采用顶空进样器的气相色谱仪，分析聚苯乙烯餐具中残留苯乙烯单体量；以校准曲线法进行定量测定；在选定的色谱条件下，测定苯乙烯含量的线性范围为5．0－1000mg/L，检出限小于0．1mg/L；本方法操作简便、快速、结果准确，适应于残留苯乙烯单体含量的测定。