顺1,4-聚丁二烯在不同溶剂中的环化反应及其机理的研究

以烯丙基氯 一氯二乙基铝 (CH2 CHCH2 Cl AlEt2 Cl)催化体系研究了顺 1 ,4 聚丁二烯在不同溶剂(三甲苯、二甲苯、甲苯、苯和环己烷 )中的环化反应 .结合环化产物红外光谱的测定 ,提出芳烃溶剂分子经受阳碳离子亲电取代作用而参与环化的机理 ,以此解释了若干实验事实 ,并对已有文献报道进行了讨论 .     

钕-铝双金属配合物催化异戊二烯聚合的原位环化反应

环化聚异戊二烯 (CPIP)具有优良的光敏性、较好的耐热性和力学性能 ,在光刻胶、胶粘剂、橡胶改性等方面得到广泛应用 [1,2 ] .CPIP可按阳离子机理经单体环聚或聚合物环化两种方法合成 .我们 [3]最近提出一种直接从单体出发在稀土催化聚合过程中引入烯丙基氯原位合成 CPIP的方法 .本文在此基础上 ,以三异丙氧基钕 -三乙基铝 -一氯二乙基铝均相体系中分离出的钕 -铝双金属配合物作为单组分催化剂 ,简化聚合体系 ,以便直观地考察氯化物、烷基铝等的作用 ,揭示稀土催化 IP聚合原位环化反应的过程 .1　实验部分　　 CPIP的合成参见文献 […     

稀土催化丁二烯顺式聚合过程中的环化改性

采用ＮｄＣｌ３·３ｉ－ＰｒＯＨ－ＡｌＥｔ３稀土催化剂进行丁二烯的顺式聚合，在聚合过程中引入烯丙基氯，进行分子内环化反应以及单体的环聚反应．考察了稀土催化剂用量、ｎ（烯丙基氯）／ｎ（ＡｌＥｔ３）、环化时间、反应温度、单体浓度等对环化反应的影响，并对产物进行了红外光谱、核磁共振光谱的表征     

二氯丙醇环化制备环氧氨丙烷的工艺及动力学研究

考察了各种因素对二氯丙醇环化反应的影响,以及无机盐NaCI的存在对粗环氧氯丙烷（ECH）溶液浓度的影响。建立了环化反应的动力学模型并验证了其正确性,得到了二氯丙醇环化反应的动力学参数。结果表明,二氯丙醇环化的最佳反应条件为：二氯丙醇与NaOH的摩尔比为1：1．2,环化温度为75℃、反应时间为90s。二氯丙醇环化反应为二级反应,1,2-二氯丙醇和1,3-二氯丙醇环化反应的活化能分别是94．19kJ／mol和92．23kJ／mol。     

钛系Ziegler－Natta催化剂下的丙烯／α－烯烃的共聚合

研究了ＴｉＣｌ＿４／ＭｇＣｌ＿２－三乙基铝（ＴＥＡ）高效载体催化体系下的丙烯／癸烯－１共聚及δ－ＴｉＣｌ＿３－－氯二乙基铝（ＤＥＡＣ）催化体系下的丙烯／辛烯－１共聚合的基本反应规律，考察了铝钛比、温度、共聚单体浓度等对共聚合的影响；对比了两种催化体系的不同，利用非均相Ｚｉｅｇｌｅｒ－Ｎａｔｔａ催化体系下共聚合的非稳态扩散动力学的观点，解释了观察到的共聚合催化效率增加，共聚物粒子增大等实验现象．     

N,N-二乙基胺乙基取代瓜尔胶的合成及结构表征

在碱催化条件下,利用N,N-二乙基氯乙胺盐酸盐与瓜尔胶和羟丙基瓜尔胶一步法合成得到N,N-二乙基胺乙基瓜尔胶和N,N-二乙基胺乙基羟丙基瓜尔胶。结果显示合成过程中温度、反应时间、羟丙基取代度及溶剂等因素对产品分子量和N,N-二乙基胺乙基取代度有影响。通过红外光谱和核磁法对N,N-二乙基胺乙基瓜尔胶和羟丙基N,N-二乙基胺乙基瓜尔胶的分子结构进行了分析,并通过碳谱对N,N-二乙基胺乙基在瓜尔胶分子链中糖环上的取代分布进行了分析。     

苄基咪唑氯镍酸盐的合成、结构及催化醛醇酯化反应活性研究

合成了三种苄基咪唑氯镍酸盐,通过红外光谱、元素分析、1H NMR以及X-射线单晶衍射对其进行结构表征,并研究了其在醛醇酯化反应中的催化活性。结果表明,在优化条件下,苄基咪唑氯镍酸盐对醛醇酯化反应有着较好的催化活性,以1,3-二(4-甲基苄基)咪唑鎓氯镍酸盐为催化剂,通过一步氧化酯化路线可以有效地催化氧化苯甲醛进行酯化反应,产率为80%。     

水中苯并[h]色烯衍生物的洁净合成

在三乙基苄基氯化铵(TEBA)存在下的水介质中，芳亚甲基丙二腈与1-萘酚发生 加成、环化反应生成2-氨基-3-氰基-4-芳基苯并[h]色烯．产物的结构通过元素分 析、红外光谱和核磁共振氢谱确证，该方法具有操作简单、产率高、环境友好的优 点．     

异喹啉酮类衍生物的合成研究

以间甲氧基苯乙胺和氯甲酸乙酯为原料,通过亲核取代、关环、四氢铝锂还原得到1,2,3,4-四氢异喹啉衍生物.其中关键步骤环化反应实现了使用多聚磷酸(PPA)简便有效地进行了关环,合成了一系列异喹啉酮类衍生物.     

O-炔丙基-N,N-二(2-氯乙基)-4-氨基苯酚的合成

以对氨基苯酚（1）为原料,经氨基的羟乙基化、酚羟基的苄基保护、氯代、脱保护制得N,N-二 (2-氯乙基) -对氨基苯酚（5）;在碳酸铯作用下,5与溴丙炔经O-烷基化反应合成了新化合物--O-炔丙基-N, N-二(2-氯乙基)-4-氨基苯酚,其结构经¹H NMR, ¹³C NMR和MS表征。     

丁苯橡胶为黏合剂的聚丙烯硫酸钡复合膜的制备

以丁苯橡胶(SBR)为黏合剂、羧甲基纤维素钠(CMC)为分散剂、聚丙烯(PP)膜为基体,在其两侧涂覆厚度2μm的硫酸钡(BaSO_4)颗粒,得到一种复合电池隔膜。对复合膜的形貌、润湿性、热稳定性、电导率等进行了研究。结果表明:BaSO_4涂层均匀涂布于PP膜表面,使复合膜中小于200nm的孔增多。同PP膜相比,复合膜具有较小的热收缩率和较好的润湿性。而与聚偏氟乙烯(PVDF)黏合剂相比,SBR具有更强的黏合性。以复合膜做为隔膜的电池在不同电流密度下具有更高的容量保持率。     

Unique rheological behavior of rubber based nanocomposites

Montmorillonite clay (N) based nanocomposites were prepared using three different grades of acrylonitrile butadiene rubber (NBR) (19%, 34%, and 50% acrylonitrile contents), styrene butadiene rubber (SBR), and polybutadiene rubber (BR). Rheological study was carried out on these nanocomposites at three different temperatures (110 °C, 120 °C, and 130 °C) over a range of shear rates for comparison. The results showed that the shear viscosity decreased with increasing shear rate and incorporation of the unmodified (N) and the modified (OC) fillers up to a certain loading, when the results were compared with the gum rubber. This effect became more prominent with increasing polarity of the rubber. The die swell, on the other hand, decreased with loading of N and OC. With increasing filler volume fraction, the die swell further decreased. Decrease of viscosity with concomitant decrease of die swell is unique in such systems. Consecutive runs of the same sample over different shear rates increased the viscosity. The results were explained with the help of X‐Ray Diffraction (XRD) data and Transmission Electron Microscopy (TEM).© 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1854–1864, 2005     

不同链化学结构丁苯橡胶与天然橡胶混容性研究

选择了三种丁苯橡胶 (SBR)———乳聚丁苯胶 (ESBR)、溶聚丁苯C(SSBR (C) )及溶聚丁苯B(SSBR(B) ) ,用红外光谱 (FTIR)分析了它们的链化学结构 .同时 ,用动态力学谱 (DMA)和示差扫描量热谱 (DSC)研究了这三种SBR与天然橡胶 (NR)的混容性 .结果表明 ,SSBR(B)与NR具有很好的混容性 .三种SBR与NR混容性的差别 ,与SBR链化学结构不同有关     

Morphology and performance of styrene butadiene rubber filled with modified graphite nanoplatelet and carbon black

In our work, effects of 2‐mercapto‐1‐methylimidazole modified graphite nanoplatelet (MMI–GN) and carbon black (CB) on static and dynamic mechanical properties of styrene butadiene rubber (SBR) composites were studied. MMI–GN is synthesized by ball‐mill process, and the result reveals that π–π interactions existed between MMI and GN. The results demonstrate that the static and dynamic mechanical performances of SBR/CB/MMI–GN composites are significantly improved over these of SBR/CB and SBR/CB/GN composites. Compared with SBR/CB, the tensile strength, tear strength, and modulus at 300% elongation of SBR/CB/MMI–GN–3 are greatly improved by 45%, 27%, and 4%, respectively. And the rolling resistance of SBR/CB/MMI–GN–3 is reduced by 3.7% with remaining almost unchanged in the wet grip property. The superiority of MMI–GN in the enhancement for the overall performance of SBR/CB composites is attributed to the well dispersion of GN throughout the SBR matrix and the enhanced interfacial interactions between GN and the SBR matrix. This work might expedite synthesis of the graphite‐based materials for enhancing rubber composites, and enlarge the potential applications of modified graphite to fabricate the high‐performance rubber composites. Copyright © 2016 John Wiley & Sons, Ltd.     

丁苯橡胶/天然橡胶复合体系动态力学性能

生热;动态力学损耗;丁苯橡胶/天然橡胶复合体系动态力学性能     

Nanoalloy Based on Clays: Intercalated‐Exfoliated Layered Silicate in High Performance Elastomer

A novel method is described for the preparation of nanocomposites comprising a high performance rubber for tire application and layered silicates clay. In this work nanocomposites of solution‐styrene butadiene rubber (S‐SBR) with montmorillonite layered silicate were prepared with carboxylated nitrile rubber (XNBR), a polar rubber, as a compatibilizer. A sufficient amount of organomodified layered silicate was loaded in carboxylated nitrile rubber (XNBR) and this compound was blended as a master batch in the S‐SBR. Mixed intercalated/exfoliated morphologies in the nanocomposite are evinced by X‐ray diffraction measurements and transmission electron microscopy. Dynamic mechanical analysis also supports the compatibility of the composites. A good dispersion of the layered silicate in the S‐SBR matrix was reflected from the physical properties of the nanocomposites, especially in terms of tensile strength and high elongation properties.     

丁苯橡胶／聚丙撑碳酸酯弹性体的结构与性能

聚丙撑碳酸酯（ＰＰＣ）是由ＣＯ２和环氧丙烷在聚合物负载的双金属催化剂作用下共聚而成的一类新型高分子材料［１］，其结构式如下：ＯＨＣＨ２ＣＨＣＨ３ＯＣＯＯｎＣＨ２ＣＨＣＨ３Ｏ］ｍＣＮＯｏＯＨ它的广泛应用对于环境保护和新资源开发具有实际意义．在...     

Study on combustion property and synergistic effect of intumescent flame retardant styrene butadiene rubber with metallic oxides

Effect of metallic oxides on flame retardancy and the thermal stability of styrene butadiene rubber (SBR) composites based on ammonium polyphosphate (APP) and pentaerythritol (PER) was studied by the limiting oxygen index (LOI), UL 94, the cone calorimeter tests, and thermogravimetry analysis (TGA), respectively. Scanning electron microscopy (SEM) and wide‐angle X‐ray diffraction (WAXD) were used to analyze the morphological structure and the component of the residue chars formed from the SBR composites accordingly. The addition of zirconium dioxide (ZrO₂) at a loading of 3.4 phr could improve the UL 94 test rating of the composite to V‐0. The TGA data illustrated that the metallic oxides could enhance the thermal stability of the SBR/Intumescent flame retardant additives (IFRs) composites at high temperature and increase the residue. Cone calorimeter test gave much clear evidence that the incorporation of ZrO₂ into SBR/IFRs composites resulted in the significant deduction of the heat release rate (HRR) values, and the SEM images showed that the char layers of the composites containing the metallic oxides became more compact. From the WAXD pattern, zirconium phosphate (ZrP₂O₇) may be formed by the reaction between ZrO₂ and APP. Due to the addition of ZrO₂ and the formation of ZrP₂O₇, the flame retardancy of the composite was improved. Copyright © 2009 John Wiley & Sons, Ltd.     

Interface and properties of epoxy resin modified by elastomeric nano-particles

Epoxy resin has been widely used as structuralmaterials and adhesives in electronics, aerospace in-dustries and etc. for its impressive overall properties.However, epoxy network is brittle and notch sensitive,which restricts its application scope. As a re…     

硼酰化钴在橡胶与镀锌钢丝粘合中的应用研究

研究硼酰化钴的用量变化对丁苯橡胶／天然橡胶与镀锌钢丝粘合的影响,通过表面分析对其粘合机理进行了研究。研究表明：硼酰化钴对丁苯橡胶／天然橡胶与镀锌钢丝粘合的粘合增强作用十分明显。硼酰化钴添加2phr左右,粘合性能最佳,同时硫化胶的物理性能得到改善。X-射线光电子能谱分析表明,粘合物镀锌钢丝界面中存在ZnO、ZnS、CoS2,说明粘合时发生了Zn的硫化反应,硼酰化钴中的钴向钢丝表面迁移,继而在锌层中扩散,提高了ZnO和ZnS晶格的缺陷浓度,这两种行为的共同作用,使橡胶与镀锌钢丝的粘合强度显著提高。