羟基取代的烷基苯磺酸盐在水/气和水/癸烷界面的结构特点（摘要）

驱油表面活性剂的分子设计是一项重要的研究课题.设计新型高效的驱油表面活性剂关键的问题在于如何洞察表面活性剂的结构和功能的关系.长线性烷基苯磺酸盐是一类非常流行的表面活性剂,广泛应用于工业和日常生活中.关于烷基苯磺酸盐的结构和功能研究已有大量的实验和理论工作报道.近来,结合分子设计的思想,实验上合成了新型的羟基取代的烷基苯磺酸盐表面活性剂,并研究了这类新型表面活性剂动态的界面行为.我们从理论上利用分子动力学模拟的方法研究了羟基取代的烷基苯磺酸盐单分子层在水/气和水/癸烷界面的结构特点.从液体密度剖面图、氢键、表面活性剂聚集结构和有序参数等方面,详细报道了2-羟基-3-癸基-5-辛基苯磺酸钠这种新型阴离子表面活性剂的界面特征.模拟结果表明随着表面活性剂分子数目的增加,每个表面活性剂在单分子层上形成分子内氢键的平均数目将下降,但形成分子内氢键的结构仍处于主导地位;烷基尾链的疏水部分,尤其是苯环3号位上取代的癸基随着表面活性剂覆盖度增大,向界面外延伸并且更加有序;二维径向分布函数描绘了表面活性剂聚集结构的特点并暗示了癸烷相将影响表面活性剂疏水部分的取向;表面活性剂分子容易形成长程氢键结构.我们的模拟结果是对实验研究的一个重要补充.此外,模拟中我们利用gromacs和ffamber程序,使用了全原子模型,这将为模拟烷基苯磺酸盐表面活性剂的界面行为提供新的方案.     

HRP-12催化剂上苯与直链烯烃的烷基化反应 Ⅰ. 本征反应动力学研究

直链烷基苯是生产阴离子表面活性剂直链烷基苯磺酸盐的重要原料。2000年以美国环球油品公司(UOP)的脱氢法工艺生产的直链烷基苯占世界直链烷基苯产量的88％。脱氢法以液体氢氟酸为催化剂由正构烯烃与苯进行烷基化反应生产直链烷基苯。由于液体氢氟酸催化剂具有较强的腐蚀     

系列烷基苯磺酸盐对烷烃的动态界面性能研究

从表面活性剂分子量、表面活性剂浓度、电解质浓度、 烷烃碳数等方面考察了系列烷基苯磺酸盐异构体纯化合物的油水动态界面张力行为。研究表明,表面活性剂分子量越大和电解质浓度增加使界面张力动态变化越慢,达到平衡所需时间越长;表面活性剂浓度增加和烷烃碳数增加使界面张力动态变化加快,达到平衡所需时间减少。     

系列烷基苯磺酸盐对烷烃的动态界面张力研究

从表面活性剂分子量、表面活性剂浓度、电解质浓度、烷烃碳数等方面考察了系列烷基苯磺酸盐异构体纯化合物的油水动态界面张力行为.研究表明,表面活性剂分子量增大和电解质浓度增加使界面张力动态变化减慢,达到平衡所需时间延长;表面活性剂浓度增加和烷烃碳数增加使界面张力动态变化加快,达到平衡所需时间减少.     

烷基苯磺酸盐在油水界面行为的介观模拟

采用耗散颗粒动力学(DPD)方法在介观层次上模拟了表面活性剂烷基苯磺酸盐在油/水界面的排布行为, 考察了分子结构、浓度、盐度、油相等因素对表面活性剂界面密度和界面效率的影响, 并探讨了利用表面活性剂复配协同效应提高界面活性的理论机制. 分子模拟给出的分子水平的微观信息为强化采油技术中配方筛选和表面活性剂的有效应用提供指导.     

流动注射测定阴离子表面活性剂注意问题的探讨

阴离子表面活性剂是合成洗涤剂的主要成分之一,主要是直链烷基苯酸钠和烷基磺酸钠类物质。阴离子表面活性剂进入水体后聚集在其它微粒表面,产生泡沫或发生乳化现象,阻断水中氧气的交换,同时消耗水中的溶解氧,导致水质恶化,该物质已成为当今水污染的一项重要指标。测定水中阴离     

热裂解-气相色谱-质谱联用法鉴定水性涂料中表面活性剂

根据烷基酚聚氧乙烯醚(APEO)、直链烷基苯磺酸盐(NABS)及脂肪醇硫酸盐(ALAS)3种表面活性剂的热裂解特征,提出了热裂解-气相色谱-质谱法(PGC-MS)检测水性涂料中上述3种表面活性剂的方法。水性涂料样品经在120℃烘干后粉碎,以正丁醇为溶剂对样品进行超声提取,除去溶剂后烘干,即得到含有表面活性剂组分的样品干膜,此样品供PGC-MS分析。样品在600℃裂解6s后,APEO的裂解产物为烷基酚和含有乙氧基单体的化合物;NABS裂解后生成烯烃和烷基苯的同系物;ALAS则裂解生成二氧化硫、烯烃和脂肪醇。根据GC-MS分析所得结果,即可对水性涂料中表面活性剂的类型作定性检测。方法的检出限(3S/N)均小于100mg·kg-1。     

直接进样电喷雾质谱分析烷基苯磺酸盐

采用直接进样法，电喷雾质谱分析三次采油用烷基苯磺酸盐，可以得到定性结果，定出该表面活性剂中各组分的分子式，操作简单易行．     

新型阴离子Gemini表面活性剂与非离子表面活性剂C10E6混合溶液的胶团化的研究

研究了烷基苯磺酸盐Gemini表面活性剂Ia与非离子表面活性剂C10E6溶液混合胶团中分子间的相互作用. 通过表面张力法测定了Ia 和C10E6不同比例不同温度下的临界胶束浓度(cmc). 结果表明, 两种表面活性剂以任何比例复配的cmc比单一表面活性剂的cmc都低, 表现出良好的协同效应. 传统型非离子表面活性剂C10E6、Gemini表面活性剂Ia及混合物的cmc都随着温度升高而降低. 而且, 任何配比的混合胶团中两种表面活性剂分子间的相互作用参数β都是负值, 这说明两种表面活性剂在混合胶团中产生了相互吸引的作用. 混合表面活性剂体系的胶团聚集数比单一Ia的大, 但比单一C10E6的小. 向Gemini表面活性剂Ia胶束中加入非离子表面活性剂C10E6会使胶束的微观极性变小.     

阳离子表面活性剂选择电极的研究

本文采用十六烷基苯磺酸根和四苯基硼根混合定域体制备的PVC膜阳离子表面活性剂选择电极,性能稳定,选择性好,对不同结构的阳离子表面活性剂的线性响应范围为1×10~(-6)—1×10~(-3)M,斜率53.0mV。用它测定了四种阳离子表面活性剂的临界胶束浓度和工业产品的百分浓度,浓度在4.97～88.6％时,相对标准偏差小于1.0％。     

异山梨醇型聚碳酸酯与ABS树脂共混体系的结构与性能研究

采用异山梨醇型聚碳酸酯(DB),与掺混型ABS熔融共混制备了具有不同聚丁二烯(PB)含量和丙烯腈(AN)含量的DB/掺混型ABS合金,并在考察掺混型ABS特征对合金结构与性能的影响的基础上,分别使用同种掺混型ABS以及各种商品化ABS树脂,比较了DB/ABS合金和双酚A型聚碳酸酯/ABS合金的性能及其变化规律.结果表明,对DB/掺混型ABS(70/30)合金而言,PB含量变化对于合金拉伸性能的影响明显大于AN含量变化所带来的影响,在PB含量为6.3 wt%条件下,各不同AN含量的合金体系均有最好的性能表现.PB含量和AN含量变化对合金分散相形态的影响与力学拉伸性能变化特征一致.DB/ABS合金体系均具有良好的热稳定性与热力学相容性,受AN含量和PB含量变化的影响较小,合金玻璃化转变温度与DB非常接近.以双酚A型聚碳酸酯为基础的聚碳酸酯(PC)/ABS合金及以异山梨醇型聚碳酸酯为基础的DB/ABS合金,在拉伸性能变化上均表现出完全相同的规律,且无论是采用掺混型ABS还是采用商品化ABS的体系,PC/ABS与DB/ABS合金在拉伸性能所反映出的规律也是基本一致的.     

PC/ABS及PC/ABS/PE-g-MAH共混体系相容性的研究

研究了聚碳酸酯与ＡＢＳ（ＰＣ／ＡＢＳ）及ＰＣ／ＡＢＳ与马来酸酐接枝聚乙烯共聚物（ＰＣ／ＡＢＳ／ＰＥ－ｇ－ＭＡＨ）共混体系的力学性能和应力开裂性能。用ＤＳＣ和ＳＥＭ研究了共混体系的相容性。结果表明：ＡＢＳ的加入能提高ＰＣ的冲击强度,ＡＢＳ的含量及品种影响ＰＣ／ＡＢＳ合金的力学性能,ＡＢＳ能提高ＰＣ的耐溶剂应力开裂性能。ＰＣ／ＡＢＳ／ＰＥ－ｇ－ＭＡＨ共混体系的力学性能和相容性优于ＰＣ／ＡＢＳ共混体系,     

Preferential melt intercalation of clay in ABS/brominated epoxy resin-antimony oxide (BER-AO) nanocomposites and its synergistic effect on thermal degradation and combustion behavior

ABS/organo montmorillonite (OMT) nanocomposites and ABS/brominated epoxy resin-antimony oxide (BER-AO)/OMT nanocomposites were prepared via melt compounding. The dispersion of OMT in nanocomposites was investigated by wide-angle X-ray diffraction and transmission electron microscopy. The results revealed an intercalated structure in ABS/OMT nanocomposites and the OMT layers mainly distribute in SAN phase. However, a completely exfoliated structure was found in ABS/BER-AO/OMT nanocomposites and OMT layers preferentially located in the BER phase which indicated that the OMT platelets had a much higher affinity with brominated epoxy resin than ABS resin. Based on the above morphological results, a schematic diagram of the ABS/OMT, ABS/BER-AO/OMT nanocomposites was established. The thermal degradation behavior was characterized by thermogravimetry. The results showed that the exfoliation of OMT can enhance the thermal stability of pure ABS resin and ABS/BER blends. An increase in the limited oxygen index (LOI) value was observed with the addition of OMT and it was found that such an enhancement is closely related to the morphologies of the chars formed after combustion. A synergistic effect between OMT and BER-AO during the combustion of the nanocomposites was found and a schematic mechanism was presented.     

Improved cell morphology and reduced shrinkage ratio of ETPU beads by reactive blending

Thermoplastic polyurethane foam beads (ETPU) have attracted attention of researchers in recent years due to their wide use in industrial applications. In this study, a small amount of acrylonitrile-butadiene-styrene copolymer (ABS) was blended with TPU under the assistance of dicumyl peroxide (DCP) and maleic anhydride (MAH) to improve the cell morphology and reduce shrinkage ratio of the resulting blends. These blends were then foamed to prepare TPU/ABS blends foam beads in an autoclave using supercritical CO₂ as the blowing agent at different temperatures and FTIR spectra, and rheological and foaming properties of the samples were evaluated. The melt viscosity, melt strength and elasticity of TPU/ABS were improved with the increase of the ABS content. These results were attributed to the grafting and heterogeneous nucleation points provided by the ABS. These enhanced properties were used to produce foams with better cell morphology and increased expansion ratio. Furthermore, the TPU/ABS blends foam beads showed lower shrinkage ratios with increasing ABS content. Thus, the addition of ABS is a facile method for improving the cell morphology and anti-shrinkage properties of ETPU.     

Morphological and thermal properties of ABS/montmorillonite nanocomposites using two different ABS polymers and four different montmorillonite clays

ABS/Clay nanocomposites were prepared using two ABS with different Acrylonitrile (AN) contents and four montmorillonite clays; a natural clay (CNa+) and three modified clays, Cloisites 10A, 20A, and 30B. The composites were prepared in a twin‐screw extruder. Results were analyzed considering the effect of clay and ABS type, on the clay dispersion, intercalation and exfoliation, as well as on the storage modulus and thermal stability of the nanocomposites. XRD and TEM confirm that when using an ABS with higher AN content (ABS2), a better dispersion and intercalation–exfoliation can be obtained. Cloisites 20A and 30B, respectively the one with greater initial intergallery spacing, but lower polarity and with smaller inter‐gallery spacing but greater polarity, produce the ABS nanocomposites with the greater intergallery spacing. Both ABS polymers have similar storage modulus and T_g and in both cases, the modulus increases with the 4 wt % clay. This increase is greater with the modified clays and slightly greater with the ABS2. T_g, from tan δ, increases very little with the 4 wt % clay, but again, this is slightly greater with ABS2. TGA and flammability tests show that the dispersed clay enhances the thermal stability and that the ABS with higher AN content produces a greater increase in fire retardancy. Tests also show that the better thermal stability and fire retardancy is obtained with the Cloisites 20A or 30B. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 190–200, 2008     

Thermal and photo-degradation of unstabilized ABS

Thermal- and photo-stabilities of unstabilized acrylonitrile-butadiene-styrene terpolymer, ABS, have been investigated by i.r. spectroscopy. Degradation of ABS samples is initiated by attack on the polybutadiene (PB) component; oxidation products containing hydroxyl and carbonyl groups are produced. The effect of prior thermal processing is to introduce into the polymer hydroperoxides arising from oxidative destruction of PB-unsaturation; these hydroperoxides act as catalysts during subsequent u.v. irradiation. The insolubility of degraded samples of ABS is associated with the formation of cross-linked structures and occurs mainly in the PB segment. It is concluded that the degradation characteristics of ABS are essentially those of the polybutadiene component.     

ABS的MAH/St多单体熔融接枝及其对PA6/ABS共混体系相形态和力学性能的影响

通过多单体熔融接枝的方法制备出了具有较高接枝率的ABS接枝物 (ABS g (MAH co St) ) ,并对其接枝机理进行了初步探讨 .研究表明 ,MAH、St接枝ABS时 ,反应主要发生在ABS中聚丁二烯的双键部位 .同时 ,当MAH与St的用量比约为 1:1时接枝率达到最高 .ABS g (MAH co St)作为尼龙 6 (PA6 ) ABS共混体系相容剂起到了良好的增容效果 .实验证明 ,相容剂使用前后 ,共混物的相区尺寸由几十 μm减小到 1μm以下 ,且分布更加均匀 ;共混物的拉伸强度和冲击强度等力学性能也同时得到均衡改善 .     

The effect of organoclay and graphene on the crystallization of PP in ABS/PP blends

In the present research, the isothermal and non-isothermal crystallization of polypropylene (PP) phase in PP-rich poly(acrylonitrile–butadiene–styrene)/polypropylene (ABS/PP) blends was studied. The effect of nanofillers’ incorporation and specialty of organically modified montmorillonite (OMMT) and graphene, into the prepared blends on the isothermal and non-isothermal crystallization of PP phase, were investigated. Moreover, kinetic study of their isothermal crystallization process was carried out, by applying the Avrami equation. The addition of ABS to the PP matrix increased the crystallization rate of PP at 130 °C. The incorporation of OMMT in pure PP accelerated slightly the crystallization process, whereas in ABS/PP blends, it seemed to retard crystallization, due to interactions between ABS phase and organoclay. The incorporation of graphene in pure PP accelerated impressively its isothermal crystallization, while the addition of ABS in graphene/PP nanocomposite slowed down the crystallization rate of PP. The effect of ABS and nanofillers, separately or in combination, on the crystallization of PP phase was reflected on the kinetic parameters of the Avrami equation. Regarding the non-isothermal crystallization, ABS/PP blends presented higher crystallization temperature (T _c) compared to pure PP. The organoclay reinforcement did not have any obvious effect on this temperature, whereas graphene caused significant increase, acting as nucleating agent. The presence of ABS to PP increased the concentration of the β-crystalline phase, reaching its maximum value at 30 mass% ABS content. The organoclay decreased the β-PP in ABS/PP blends, whereas graphene eliminated it.     

The research on the mechanical properties improvement of HDPE/ABS blends reinforced with acid‐treated wood fiber

In this study, the effect of acid‐treated wood fiber modifications on the mechanical behaviors of HDPE/ABS blend is investigated. Wood fiber/HDPE/ABS composites were fabricated by incorporating acid‐treated wood fiber into HDPE/ABS blends. The results showed that both the tensile strength and flexural strength of wood fiber/HDPE/ABS composites were greater than those of HDPE/ABS blend, regardless of wood fiber modification. The results also showed that the impact strength of HDPE/ABS composites is improved by the addition of wood fiber. Scanning electron microscopic (SEM) examination of fractured surfaces showed that the improvement in the mechanical properties of the wood fiber/HDPE/ABS composites was attributed to the improved dispersion of wood fiber in the HDPE/ABS and the better interfacial characteristics caused by the acid treatment of the wood fiber.     

纳米级金红石型二氧化钛与受阻胺光稳定剂协同改进ABS的抗老化性能研究

分别采用纳米级金红石型TiO2和受阻胺光稳定剂(HALS)对ABS进行改性,通过熔融共混法制备了ABS/纳米TiO2、ABS/纳米TiO2/HALS和ABS/HALS复合材料,采用GB/T16422.2~1999所述的塑料实验室光源暴露实验方法,用氙灯气候试验机对其进行28天人工加速老化,通过测定其老化过程中的无缺口和缺口试样冲击强度的变化来对其抗老化性能进行表征,同时利用光学显微镜和扫描电镜对其老化过程中的冲击断口形貌变化进行了研究.结果表明,纳米TiO2在ABS基体中分散良好,改性后的复合材料均具有较好的抗老化性能,纳米TiO2与HALS复合改性ABS对其耐候性的提高具有明显的协同作用,其老化后的抗冲击性能超过了单一使用HALS或纳米TiO2的改性效果,老化28天后纯ABS树脂试样的无缺口冲击强度保持率只有20%左右,添加2.0 wt%纳米TiO2后,老化28天后的ABS/纳米TiO2/HALS复合材料试样的保持率则提高到47.9%,为纯ABS树脂试样的2.5倍.