963 resultados para BLENDS


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O objetivo deste trabalho foi estabelecer um modelo empregando-se ferramentas de regressão multivariada para a previsão do teor em ésteres metílicos e, simultaneamente, de propriedades físico-químicas de misturas de óleo de soja e biodiesel de soja. O modelo foi proposto a partir da correlação das propriedades de interesse com os espectros de reflectância total atenuada no infravermelho médio das misturas. Para a determinação dos teores de ésteres metílicos foi utilizada a cromatografia líquida de alta eficiência (HPLC), podendo esta ser uma técnica alternativa aos método de referência que utilizam a cromatografia em fase gasosa (EN 14103 e EN 14105). As propriedades físico-químicas selecionadas foram índice de refração, massa específica e viscosidade. Para o estudo, foram preparadas 11 misturas com diferentes proporções de biodiesel de soja e de óleo de soja (0-100 % em massa de biodiesel de soja), em quintuplicata, totalizando 55 amostras. A região do infravermelho estudada foi a faixa de 3801 a 650 cm-1. Os espectros foram submetidos aos pré-tratamentos de correção de sinal multiplicativo (MSC) e, em seguida, à centralização na média (MC). As propriedades de interesse foram submetidas ao autoescalamento. Em seguida foi aplicada análise de componentes principais (PCA) com a finalidade de reduzir a dimensionalidade dos dados e detectar a presença de valores anômalos. Quando estes foram detectados, a amostra era descartada. Os dados originais foram submetidos ao algoritmo de Kennard-Stone dividindo-os em um conjunto de calibração, para a construção do modelo, e um conjunto de validação, para verificar a sua confiabilidade. Os resultados mostraram que o modelo proposto por PLS2 (Mínimos Quadrados Parciais) foi capaz de se ajustar bem os dados de índice de refração e de massa específica, podendo ser observado um comportamento aleatório dos erros, indicando a presença de homocedasticidade nos valores residuais, em outras palavras, o modelo construído apresentou uma capacidade de previsão para as propriedades de massa específica e índice de refração com 95% de confiança. A exatidão do modelo foi também avaliada através da estimativa dos parâmetros de regressão que são a inclinação e o intercepto pela Região Conjunta da Elipse de Confiança (EJCR). Os resultados confirmaram que o modelo MIR-PLS desenvolvido foi capaz de prever, simultaneamente, as propriedades índice de refração e massa específica. Para os teores de éteres metílicos determinados por HPLC, foi também desenvolvido um modelo MIR-PLS para correlacionar estes valores com os espectros de MIR, porém a qualidade do ajuste não foi tão boa. Apesar disso, foi possível mostrar que os dados podem ser modelados e correlacionados com os espectros de infravermelho utilizando calibração multivariada

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O estudo da estabilidade de emulsões de biocombustíveis destaca-se, dentre outros aspectos, pela necessidade de identificação das características destas. Esta necessidade reforça-se pela dificuldade de detecção de biodiesel e suas misturas quando estão fora de especificação, além de se aplicar aos processos de separação e purificação do biodiesel após a transesterificação. O entendimento deste problema poderá ser alcançado a partir de estudos de estabilidade associados aos modelos termodinâmicos de equilíbrio líquido-líquido (modelo NRTL) em sistemas ternários, que serão a base da modelagem proposta neste trabalho. O levantamento de dados envolve técnicas de observação direta em titulação, e ensaios de estabilidade e tensiometria, com algumas alterações das técnicas clássicas. Desta forma, o objetivo principal do trabalho é propor uma maneira de identificar e caracterizar as interfaces das emulsões formadas e estudar a estabilidade das fases envolvidas. Além disso, estuda-se a introdução de alcoóis como agentes tensoativos para viabilizar a utilização de misturas de combustíveis, mesmo na região de mais de uma fase. Para o desenvolvimento do trabalho, emulsões envolvendo os constituintes básicos serão combinadas entre si em diferentes proporções. A etapa inicial constitui-se de um mapeamento das misturas e proporções que formam as emulsões, baseadas nas curvas de equilíbrio. Em seguida, faz-se o estudo de caracterização e estabilidade destes sistemas. Com estas informações é possível mapear o sentido de incremento de tensão na interface e instabilidade da separação de fases das emulsões em relação aos diagramas ternários correspondentes. Por fim, propõe-se uma estratégia para estimar os parâmetros termodinâmicos do NRTL para as espécies presentes nos sistemas estudados e prever o comportamento dos mesmos e de sistemas similares. Este modelo matemático proposto tem como objetivo complementar a técnica experimental adotada para construção das curvas de equilíbrio, sendo bem sucedido

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Stabilisation/solidification (S/S) is an effective technique for reducing the leachability of contaminants in soils. Very few studies have investigated the use of ground granulated blast furnace slag (GGBS) for S/S treatment of contaminated soils, although it has been shown to be effective in ground improvement. This study sought to investigate the potential of GGBS activated by cement and lime for S/S treatment of a mixed contaminated soil. A sandy soil spiked with 3000mg/kg each of a cocktail of heavy metals (Cd, Ni, Zn, Cu and Pb) and 10,000mg/kg of diesel was treated with binder blends of one part hydrated lime to four parts GGBS (lime-slag), and one part cement to nine parts GGBS (slag-cement). Three binder dosages, 5, 10 and 20% (m/m) were used and contaminated soil-cement samples were compacted to their optimum water contents. The effectiveness of the treatment was assessed using unconfined compressive strength (UCS), permeability and acid neutralisation capacity (ANC) tests with determination of contaminant leachability at the different acid additions. UCS values of up to 800kPa were recorded at 28days. The lowest coefficient of permeability recorded was 5×10(-9)m/s. With up to 20% binder dosage, the leachability of the contaminants was reduced to meet relevant environmental quality standards and landfill waste acceptance criteria. The pH-dependent leachability of the metals decreased over time. The results show that GGBS activated by cement and lime would be effective in reducing the leachability of contaminants in contaminated soils.

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The paper presents the three categories of food coatings that are used, individually or in combination, to produce battered or breaded foods. These are predust, batters and breadcrumbs. Predusts are usually a blend of flours, starches and other functional ingredients such as proteins, vegetable gums and seasonings or flavors; batters are blends of flours, starches, leavening agents and seasonings which, when mixed with water, forms a viscous liquid used to evenly coat a food item; while breadcrumbs are baked or otherwise thermally processed cereal-based ingredients which are applied to a moistened food item prior to cooking.

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Bioethanol is the world's largest-produced alternative to petroleum-derived transportation fuels due to its compatibility within existing spark-ignition engines and its relatively mature production technology. Despite its success, questions remain over the greenhouse gas (GHG) implications of fuel ethanol use with many studies showing significant impacts of differences in land use, feedstock, and refinery operation. While most efforts to quantify life-cycle GHG impacts have focused on the production stage, a few recent studies have acknowledged the effect of ethanol on engine performance and incorporated these effects into the fuel life cycle. These studies have broadly asserted that vehicle efficiency increases with ethanol use to justify reducing the GHG impact of ethanol. These results seem to conflict with the general notion that ethanol decreases the fuel efficiency (or increases the fuel consumption) of vehicles due to the lower volumetric energy content of ethanol when compared to gasoline. Here we argue that due to the increased emphasis on alternative fuels with drastically differing energy densities, vehicle efficiency should be evaluated based on energy rather than volume. When done so, we show that efficiency of existing vehicles can be affected by ethanol content, but these impacts can serve to have both positive and negative effects and are highly uncertain (ranging from -15% to +24%). As a result, uncertainties in the net GHG effect of ethanol, particularly when used in a low-level blend with gasoline, are considerably larger than previously estimated (standard deviations increase by >10% and >200% when used in high and low blends, respectively). Technical options exist to improve vehicle efficiency through smarter use of ethanol though changes to the vehicle fleets and fuel infrastructure would be required. Future biofuel policies should promote synergies between the vehicle and fuel industries in order to maximize the society-wise benefits or minimize the risks of adverse impacts of ethanol.

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We describe studies of new nanostructured materials consisting of carbon nanotubes wrapped in sequential coatings of two different semiconducting polymers, namely, poly(3-hexylthiophene) (P3HT) and poly(9,9'-dioctylfluorene-co-benzothiadiazole) (F8BT). Using absorption spectroscopy and steady-state and ultrafast photoluminescence measurements, we demonstrate the role of the different layer structures in controlling energy levels and charge transfer in both solution and film samples. By varying the simple solution processing steps, we can control the ordering and proportions of the wrapping polymers in the solid state. The resulting novel coaxial structures open up a variety of new applications for nanotube blends and are particularly promising for implementation into organic photovoltaic devices. The carbon nanotube template can also be used to optimize both the electronic properties and morphology of polymer composites in a much more controlled fashion than achieved previously, offering a route to producing a new generation of polymer nanostructures.

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Biodegradable polymers can be applied to a variety of implants for controlled and local drug delivery. The aim of this study is to develop a biodegradable and nanoporous polymeric platform for a wide spectrum of drug-eluting implants with special focus on stent-coating applications. It was synthesized by poly(DL-lactide-co-glycolide) (PLGA 65:35, PLGA 75:25) and polycaprolactone (PCL) in a multilayer configuration by means of a spin-coating technique. The antiplatelet drug dipyridamole was loaded into the surface nanopores of the platform. Surface characterization was made by atomic force microscopy (AFM) and spectroscopic ellipsometry (SE). Platelet adhesion and drug-release kinetic studies were then carried out. The study revealed that the multilayer films are highly nanoporous, whereas the single layers of PLGA are atomically smooth and spherulites are formed in PCL. Their nanoporosity (pore diameter, depth, density, surface roughness) can be tailored by tuning the growth parameters (eg, spinning speed, polymer concentration), essential for drug-delivery performance. The origin of pore formation may be attributed to the phase separation of polymer blends via the spinodal decomposition mechanism. SE studies revealed the structural characteristics, film thickness, and optical properties even of the single layers in the triple-layer construct, providing substantial information for drug loading and complement AFM findings. Platelet adhesion studies showed that the dipyridamole-loaded coatings inhibit platelet aggregation that is a prerequisite for clotting. Finally, the films exhibited sustained release profiles of dipyridamole over 70 days. These results indicate that the current multilayer phase therapeutic approach constitutes an effective drug-delivery platform for drug-eluting implants and especially for cardiovascular stent applications.

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Roll-to-roll (R2R) gravure exhibits significant advantages such as high precision and throughput for the printing of photoactive and conductive materials and the fabrication of flexible organic electronics such as organic photovoltaics (OPVs). Since the photoactive layer is the core of the OPV, it is important to investigate and finally control the process parameters and mechanisms that define the film morphology in a R2R process. The scope of this work is to study the effect of the R2R gravure printing and drying process on the nanomorphology and nanostructure of the photoactive P3HT:PCBM thin films printed on PEDOT:PSS electrodes towards the fabrication of indium tin oxide (ITO)-free flexible OPVs. In order to achieve this, P3HT:PCBM blends of different concentration were R2R printed under various speeds on the PEDOT:PSS layers. Due to the limited drying time during the rolling, an amount of solvent remains in the P3HT:PCBM films and the slow-drying process takes place which leads to the vertical and lateral phase separation, according to the Spectroscopic Ellipsometry and Atomic Force Microscopy analysis. The enhanced slow-drying leads to stronger phase separation, larger P3HT crystallites according to the Grazing Incidence X-Ray Diffraction data and to weaker mechanical response as it was shown by the nanoindentation creep. However, in the surface of the films the P3HT crystallization is controlled by the impinged hot air during the drying, where the more the drying time the larger the surface P3HT crystallites. The integration of the printed P3HT:PCBM and PEDOT:PSS layers in an OPV device underlined the feasibility of fabricating ITO-free flexible OPVs by R2R gravure processes. © 2013 Elsevier B.V.

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Nanostructured polymer-fullerene thin films are among the most prominent materials for application in high efficient polymer solar cells. Specifically, poly(3-hexylthiophene) (P3HT) and fullerene derivatives (PCBM) blends are used as the donor/acceptor materials forming a bulk heterojunction. Although P3HT:PCBM properties have been extensively studied, less light has been set on its nanomechanical properties, which affect the device service life. In this work Atomic Force Acoustic Microscopy (AFAM), Atomic Force Spectroscopy and Nanoindentation were used to study the effect of the fullerene presence and the annealing on the P3HT:PCBM nanomechanical behavior. The P3HT:PCBM thin films were prepared by spin coating on glass substrates and then annealed at 100 °C and 145 °C for 30 min. Large phase separation was identified by optical and Atomic Force Microscopy (AFM) for the annealed samples. Needle-like PCBM crystals were formed and an increase of the polymer crystallinity degree with the increase of the annealing temperature was confirmed by X-ray diffraction. AFAM characterization revealed the presence of aggregates close to stiff PCBM crystals, possibly consisting of amorphous P3HT material. AFM force-distance curves showed a continuous change in stiffness in the vicinity of the PCBM crystals, due to the PCBM depletion near its crystals, and the AFM indentation provided qualitative results about the changes in P3HT nanomechanical response after annealing. © 2011 Elsevier B.V. All rights reserved.

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The dithiophene donor-acceptor copolymers that are bridged either with carbon (C-PCPDTBT) or silicon atoms (Si-PCPDTBT) belong to a promising family of materials for use in photoactive layers for organic photovoltaic cells (OPVs). In this work, we implement the non-destructive Spectroscopic Ellipsometry technique in the near infrared to the far ultraviolet spectral region in combination with advanced theoretical modeling to investigate the vertical distribution of the C-PCPDTBT and Si-PCPDTBT polymer and fullerene ([6,6]-phenyl C71-butyric acid methyl ester - PC70BM) phases in the blend, as well as the effect of the polymer-to-fullerene ratio on the distribution mechanism. It was found that the C-PCPDTBT:PC70BM blends have donor-enriched top regions and acceptor-enriched bottom regions, whereas the donor and acceptor phases are more homogeneously intermixed in the Si-PCPDTBT:PC70BM blends. We suggest that the chemical incompatibility of the two phases as expressed by the difference in their surface energy, may be a key element in promoting the segregation of the lower surface phase to the top region of the photoactive layer. We found that the increase of the photoactive layer thickness reduces the polymer enrichment at the cathode, producing a more homogeneous phase distribution of donor and acceptor in the bulk that leads to the increase of the OPV efficiency. © 2014 Elsevier B.V.

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The reaction between MgO and microsilica has been studied by many researchers, who confirmed the formation of magnesium silicate hydrate. The blend was reported to have the potential as a novel material for construction and environment purposes. However, the characteristics of MgO vary significantly, e.g., reactivity and purity, which would have an effect on the hydration process of MgO-silica blend. This paper investigated the strength and hydration products of reactive MgO and silica blend at room temperature up to 90 days. The existence of magnesium silicate hydrate after 7 days' curing was confirmed with the help of infrared spectroscopy, thermogravimetric analysis and X-ray diffraction. The microstructural and elemental analysis of the resulting magnesium silicate hydrate was conducted using scanning electron microscopy and energy dispersive spectroscopy. In addition, the effect of characteristics of MgO on the hydration process was discussed. It was found that the synthesis of magnesium silicate hydrate was highly dependent on the reactivity of the precursors. MgO and silica with higher reactivity resulted in higher formation rate of magnesium silicate hydrate. In addition, the impurity in the MgO affects the pH value of the blends, which in turn determines the solubility of silica and the formation of magnesium silicate hydrate. © 2014 Elsevier Ltd. All rights reserved.

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聚对苯二甲酸丁二醇酯(PBT)是一种多用途的工程塑料。本文中,主要研究了PBT/Epoxy(E)合金及PBT/ABS-g-GMA/E合金的结晶行为和力学性能。 使用示差扫描量热法对PBT/Epoxy合金的等温结晶过程进行了研究。发现PBT和E03 609环氧树脂在所研究的组成范围内完全相容。环氧树脂起到异相成核剂的作用,使PBT产生更强的瞬间结晶三维生长趋势。PBT和环氧树脂的Flory相互作用参数为负值,说明PBT和环氧树脂形成了热力学上的稳定混合物。 使用几种方法对PBT/Epoxy合金的非等温结晶过程进行了研究,Ozawa方程不能充分描述PBT/Epoxy合金的非等温结晶过程;使用莫志深等人提出的方法,成功地描述了该过程。实验结果显示1%环氧树脂可使PBT/Epoxy合金结晶速率明显增加。 对PBT/Epoxy合金的热和力学性能进行了研究。1%环氧树脂的加入提高PBT/Epoxy合金的缺口冲击强度20%;从红外光谱分析,环氧树脂与PBT发生了相互作用;环氧树脂影响了PBT/Epoxy合金的力学性质和结晶行为。 采用乳液聚合技术将甲基丙烯酸环氧丙酯(GMA)引入到ABS的壳层,合成了环氧官能化的ABS共聚物(ABS-g-GMA),将环氧树脂加入到PBT/ABS-g-GMA合金中,利用环氧官能团与PBT端羧基/羟基的反应达到增容PBT/ABS合金的目的。当环氧树脂的含量为5%时,PBT/ABS-g-GMA/E共混物比PBT/ABS-g-GMA共混物有更优异的力学性质。 研究了聚亚丙基碳酸酯(PPC)和聚丁二酸二甲酯(PBS)共混物的相容性、结晶和力学性能。结果显示组份PPC/PBS(90/10)可能产生部分相容。采用偏光显微镜观察了PPC/PBS共混物的形态,对于90/10 PPC/PBS共混物,发现很大数量的PBS小球晶分散在PPC基质中。力学结果显示90/10 PPC/PBS共混物拉伸强度比纯PPC提高了30%,冲击强度提高了11%。

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本工作通过电子束预辐照处理和反应挤出方法,制备了丙烯酸功能化预辐照聚丙烯rPP-g-AA,采用化学滴定和红外光谱方法均证明接枝共聚物的存在,同时确定了预辐照剂量和单体浓度对接枝率的影响:(1)当单体浓度一定时,接枝率随预辐照剂量的增加而增加并逐渐达到平台值;(2)当预辐照剂量固定时,单体浓度在0~4.0wt%范围内,接枝率几乎呈线性增加。研究发现,丙烯酸(AA)接枝链能起到异相成核作用而促进预辐照聚丙烯(rPP)的结晶过程,但却不改变结晶晶型;虽然接枝反应可以部分抑制降解反应,但相对于原料聚丙烯(PP),接枝产物的力学性能仍大大下降;因此提出的反应机理认为接枝反应主要是通过链断裂降解反应形成的端自由基引发的,从而形成了以端基接枝为主的产物。 为了控制PP接枝过程中的严重降解,本工作首次提出了均相和异相引发接枝反应的原理,即采用部分rPP和预辐照聚乙烯(rPE)分别作为PP接枝反应的均相和异相“引发剂”,经反应挤出制备丙烯酸功能化聚丙烯PP-g-AA。对于均相引发体系:(1)当rPP用量为20phr时,PP-g-AA的接枝率已经达到rPP-g-AA的水平,而且降解反应得到有效控制;(2)和PP/rPP-g-AA共混物的对比研究证明,均相引发接枝产物不但接枝率明显提高,而且接枝分布非常均匀;(3)由此提出均相引发主要是发生rPP和PP分子间夺氢反应并形成以基体PP接枝为主的产物,而rPP分子内夺氢反应形成的接枝产物rPP-g-AA只占较少比例。对于异相引发体系: (1)通过红外光谱表征及接枝率计算得出异相引发接枝产物的接枝率比相应的PP/ rPE-g-AA共混物略高;(2)由于rPE及rPE-g-AA对基体PP的结晶没有影响,通过异相引发接枝产物中PP的结晶温度升高直接验证了异相引发接枝反应的实现;(3)提出的机理认为异相引发主要发生在rPE的分子内夺氢并形成rPE-g-AA,造成rPE引发的PP分子间夺氢反应形成PP-g-AA产物的比例下降。 本工作还详细研究了rPP预辐照剂量、rPP用量和单体浓度对均相引发反应的影响。得到的结果如下:(1)高预辐照剂量导致了接枝率下降的“假相”是由于形成的微凝胶造成的;(2)rPP用量的增大在提高接枝率的同时也导致降解反应的逐渐增强;(3)单体浓度的增加导致接枝率的逐步提高并最终达到最大值,而且可能导致部分微凝胶的产生;(4)接枝没有破坏PP-g-AA结晶的完善性和晶型,却能促进了晶体在(040)晶面的生长并可能产生部分横晶形态;(5)PP-g-AA和金属能形成良好的粘接作用。 以上述制备的rPP-g-AA和PP-g-AA增容PP/聚对苯二甲酸丁二醇酯(PBT)共混体系,发现高分子量的PP-g-AA比低分子量的rPP-g-AA的增容效果要好,因此认为PP-g-AA和PBT通过酯化反应形成的长链接枝共聚物PP-g-PBT对PBT相的分散和界面作用增强更加有效。而随着增容剂PP-g-AA比例的增加,原位反应生成的PP-g-PBT逐渐增加,使得PBT相分散和界面增强效果更加显著,因此共混物的力学性能也更佳;DSC研究发现,随着PBT相尺寸减小到1μm以下,PBT出现了结晶受限行为。 将引发剂rPP和单体AA加入到PP/PBT共混体系中实现了一步法反应增容,得到共混物的扭矩、相形态、力学性能都和分步法增容共混物的结果几乎相同,这说明一步法共混能使PBT产生良好分散并得到性能较佳的产物,从而为高分子合金材料制备提供了一种简单有效的方法。 采用该方法对AA、马来酸酐(MAH)和甲基丙烯酸甘油酯(GMA)三种单体的接枝和增容反应对比研究证明,AA的效果最好,MAH次之,而GMA的效果最差,分析认为,AA和MAH通过接枝反应形成PP-g-AA和PP-g-MAH,随后再和PBT发生酯化增容反应形成PP-g-MAH-PBT共聚产物,而GMA首先和PBT反应形成PBT-GMA,而后由长链PBT-GMA发生接枝反应生成PP-g-GMA-g-PBT,但是这种接枝反应的效率很低,由此造成增容效果较差。

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本文以单组分和双组分Lewis酸为催化剂,采用反应加工的方法,制备了原位反应增容的线性低密度聚乙烯/聚苯乙烯共混物(LLDPE/PS),并对原位反应增容的机理、增容体系的结构性能以及Lewis酸对共混组分的降解作用进行了系统研究。 以FTIR和NMR为手段、二甲苯为模拟化合物,确认LLDPE/PS共混体系在Lewis酸为催化剂作用下发生了LLDPE与PS的接枝反应,LLDPE接枝在PS苯环的对位上。形成的原位接枝共聚物对体系起增容作用。 使用溶剂抽提、SEM、DMA、流变和DSC等手段对以单组分Lewis酸AlCl3 为催化剂的LLDPE/PS共混物的结构性能进行了研究。从溶剂抽提前后的重量比计算了接枝物的含量。催化剂用量较低时体系中的接枝物含量随AlCl3的增加而提高,随着AlCl3进一步增加,接枝物含量不会增加反而下降,发现AlCl3导致均聚物的降解。研究结果表明,共混体系中加入适量的AlCl3催化剂后,分散相尺寸减小,分布均匀,储能模量增加,低频区的复数黏度升高。但AlCl3用量过高时使共混物的分散相尺寸增加,分布均匀度下降,储能模量和复数黏度降低。以GPC为手段研究了单组分 Lewis酸AlCl3对共混组分的降解作用,发现对PS的降解作用显著。 由于单组分Lewis酸催化剂会导致共混组分降解,使共混体系的物理机械性能变劣,为此,我们在LLDPE/PS共混物中引入了双组分Lewis酸催化剂(Me3SiCl、InCl3•4H2O)。结果表明双组分Lewis酸催化剂不但能够催化LLDPE和PS的原位接枝反应,获得高性能的LLDPE/PS合金材料,而且不会引发共混组分PS的降解。在催化剂用量固定时,采用双组分催化剂时共混物的拉伸强度随着LLDPE含量的增加几乎保持不变,但冲击强度有十分明显的提高。对比了加入催化剂前后共混物形貌的变化,增容后的共混物中分散相粒子尺寸显著降低,证明了双Lewis酸良好的催化性能。 对以双Lewis酸为催化剂的共混物的流变行为和结晶行为进行了研究。随着催化剂的加入,两相之间的相互作用增强,因此共混物的复数黏度,储能模量和损耗模量都有不同程度的提高。增容后的LLDPE相区变小,因而在冷却过程中出现不同程度的分步结晶现象。 对单组分和双组分Lewis酸催化剂原位反应增容LLDPE/PS共混体系的机理进行了探讨。机理为Friedel-Crafts烷基化反应。在采用单组分Lewis酸催化剂时, AlCl3与体系中含有的微量水等杂质发生反应,形成一个复合物,然后进一步与聚乙烯中的不饱和的双键发生反应形成碳正离子,并攻击LLDPE分子链从而形成大分子的碳正离子LLDPE+,而这些LLDPE+则通过电子的重排而发生剪切断裂。在催化剂的存在下,这些断裂的LLDPE片断取代PS中的苯环上的质子而发生接枝反应,从而形成LLDPE-g-PS共聚物。采用双组分Lewis酸催化剂时,首先发生双Lewis酸的耦合;耦合后的Lewis酸与水等杂质反应生成复合物,然后与非饱和的LLDPE分子反应生成初级碳正离子;初级碳正离子进攻LLDPE主链,生成较大的碳正离子;LLDPE+碳正离子取代PS苯环对位的质子而生成接枝共聚物。

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本工作采用熔融反应接枝的方法将(3-异氰酸酯基-4-甲基)苯氨基甲酸-2-丙烯酯(TAI)引入到聚苯乙烯-b-聚(乙烯-co-丁烯)-b-聚苯乙烯三嵌段共聚物(SEBS)上,以实现SEBS的功能化。红外光谱表明TAI已经成功接枝到SEBS上。GPC测试表明接枝后SEBS具有高的分子量与宽的分子量分布。DMA分析证明,接枝后聚(乙烯-co-丁烯) (PEB)段的玻璃化转变提高。对未参与接枝的单体的分析表明,单体TAI是个不容易自聚的单体,并对接枝过程的机理进行了研究。 为了提高TAI的存储稳定性和解决反应过程中的毒性大的问题,采用己内酰胺为封端剂对TAI中的异氰酸酯进行了封端。红外光谱和核磁共振结果表明,己内酰胺封端的TAI(BTAI)中含有双键和封闭型异氰酸酯结构,不存在着活泼的异氰酸酯。红外光谱结果表明,在高温下BTAI可以重新产生活泼的异氰酸酯基团。DSC与TG/DTA研究证明,BTAI的初始解离温度大约为135 C。采用熔融反应接枝的方法将BTAI接枝到SEBS和乙烯-辛烯共聚物(POE)分子上。研究表明,接枝率随着单体含量或引发剂含量的增加而增加。接枝以后的SEBS与POE的剪切变稀行为都比未接枝的SEBS与POE要明显。 利用BTAI功能化的SEBS和POE两种弹性体,通过熔融反应共混方法制备了PA6合金。两种弹性体与PA6共混物的红外光谱和流变行为的研究表明,在反应共混中形成了新的接枝共聚物。共混物的脆断面的场发射扫描电镜照片表明,共混物形成一种海-岛结构,而反应共混物的具有更均匀的粒子分散性,更小的粒子尺寸。PA6/SEBS-g-BTAI共混的透射电镜照片说明,共混物中形成了一种以PS为核-PEB为壳的核壳结构。与相应的物理共混物相比,通过反应共混制备的PA6合金(PA6/SEBS-g-BTAI合金和PA6/POE-g-BTAI合金)的拉伸强度、杨氏模量得到了提高。两种反应共混物的缺口冲击强度得到了非常明显的提高,合金材料的缺口冲击强度可以达到1000 J/m 以上。共混物中弹性体对PA6的结晶起到了成核的作用,结晶温度提高。形成的共聚物阻碍了PA6的分子链的运动,使得PA6的结晶温度下降。 本工作还利用上述制备的POE-g-BTAI和SEBS-g-BTAI两种功能化的弹性体与聚对苯二甲酸丁二醇酯(PBT)进行共混。研究表明,在反应共混过程中PBT中的反应基团与释放出的异氰酸酯发生反应,生成了新的共聚物。通过共混物的脆断面的FESEM图片可以看到,POE与PBT的共混物中,POE以球状粒子分散在PBT中,并且反应共混物的粒子分散均匀,粒子尺寸变小。与POE/PBT共混不同的是,在PBT与SEBS共混过程中,二者形成了交错结构,而反应共混在较低含量就形成了交错结构。POE与PBT反应共混物的缺口冲击强度得到了很大的提高,冲击强度可以达到1100 J/m以上,而PBT与SEBS的反应共混物的冲击强度改变不大。相对于物理共混物,两种弹性体与PBT的反应共混物的拉伸强度与拉伸模量都得到了提高。弹性体的加入提高了PBT的结晶温度,反应共混物的结晶温度低于物理共混物的结晶温度,说明弹性体的加入起到了PBT的成核剂的作用,生成的共聚物亦阻碍了PBT的分子链的移动。 关键词:聚苯乙烯-b-聚(乙烯-co-丁烯)-b-聚苯乙烯三嵌段共聚物;乙烯-辛烯共聚物;封闭型异氰酸酯;反应加工;聚酰胺6;聚对苯二甲酸丁二醇酯