线性低密度聚乙烯和聚苯乙烯共混物的原位增容

采用反应挤出的方法，通过使用Friedel-Crofts反应，以AICl3为催化剂对原位增容线性低密度聚乙烯（LLDPE）和聚苯乙烯（PS）共混体系的反应机理、接枝物结构、材料的结构一性能关系、共混物的相分布形态以及多重结晶行为进行了深入研究。使用激光拉曼光谱研究了以AICl3作为LLDPE/PS共混体系的Friedel-Crafts反应的催化剂生成的接枝物的结构，通过对一系列模型化合物结构的分析，确定了发生接枝反应的点应为聚苯乙烯苯环上次甲基的对位。对于增容后共混物的力学性能进行了分析，并找出有效提高力学性能的工艺。根据测定，增容后的LLDPE/PS（80／20）共混物的Izod冲击性能从80J／m提高到了400）／m以上。断裂伸长率从350％提高到了800％以上。相对应的共混物的相分布形态也得到了极大的改善。这种力学性能上的提高，使得LLDPE／PS共混物真正具有了使用价值及商业前景。这也是研究LLDPE/PS共混物主要目的之一。随着含量AICl3的增加，共混物中PS分散相粒子的尺寸逐渐减小，直至共混物的相分布形态由原来的分散相一连续相结构变为双连续结构。这种形态上的改变，正是力学性能提高的基础。添加过量的AlCl3会对共混物产生一定的降解作用。通过GPC和MER等手段的分析，发现这种降解作用对于共混物中的 PS组分更加明显，而且这种降解只发生在接枝反应之后，与接枝反应是一对竞争的反应。研究了增容后的LLDP／PS（20／80）共混物的熔融结晶行为，发现了这个共混物具有复杂的多重结晶行为。通过对共混物界面层的SEM和TEM观察分析发现：在共混物的LLDPE和PS两相的中间，具有一层由LLDPE-g-PS接枝共聚物形成的界面层。这个界面层中的LLDPE链段与LLDPE均聚物在熔体中紧密的缠结着。当共混体系从较高的熔融温度逐渐下降的时候，接枝共聚物会因为链段之间的相互作用而在熔体下就形成相分离。在接枝共聚物的有序化过程中，与之紧密缠结的LLDPE均聚物分子也会随着有序化的过程而进入相分离所形成的微域结构中。研究了共棍物的这种多重结晶行为。根据共聚物的特性，首次采用了对共混物进行熔点温度之上的高温退火来研究有序一无序转变对共混物多重结晶行为的影响。由于在两相界面层的LLDPE-g-PS接枝共聚物有序化所形成的大量的微域结构限制了处于其中的LLDPE分子的结晶，导致这部分LLDPE分子结晶所需的过冷程度增加，最终只能采用均相成核的方式结晶所致。研究发现，在不同的熔融温度、退火温度以及退火时间都会对共混物的这种受限结晶行为产生很大的影响。在低于接枝共聚物的有序一无序转化温度下退火时，受限于接枝物形成的微域结构中的LLDPE均聚物分子会在这个过程中从微域结构中脱离，重新进入更大的LLDPE分散相粒子中。如果退火的温度高于接枝共聚物的有序一无序转化温度，那么这些LLDPE均聚物分子仍然会在降温的时候被“吞入”有序化所形成的微域结构中而无法脱离这种受限环境。

Blends of Polypropylene and Syndiotactic 1,2-Polybutadiene: Morphology, Crystallization Behaviors and Mechanical Properties

Morphologies, crystallization behavior and mechanical properties of polypropylene(PP)/syndiotactic 1,2-polybutadiene(s-1,2 PB) blends were investigated. Morphology observation shows the well dispersed domains of s-1,2 PB in PP matrix with the rather small domain sizes from 0.1 to 0.5 mu m when the s-1,2 PB content increases from 5% to 20% (mass fraction) in the blends, and the phase structure tends to become co-continuous as s-1,2 PB content further increases.

Thermoplastic Elastomers Based on Compatibilized Poly(butylene terephthalate) Blends: Effect of Functional Groups and Dynamic Curing

Two sets of graft copolymers were prepared by grafting glycidyl methacrylate (GMA) or ally] (3-isocyanate-4-tolyl) carbamate (TAI) onto ethylene/propylene/diene terpolymer (EPDM) in an internal mixer. These graft copolymers were used as the compatibilizer to prepare the thermoplastic elastomers (TPEs) containing 50 wt%, of poly(butylene terephthalate), PBT, 30 wt% of compatibilizer, and 20 wt% of nitrile-butadiene rubber, NBR. The indirect, two-step mixer process was chosen for dynamic curing.

Rheology, morphology and mechanical properties of compatibilized poly(vinylidene fluoride) (PVDF)/thermoplastic polyurethane (TPU) blends

Compatibilized blends of poly(vinylidene fluoride) (PVDF) and thermoplastic polyurethane (TPU) were developed using maleated PVDF (PVDF-g-MA). Excellent compatibilization between PVDF and TPU was demonstrated by theological, morphological, and mechanical measurements. The introduction of PVDF-g-MA into the PVDF/TPU blends caused an increase in viscosity and storage modulus. Much finer morphology was clearly observed by SEM. The tensile tests showed that the tensile strength and ultimate elongation achieved a significant improvement with addition of PVDF-g-MA.

Thermal and mechanical properties of poly(butylene terephthalate)/epoxy blends

In this study, melt blends of poly(butylene terephthalate) (PBT) with epoxy resin were characterized by dynamic mechanical analysis, differential scanning calorimetry, tensile testing, Fourier transform infrared spectroscopy, and wide-angle X-ray diffraction. The results indicate that the presence of epoxy resin influenced either the mechanical properties of the PBT/epoxy blends or the crystallization of PBT. The epoxy resin was completely miscible with the PBT matrix. This was beneficial to the improvement of the impact performance of the PBT/epoxy blends.

A strategy of fabricating exfoliated thermoplastic polyurethane/clay nanocomposites via introducing maleated polypropylene

By reducing the attraction between the platelets of octaclecylammonium chloride modified montmorillonite (OMMT-C18) via pre-intercalation of maleated polypropylene (MAPP), OMMT-C18 was exfoliated in thermoplastic polyurethane (TPU) matrix during melt-mixing. Wide angle X-ray diffraction, transmission electron microscopy and thermogravimetric analysis were used to investigate the microstructure of TPU nanocomposites. Three factors (including introducing sequence, the kind and the content of MAPP) showed important effects on the dispersion degree of OMMT-C18 in TPU matrix. The results confirmed that the pre-intercalation of MAPP was necessary for the exfoliation of OMMT-C18; however, the role of MAPP in TPU nanocomposites was different from that in polypropylene nanocomposites.

Toughening effects of poly(butylene terephthalate) with blocked isocyanate-functionalized poly(ethylene octene)

BACKGROUND: Blocked isocyanate-functionalized polyolefins have great potential for use in semicrystalline polymer blends to obtain toughened polymers. In this study, poly(butylene terephthalate) (PBT) was blended with allyl N-[2-methyl-4-(2-oxohexahydroazepine-1 -carboxamido)phenyl] carbamate-functionalized poly(ethylene octene) (POE-g-AMPC).RESULTS: New peaks at 2272 and 1720 cm(-1), corresponding to the stretching vibrations of NCO and the carbonyl of NH-CO-N, respectively, in AMPC, appeared in the infrared spectrum of POE-g-AMPC. Both rheological and X-ray photoelectron spectroscopy results indicated a new copolymer was formed in the reactive blends. Compared to uncompatibilized PBT/POE blends, smaller dispersed particle sizes with narrower distribution were found in the compatibilized PBT/POE-g-AMPC blends. There was a marked increase in impact strength by about 10-fold over that of PBT/POE blends with the same rubber content and almost 30-fold higher than that of pure PBT when the POE-g-AMPC content was 25 wt%.

Rheology, morphology and mechanical properties of LLDPE/PS blends catalyzed by combined Lewis acids

The rheological, morphological and mechanical properties of LLDPE/PS blends with a combined catalyst, Me3SiCl and InCl3 center dot 4H(2)O, were studied in this work. The higher complex viscosity and storage modulus at low frequency were ascribed to the presence of graft copolymers, which were in situ formed during the mixing process. From the rheological experiments, the complex viscosity and storage modulus of reactive blends were higher than the physical blends. The dispersion of LLDPE particles of reactive blending becomes finer than that of physical blends, consistent with the rheological results. As a result of increased compatibility between LLDPE/PS, the mechanical properties of reactive blends show much higher tensile and Izod impact strength than those of physical blends.

Preparation and Characterization of Melt Grafting 2-acrylamido-2-methyl-1-propanesulfonic Acid onto Pre-Irradiated Linear Low Density Polyethylene

Linear low density polyethylene (LLDPE) was functionalized with 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) by using -ray pre-irradiation in air in a twin-screw extruder. Fourier-transformed infrared spectroscopy (FT-IR) and electron spectroscopy for chemical analysis (ESCA) were used to characterize the formation of LLDPE-g-AMPS copolymers. The content of AMPS in LLDPE-g-AMPS was determined by using element analysis instrument. The effects of concentrations of monomer, reaction temperature and pre-irradiation dose on degree of grafting were investigated. The critical surface tension of LLDPE-g-AMPS was measured by using contact angle method. The influences of the degree of grafting on crystallization properties were studied by using DSC. Compared with neat LLDPE, the crystallization temperature increased about 4C, and crystallinity decreased with increasing degree of grafting. Crystallization rates of grafted LLDPE were faster than that of plain LLDPE at the same crystallization temperature.

Suppression of phase separation in PC/PMMA blend film by thermoset oligomer

Phase separation of bisphenol A polycarbonate (PC) and poly(methyl methacrylate) (PMMA) thin blend film is suppressed by addition of solid epoxy oligomer. Epoxy has strong intermolecular interactions with both PC and PMMA, while PC and PMMA are quite incompatible with each other. Consequently, phase separation in the PC/PMMA blend film pushes epoxy to the interface; at the same time, PC and epoxy react readily at the interface to form a cross-linking structure, binding PMMA chains together. Therefore, the interface between PC and PMMA is effectively reinforced, and the PC/PMMA thin blend film is stabilized against phase separation. On the other hand, only an optimal content of epoxy (i.e., 10 wt %) can serve as an efficient interfacial agent. In contrast to the traditional reactive compatibilization, here we observed that the cross-linking structure along the interface is much more stable than block or graft copolymers. Atomic force microscopy (AFM) is used to characterize the morphological changes of the blend films as a function of annealing time. Two-dimensional fast Fourier transform (2D-FFT) of AFM data allows quantitative investigation of the scaling behavior of phase separation kinetics.

Chain propagation kinetics on melt grafting reaction

Graft copolymerization in the molten state is of fundamental importance as a probe of chemical modification and reactive compatibilization. However, few grafting kinetic studies on reactive extrusion have been carried out because of the inherent difficulties, as expected. In this work, we have studied chain propagation kinetics on melt grafting using pre-irradiated linear low density polyethylene (LLDPE) and three monomers, acrylic acid (AA), methacrylic acid (MAA), and methyl methacrylate (MMA), as the model system. We measured the apparent chain propagation rate coefficients of grafting (k(p,g)) and homopolymerization (k(p,h)) at an initial stage for the melt grafting by FT-IR spectroscopy and electron spin resonance spectroscopy. It was observed that the convective mixing affected the rate coefficients. The magnitude of k(p,h) and k(p,g) were in the same order, but k(p,h) was slightly larger than k(p,g) The k(p,g) of the three grafting systems increased in the order: LLDPE/MMA < LLDPE/MAA < LLDPE/AA. These results are explained in terms of phase separation, solubility, and inherent reactivity of the monomer.

Biodegradable poly(L-lactide)/poly(epsilon-caprolactone)-modified montmorillonite nanocomposites: Preparation and characterization

New nanocomposites were prepared by melt blending poly(L-lactide) (PLLA), poly(epsilon-caprolactone) (PCL), and organically modified montmorillonite (OMMT). The obtained nanocomposites showed enhanced tensile strength, modulus and elongation at break than that of PLLA/PCL blends. The dynamic mechanical analysis showed the increasing mechanical properties with temperature dependence of nanocomposites. Wide-angle X-ray diffraction analysis and transmission electron microscopy indicated that the material formed the nanostructure. Adding OMMT improved the thermal stability and crystalline abilities of nanocomposites. The morphology was investigated by environmental scanning electron microscopy, which showed that increasing content of OMMT reduces the domain size of phase-separated particles. The specific interaction between each polymer and OMMT was characterized by the Flory-Huggins interaction parameter, B, which was determined by the equilibrium melting point depression of nanocomposites. The final values of B showed that PLLA was more compatible with OMMT than PCL.

Preparation of fully cross-linked CNBR/PP-g-GMA and CNBR/PP/PP-g-GMA thermoplastic elastomers and their morphology, structure and properties

Binary CNBR/PP-g-GMA and ternary CNBR/PP/PP-g-GMA thermoplastic elastomers were prepared by reactive blending carboxy nitrile rubber (CNBR) powder with nanometer dimension and polypropylene functionalized with glycidyl methacrylate (PP-g-GMA). Morphology observation by using an atomic force microscope (AFM) and TEM revealed that the size of CNBR dispersed phase in CNBR/PP-g-GMA binary blends was much smaller than that of the corresponding CNBR/PP binary blends. Thermal behavior of CNBR/PP-g-GMA and CNBR/PP blends was studied by DSC. Comparing with the plain PP-g-GMA, T, of PP-g-GMA in CNBR/PP-g-GMA blends increased about 10degreesC. Both thermodynamic and kinetic effects would influence the crystallization behavior of PP-g-GMA in CNBR/PP-g-GMA blends. At a fixed content of CNBR, the apparent viscosity of the blending system increased with increasing the content of PP-g-GMA. FTIR spectrum verified that the improvement of miscibility of CNBR and PP-g-GMA was originated from the reaction between carboxy end groups of CNBR and epoxy groups of GMA grafted onto PP molecular chains. Comparing with CNBR/PP blends, the tensile strength, stress at 100% strain, and elongation at break of CNBR/PP-g-GMA blends were greatly improved.

Kinetics study on melt grafting copolymerization of LLDPE with acid monomers using reactive extrusion method

Graft copolymerization in the molten state is of fundamental importance as a probe of chemical modification and reactive compatibilization. However, few grafting kinetics studies on reactive extrusion were carried out for the difficulties as expected. In this work, the macromolecular peroxide-induced grafting of acrylic acid and methyl methacrylate onto linear low density polyethylene by reactive extrusion was chosen as the model system for the kinetics study; the samples were taken out from the barrel at five ports along screw axis and analyzed by FTIR, H-1 NMR, and ESR. For the first time, the time-evolution of reaction rate, the reaction order, and the activation energy of graft copolymerization and homopolymerization in the twin screw extruder were directly obtained. On the basis of these results, the general reaction mechanism was tentatively proposed. It was demonstrated that an amount of chain propagation free radicals could keep alive for several minutes even the peroxides completely decomposed and the addition of monomer to polymeric radicals was the rate-controlled step for the graft copolymerization.