Physical crosslinking effects in α,ω-dihydroxy terminated polybutadienes

Structure and molecular dynamics of α,ω-dihydroxy terminated polybutadienes of varying number averaged molecular weight (1320-10?500 g/mol) have been investigated by Fourier-transformed infrared (FTIR) spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, dielectric relaxation spectroscopy (DRS), differential scanning calorimetry (DSC) and wide-angle X-ray scattering (WAXS). DSC and DRS revealed an increase in the glass transition temperature upon decrease of the molecular weight, accompanied by an increasing dynamic fragility m (or steepness index) of the dielectric α-process. This correlation between T_g and m for different molecular weights indicates the presence of a physical network, where H-bonded end-group clusters act as temporary crosslinks. From the dielectric relaxation strength Δ?_α(M_n), the fraction of associated hydroxy groups (f_bond) was estimated showing a peak value for the two but shortest polymers, a behaviour that strongly resembles the molecular weight dependence of the fragility. By considering the quantity f_bond(M_n) in a modified Fox-Flory approach, the measured T_g(M_n) behaviour could be reproduced in a satisfying way. FTIR results support this general picture and show a considerable dependence of the extent of hydrogen bonding and formation of hydroxy groups associates on the molecular weight. Further, WAXS and DSC results disprove the idea of formation of pseudo-crystalline hydrophobic microdomains in these compounds as suggested by other authors.     

Solvent induced crystallization of syndiotactic poly(methyl methacrylate) relation to the formation of polymer aggregates in solution

Polymer Bulletin - Solutions of syndiotactic (s) poly (methyl methacrylate) (PMMA) and samples of solid s-PMMA prepared from these solutions were studied by NMR and infrared (IR) spectroscopy and...     

The effect of specific β‐nucleation on morphology and mechanical behavior of isotactic polypropylene

The commercial grade of isotactic polypropylene was modified by a specific β‐nucleating agent in a broad concentration range. The supermolecular structure of the specimens prepared by injection molding was characterized by X‐ray scattering and correlated with mechanical behavior. It was found that at a critical nucleant concentration of 0.03 wt % the content of the β‐modification virtually reaches a saturation level. With further addition of the nucleant, the β‐phase content increases only slightly. The long period passes through a distinct maximum at the same nucleant concentration. This singularity in structure remarkably correlates with a minimum of the yield stress and maxima of strain at break and fracture toughness. Such general behavior is also reflected in the correlation between the β‐phase concentration and fracture toughness profiles along the injection‐molded bars. It is suggested that in the critically nucleated material an optimum thickness of the amorphous interlayer with connecting chains between the β‐crystallites is established, rendering the material the highest possible ductility and toughness. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1174–1184, 2002     

Behavior of Deformed Droplets in an Immiscible Polymer Blend: A Comparative Study of Electron Microscopy and Small‐Angle X‐Ray Scattering

The deformation of dispersed droplets in a PS/LLDPE 95:5 blend during uniaxial elongation and after cessation of the flow was studied. The behavior of the dispersed droplets during elongation is in a good agreement with a prediction of the modified capillary number model using transient elongational viscosities. The phase structure changes after the elongation was studied in relaxation and recovery modes. The morphology was investigated using scanning electron microscopy and small‐angle X‐ray scattering. Thus the dimensions of the dispersed particles and their degree of orientation were estimated. It was shown that the SAXS as an integral method gives new additional information which is hardly accessible by SEM as a method providing local information about discrete locations in the sample. The results of both methods proved that the stress in the sample is a decisive parameter determining the morphology development after cessation of the flow.

     

Polymer-clay nanocomposites prepared via in situ emulsion polymerization

A series of novel polystyrene and poly(butyl methacrylate) montmorillonites (MMT-Na) nanocomposite latexes have been successfully prepared by emulsion polymerization. First of all, chemical modification of MMT-Na with a reactive coupling agent (MMT-QS) has been employed for the synthesis of hybrids. Subsequently, in situ seeded emulsion polymerization of hydrophobic vinyl monomers, such as butyl methacrylate and styrene, using sodium dodecyl sulfate (SDS) and ammonium persulfate (APS) as surfactant and initiator, respectively, were used for nanocomposite preparation. This technique allowed preparing of stable nanocomposite latexes with high (30–45 wt.%) solids contents and with loading of inorganic particles up to 5 wt.%. The prepared wet dispersions were subsequently characterized by light scattering method. In order to characterize the microstructure of the clay layers, and that of the organoclay in polystyrene and poly(butyl methacrylate) nanocomposites, wide and small angle X-ray analyses (WAXS, SAXS) and transmission electron microscopy (TEM) techniques were used.     

Self‐assembled structures in polystyrene‐block‐polyisoprene‐blend‐polystyrene and polystyrene‐block‐poly(methyl methacrylate)‐blend‐polystyrene or ‐blend‐poly(methyl methacrylate) in the strong segregation regime

This study deals with the investigation of microphase‐separated morphology and phase behaviour in blends of polystyrene‐block‐polyisoprene with homopolystyrene and blends of polystyrene‐block‐poly(methyl methacrylate) with homopoly(methyl methacrylate) or homopolystyrene in the strong segregation regime using small‐angle X‐ray scattering and transmission electron microscopy as a function of composition, molecular weight of homopolymers, r_M and temperature. Parameter r_M = M_H/M_C (where M_H is the molecular weight of homopolymer and M_C that of the corresponding block copolymer) was selected to encompass behaviour of the chains denoted as a ‘wet brush’ (i.e. r_M < 1). The relative domain spacing D/D_o increases in the regime 0 < r_M?1 with increasing concentration of homopolymer w_P and increasing r_M but depends on the specific implemented morphology. We tested a new approximate D/D_o versus w_P relation in the strong segregation regime using block copolymers of high molecular weights. It is shown that the parameters r_M and χ^3/2N determine the slope of the D/D_o versus w_P relation in the strong segregation regime and the new approximation generally matches the experimental data better than the approximations used so far. Copyright © 2010 Society of Chemical Industry     

Epoxy‐clay nanocomposites: Influence of the clay surface modification on structure

In this article, the effect of four different clay surface modifiers on the structure of epoxy‐clay nanocomposites was studied. Various organoclays were prepared via cation exchange reaction between inorganic cations naturally occuring in the clay gallery and different alkylammonium ions. Epoxy‐clay nanocomposites were prepared by in situ intercalative polymerization using a hardener of polyoxypropylenediamine type. It was found that various clay surface modifiers exhibit different catalytic effect on curing of epoxy inside the clay gallery as observed by measuring of the gel time with dynamic mechanical analysis. This was confirmed by monitoring the change in the d‐spacing by wide angle X‐ray scattering performed in situ during curing. Morphology of the cured systems was probed by transmission electron microscopy (TEM) and wide angle X‐ray scattering (WAXS). The degree of dispersion observed by TEM and WAXS corresponds with achieved mechanical properties of cured composites. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Influence of a compatibilizer on the morphology development in polymer blends under elongation

Compatibilization is the modification of the interface in immiscible polymer blends in order to refine and stabilize their phase structure. The presence of a compatibilizer at the interface markedly affects the deformation behaviour of the dispersed droplets during and after cessation of flow. In this work the morphology development in blends of polystyrene and linear low-density polyethylene compatibilized with styrene-butadiene-styrene triblock copolymer during and after uniaxial elongation was investigated by means of electron microscopy and small-angle X-ray scattering. The incorporation of only 1 wt.-% of the compatibilizer led to a pronounced increase of the stationary elongational viscosity of the blend. It was found, that at moderate capillary number (Ca ≈ Ca_CR) the compatibilizer stabilises the droplets against break-ups during the flow. When Ca >> Ca_CR no differences in the deformation of uncompatibilized and compatibilized droplets were observed. After cessation of the flow, the presence of the compatibilizer prevented the droplet break-up and supported and accelerated the shape recovery of the elongated particles.     

Chlorosulfonated polypropylene: preparation and its application as a coupling agent in polypropylene-clay nanocomposites

Polypropylene nanocomposites containing organophilic layered silicate were prepared by melt mixing. In order to increase polypropylene polarity, Cl and SO₂Cl groups were introduced by reaction with sulfuryl chloride under UV irradiation. Chlorosulfonated polypropylene was subsequently melt-compounded with organophilized montmorillonite clay to produce a masterbatch. The masterbatch was then blended with commercial isotactic polypropylene. An organophilized silicate (Cloisite 15A) and three chlorosulfonated polypropylenes with different degrees of functionalization were used in this study. The effect of various processing procedures was examined as well. The morphology of nanocomposites obtained was examined using TEM and X-ray diffraction. It has been shown that the presence of polar groups leads to an increased gallery distance and partial exfoliation. Nevertheless, full exfoliation of clay platelets has not been achieved. The observed morphologies affected the resulting tensile mechanical behaviour: both stiffness and strength significantly increased.