Heterophase polymers systems

As described below, the HAS-derived nitroxides in heterophasic polymer systems perform a triple role. First, they provide the contrast needed in the imaging experiments. Second, they enable the visualization of polymer morphology, based on the detection of two dynamically different components detected in the ESR spectra of the nitroxides in ABS, for example, the two sites, fast (F) and slow (S), have been assigned to location of nitroxides in butadiene-rich and styrene-acrylonitrile (SAN)-rich domains, respectively. Third, the spatial variation of the ESR spectra of nitroxides (in terms of intensity and line shapes) with treatment time, t, provides detailed information on the extent of degradation in the different miCTodomains. These experiments made possible the determination of the concentration profiles of the nitroxides from ID ESRl, and also of the spectral profiles from 2D spectral-spatial ESRI, both in a nondestructive way. In these studies the nitroxides, which are the contrast agents, are part of the systan therefore these studies represent the evolution of ESRl techniques beyond phantoms. 

The diffusion coefficients of nitroxide radicals derived from HASs in a heterophasic polymer system have been measured recently by ID ESRI. ° ... 

An ESRI system can be built with small modifications of commercial spectrometers by, for example, gradient coils fixed on the poles of the spectrometer magnet, regulated direct current (DC) power supplies, and required computer connections [40,53,55]. Gradients can be applied in the three spatial dimensions, and a spectral dimension can be added by the method of stepped gradients. The spectral dimension is important when the spatial variation of ESR line shapes (as a function of sample depth) is of interest this situation will be described below, in the ESRI studies of heterophasic polymers. In most systems, the software for image reconstruction in ESRI experiments must be developed in-house. 

Detailed analysis of the isothermal dynamic mechanical data obtained as a function of frequency on the Rheometrics apparatus lends strong support to the tentative conclusions outlined above. It is important to note that heterophase (21) polymer systems are now known to be thermo-rheologically complex (22,23,24,25), resulting in the inapplicability of traditional time-temperature superposition (26) to isothermal sets of viscoelastic data limitations on the time or frequency range of the data may lead to the appearance of successful superposition in some ranges of temperature (25), but the approximate shift factors (26) thus obtained show clearly the transfer viscoelastic response... 

Michailov YM, Ganina LV, Smirnov VS. (2002) Phase equilibrium in biphase polymer systems based on Diglycidyl Ether of Bisphenol A. In Rozenberg BA, Sigalov GM (eds.). Heterophase Network Polymers Synthesis, Characterization, and Properties, pp. 33-42, CRC Press. 

As has already been stated, the verified possibility of extending the reduced variables principles to ABS resins makes it possible to treat these typical heterophase systems as blends of amorphous homophase polymers and plasticizers. One possible explanation is that over the experimental y range it is not possible to separate the contributions of the two different phases, and the materials will behave as homophase polymer. In fact, long-time molten polymer rheology experiments measure viscoelastic processes over the entire molecule, and, as a consequence, molecular compatibility is evaluated (13). On the other hand, high frequency and/or low temperature tests involve the main chain as well as the side chains of the polymer system the segmental miscibility of the polymer-polymer system is then evaluated. It is important in experimental measurements of polymer compatibility to evaluate the actual size of the volume subject to the test. 

The advantages of localizing the reaction centers of heterophase catalytic systems on the surface or in a thin surface layer of polymer were emphasized in Section 12.3.1. The same conclusion is valid for the hydroformylation of hexene-1 in the presence of Rh(AcAc)(CO)2 supported on the surface of polypropylene-gr-poly(styryldiphenylphosphine) [160]. Under mild conditions (338 K, 1.6 MPa) the ratio between n- and wo-aldehydes for this system is at least 3.5 times higher than that for the homogeneous analogue. 

Heterophase polymerization systems can be defined as two-phase systems in which the resulting polymer and/or starting monomer are in the form of a fine dispersion in an immiscible liquid medium defined as the polymerization medium , continuous phase , or outer phase . Even if oil-in-water (o/w) systems are greatly preferred on an industrial scale, water-in-oil (w/o) systems may also be envisaged for specific purposes. Heterogeneous polymerization processes can be classified as suspension, dispersion, precipitation, emulsion, or miniemulsion techniques according to interdependent criteria which are the initial state of the polymerization mixture, the kinetics of polymerization, the mechanism of particle formation and the size and shape of the final polymer particles (Fig. 4.2) [18]. 

This chapter is organized as follows. Section 2 desolbes selected experimental details on sample preparation and treatment, as well as on the determination of the nitroxide profile (ID ESRl) and on 2D spectral-spatial ESRl. The ESR spectra of HAS-NO in the heterophasic polymers are described in Section 3. Both ID and 2D ESRl experiments are desolbed in Section 4, which includes results for the ABS and HPEC systems, a comparison of ESRl and Eourier transform (FT IR) methods, and our experience with the effect of microtoming on crystalline polymers. Conclusions are presented in Section 5. 

Thermoplastic Elastomers (TPE) are classes of heterophasic polymers, characterized by thermo-reversible interaction among the polymeric chains. The new polymeric materials that are considered to produce easy recyclable automotive systems, can be defined as a sort of a new generation of Olefinic Thermoplastic Elastomers (TPO), belonging to a broad family of polyolefinic alloys that can now be produced directly dining the polymerization phase. These completely new materials, resulting from advanced research and development carried out by HIMONT, can be tailored in order to meet different requirements of most of car apphcations. The basic partly finished components suitable for the constructions of the main automotive composite structru-es will be described. 

Some of the most difficult heterophase systems to characterize are those based on hydrocarbon polymers such as mbber-toughened polypropylene or other blends of mbbers and polyolefins. Eecause of its selectivity, RuO staining has been found to be usehil in these cases (221,222,230). Also, OsO staining of the amorphous blend components has been reported after sorption of double-bond-containing molecules such as 1,7-octadiene (231) or styrene (232). In these cases, the solvent is preferentially sorbed into the amorphous phase, and the reaction with OsO renders contrast between the phases. 

The formation mechanism of structure of the crosslinked copolymer in the presence of solvents described on the basis of the Flory-Huggins theory of polymer solutions has been considered by Dusek [1,2]. In accordance with the proposed thermodynamic model [3], the main factors affecting phase separation in the course of heterophase crosslinking polymerization are the thermodynamic quality of the solvent determined by Huggins constant x for the polymer-solvent system and the quantity of the crosslinking agent introduced (polyvinyl comonomers). The theory makes it possible to determine the critical degree of copolymerization at which phase separation takes place. The study of this phenomenon is complex also because the comonomers act as diluents. 

Analyzing the behavior of filled polymers, as any other heterophase systems, two aspects should be distinguished. First, these are the properties of such systems, i.e. their inherent characteristics, independent of a measuring method if, of course, the measurements are correct (to select criteria of correctness of an experiment, carried out with multiphase systems, seems to be an independent and by no means a simple problem). Second, this is a manifestation of these properties when heterophase systems flow in channels of different geometrical form. Behind all this stands the basic applied problem—finding out how the properties of filled polymers, appearing during their flow, affect the properties of finished articles. 

As has already been emphasized in Fig. 1.1, there is the further problem of connecting the mesoscopic scale, where one considers length scales from the size of effective monomers to the scale of the whole coils, to still much larger scales, to describe structures formed by multichain heterophase systems. Examples of such problems are polymer blends, where droplets of the minority phase exist on the background of the majority matrix, etc. The treatment of... 

ESRI methods have been developed in our Detroit laboratory for the study of heterophasic systems such as ABS [14,40,59,87-89] and HPEC [61,90], both containing bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate (Tinuvin 770) as the stabilizer, and exposed to thermal treatment and UV irradiation. The HAS-NO provided the contrast necessary in the imaging experiments. The major objectives were to examine polymer degradation under different conditions to assess the effect of rubber phase, polybutadiene (PB) in ABS and ethylene-propylene rubber (EPR) in HPEC, on the extent of degradation and to evaluate the extent of... 

The ESRI experiments described in our publications and summarized in this chapter led to spatially resolved information on the effect of treatment conditions, amount of stabilizer, and polymer composition on the degradation rate. In the heterophasic systems studied in our laboratory, ESRI has identified specific morphological domains where chemical processes are accelerated. The combination of ID and 2D spectral-spatial ESRI experiments led to mapping of the stabilizer consumption on two length scales within the sample depth on the scale of a few mm, and within morphological domains on the scale of a few gm. 

In more recent years, Herman Mark has, as we all know, concentrated more on the effects of heterophase morphology of polymers on their mechanical properties. This has enabled him to set up a useful classification system of the various types of heterogeneities which can occur in polymers, e.g., crystallinity, incompatibility, particulate and fibrous inclusions, etc. and to discuss these in the context of their effect on the mechanical properties. Such an "overview" has again kept Mark in great demand as a speaker. 

Absorbance subtraction can be considered as a spectroscopic separation technique for some problems in polymers. An interesting application in FT-IR difference spectroscopy is the spectral separation of a composite spectrum of a heterophase system. One such example is a semicrystalline polymer which may be viewed as a composite system containing an amorphous and crystalline phase53). In general, the infrared spectrum of each of these phases will be different because in the crystalline phase one particular rotational conformation will predominate whereas in the disordered amorphous regions a different rotamer will dominate. Since the infrared spectrum is sensitive to conformations of the backbone, the spectral contributions will be different if they can be isolated. The total absorbance A, at a frequency v of a semicrystalline polymer may be decomposed into the following contributions... 

In the case of the heterophase systems resulting from the ABA block polymers, the strength is reinforced because of the ability of the plastic,... 

With the advent of advanced characterization techniques such as multiple detector liquid exclusion chromatography and - C Fourier transform nuclear magnetic resonance spectroscopy, the study of structure/property relationships in polymers has become technically feasible (l -(5). Understanding the relationship between structure and properties alone does not always allow for the solution of problems encountered in commercial polymer synthesis. Certain processes, of which emulsion polymerization is one, are controlled by variables which exert a large influence on polymer infrastructure (sequence distribution, tacticity, branching, enchainment) and hence properties. In addition, because the emulsion polymerization takes place in an heterophase system and because the product is an aqueous dispersion, it is important to understand which performance characteristics are influended by the colloidal state, (i.e., particle size and size distribution) and which by the polymer infrastructure. 

Polymer colloids involve dispersions containing polymer particles having sizes greater than about 1 nm. If dispersed in aqueous solution, such a polymer dispersion is called a latex. These are usually synthetic polymer particles formed by free radical polymerization [784], Many kinds of polymerization systems exist, involving almost all of the possible kinds of colloidal dispersion, including emulsion polymerization, hence the more general term heterophase polymerization is sometimes used. Several reviews are available [785-789]. Emulsion polymerization provides a convenient means of controlling the polymerization of monomers and is used to make, for example, synthetic rubber which is mostly a co-polymer of butadiene and styrene. 

The aim of developing a new polymer blend is to synergistically combine the properties of the individual polymers resulting in an improved material. A general precondition to this scheme of fabrication, however, is that in order for the final blended material to have the desired properties, the final polymeric phases must form a heterophasic blend, i.e., they must have at least partial thermodynamic immiscibility. This is in contrast to the requirement that the initial reactants must form initially miscible solutions. These conditions do not seem to be met by most polyimide-epoxy systems. 

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