Heterophase

Polypropylene polymers are typically modified with ethylene to obtain desirable properties for specific applications. Specifically, ethylene—propylene mbbers are introduced as a discrete phase in heterophasic copolymers to improve toughness and low temperature impact resistance (see Elastomers, ETHYLENE-PROPYLENE rubber). This is done by sequential polymerisation of homopolymer polypropylene and ethylene—propylene mbber in a multistage reactor process or by the extmsion compounding of ethylene—propylene mbber with a homopolymer. Addition of high density polyethylene, by polymerisation or compounding, is sometimes used to reduce stress whitening. In all cases, a superior balance of properties is obtained when the sise of the discrete mbber phase is approximately one micrometer. Examples of these polymers and their properties are shown in Table 2. Mineral fillers, such as talc or calcium carbonate, can be added to polypropylene to increase stiffness and high temperature properties, as shown in Table 3. 

Random insertion of ethylene as comonomer and, in some cases, butene as termonomer, enhances clarity and depresses the polymer melting point and stiffness. Propylene—butene copolymers are also available (47). Consequendy, these polymers are used in apphcations where clarity is essential and as a sealant layer in polypropylene films. The impact resistance of these polymers is sligbdy superior to propylene homopolymers, especially at refrigeration temperatures, but still vastiy inferior to that of heterophasic copolymers. Properties of these polymers are shown in Table 4. 

Since 1980, mthenium tetroxide, RuO, has been used for staining a number of heterophase polymers for tern (221) it seems to be a more versatile staining agent than OsO. For instance, in SAN modified with acrylate mbber, where the mbber phase is fully saturated, an excellent contrast between the mbber and the matrix has been achieved (222). Crystalline polymers have been stained with RuO (223), and excellent cra2e stmctures have been revealed (221). The stain may be prepared by dissolving RuCl - 3H2O in aqueous sodium hypochlorite for immediate use (224). 

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. 

Studies of the particle—epoxy interface and particle composition have been helphil in understanding the mbber-particle formation in epoxy resins (306). Based on extensive dynamic mechanical studies of epoxy resin cure, a mechanism was proposed for the development of a heterophase morphology in mbber-modifted epoxy resins (307). Other functionalized mbbers, such as amine-terminated butadiene—acrylonitrile copolymers (308) and -butyl acrylate—acryhc acid copolymers (309), have been used for toughening epoxy resins. 

Further heating of heterophase X-ray amoi phous system to 725 K lead to simplification of composition of burning products and to formation only phase... 

In the present work, heterophase catalymetric method was shown to be suitable for metalloid determination using Selenium as an example. 

Figure 12-3. The Himont Inc. Spheripol process for producing polypropylene in a liquid-phase (1) tubular reactor, (2,4) two-stage flash pressure system (to separate unreacted monomer for recycle), (3) heterophasic copolymerization gas-phase reactor, (5) stripper.

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. 

Polymerizations conducted in nonaqueous media in which the polymer is insoluble also display the characteristics of emulsion polymerization. When either vinyl acetate or methyl methacrylate is polymerized in a poor solvent for the polymer, for example, the rate accelerates as the polymerization progresses. This acceleration, which has been called the gel effect,probably is associated with the precipitation of minute droplets of polymer highly swollen with monomer. These droplets may provide polymerization loci in which a single chain radical may be isolated from all others. A similar heterophase polymerization is observed even in the polymerization of the pure monomer in those cases in which the polymer is insoluble in its own monomer. Vinyl chloride, vinylidene chloride, acrylonitrile, and methacryloni-trile polymerize with precipitation of the polymer in a finely divided dispersion as rapidly as it is formed. The reaction rate increases as these polymer particles are generated. In the case of vinyl chloride ... 

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... 

HECO Heterophasic ethylene-propylene PDMS Polydimethylsiloxane... 

In microphase-separated systems, ESR spectra may consist of a superposition of two contributions, from nitroxides in both fast and slow-tumbling regimes. Such spectra provide evidence for the presence of two types of domains with different dynamics and transition temperatures. This case was detected for a HAS-derived nitroxide radical in heterophasic polyfacrylonitrile-butadiene-styrene) (ABS) as shown in Figure 5, the fast and slow components in the ESR spectrum measured represent nitroxide radicals located in butadiene-rich (B-rich) and styrene/acrylonitrile-rich (SAN-rich) domains, respectively [40]. These two components were determined by deconvoluting the ESR spectrum of HAS-NO measured at 300 K. 

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. 

To illustrate the potential of the method, we present in Figure 7 the 2D ESRI perspective plot of a phantom sample consisting of nitroxide biradicals derived from Tinuvin 770 (obtained by oxidation of the amine) in two different environments in a plaque of heterophasic propylene-ethylene copolymers (HPEC). One side of the plaque was doped with the biradical by contact with a biradical solution in toluene. The same biradical solution was placed on transparent tape and the solvent was evaporated the tape was then folded and attached to the other side of the plaque. The corresponding spectral slices are... 

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 following major conclusions were deduced from the ESRI studies of degradation in the heterophasic polymers ... 

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. 

ABA triblock copolymers of the styrene-diene type are well known, and owe their unique properties to their heterophase morphology. This arises from the incompatibility between the polystyrene A blocks and the polydiene B blocks, leading to the formation of a dispersion of very small polystyrene domains within the polydiene matrix. This type of elastic network, held together by the polystyrene "junctions", results in thermoplastic elastomer properties. 

Bigg, D. M. Thermal Conductivity of Heterophase Polymer Compositions. Vol. 119, pp. 1-30. 

The well-known acid-catalyzed conversion of sugars into furan derivatives obviously consists of a complex sequence of reactions, and the industrial heterophasic conversion of pentosans in plant tissues has been discussed in detail.11 The reactions themselves are still not well understood, although xylose and glucuronic acid in deuterium oxide afford 2-furaldehyde without uptake of isotope thus limiting the mechanistic possibilities to those not permitting reversible enolization.12 The bacterial sugar streptose yields... 

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