Poly , crystalline phase structur

Much work has been reported on studying the structure of thermoset resins via SAXS, especially focussing on interpenetrating network polymers (IPNs), thermoset nanocomposites, rubber-modified thermosets and thermoset-thermoplastic blends. Most recently Guo et al, (2003) have examined the use of SAXS to monitor the nanostructure and crystalline phase structure of epoxy-poly(ethylene-ethylene oxide) thermoset-thermoplastic blends. This work proposes novel controlled crystallization due to nanoscale confinements. 

From X-ray diffraction experiments28 it is known that in the crystalline phase the erythrodiisotactic poly(l,2-dimethyltetramethylene) has a (g+aaa g aaa)n structure as shown in Fig. 13. The bold printed letters in the denotation give the conformation of the CH—CH bond. In agreement with this structure and low temperature solution state spectra of 2,3-dimethylbutane, 3,4-dimethylhexane, and 4,5-dimethyloctane 29 30) in which the CHCH bond rotation is frozen the crystalline signals can be assigned conclusively. Like for the crystalline state of poly(l,2-... 

This rule of thumb does not apply to all polymers. For certain polymers, such as poly (propylene), the relationship is complicated because the value of Tg itself is raised when some of the crystalline phase is present. This is because the morphology of poly(propylene) is such that the amorphous regions are relatively small and frequently interrupted by crystallites. In such a structure there are significant constraints on the freedom of rotation in an individual molecule which becomes effectively tied down in places by the crystalhtes. The reduction in total chain mobility as crystallisation develops has the effect of raising the of the amorphous regions. By contrast, in polymers that do not show this shift in T, the degree of freedom in the amorphous sections remains unaffected by the presence of crystallites, because they are more widely spaced. In these polymers the crystallites behave more like inert fillers in an otherwise unaffected matrix. 

It has also been inferred that differences found between crystallinities measured by density and those from heat of fusion by DSC area determination, as given for polyethylenes in the example of Figure 4 [72], may be related to baseline uncertainties, or not accounting for the temperature correction of AHc. Given that similar differences in crystallinity from density and heat of fusion were reported for isotactic poly(propylene) [43] and polyfaryl ether ether ketone ketone), PEEKK [73], other features of phase structure that deviate from the two-phase model may be involved in the crystallinity discrepancy. 

Structural characterization of crystalline phases of poly(methylene-l,3-cyclopentane) samples of different microstructures have also been reported (a) Ruiz de Ballesteros, O. Venditto, V. Auriemma, F. Guerra, G. Resconi, L. Waymouth, R. M. Mogstad, A. L. Macromolecules 1995, 28, 2383. (b) Ruiz de Ballesteros, O. Cavallo, L. Auriemma, F. Guerra, G. Macromolecules 1995, 28, 7355. 

Copoly(ether ester)s consisting of short-chain crystalline segments of PBT and amorphous poly(ether ester) of poly(tetramethylene terephthalate) exhibit a two-phase structure and can be used for the production of high-impact-strength engineering plastics. These very interesting materials with their outstanding properties understandably require stabilization to heat and UV exposure [45],... 

As a consequence of this almost perfect alignment of molecule structures, such polyamides are able to orientate in solution and to form liquid crystalline phases (see Sect. 1.3.4). Out of these solutions one obtains fibers of poly(p-phenylene terephthalamide) (PPTA) having 5-10-fold higher values for stiffness and strength as the all-mefa linked polymers. In addition, PPTA crystallizes, whereupon the fibers achieve an extraordinary temperature resistance in a nitrogen atmosphere they decompose at temperatures above 550 °C without melting. 

Information on the crystal to liquid crystal transitions is scarce and is to be treated with caution since partial crystallization is prominent and polymorphism of the smectic phase is frequent. Only the data on poly(acryloyloxybenzoic acid) (entry 2 of Table 5) have been extrapolated to 100% crystallinity. As with the low molecular weight liquid crystals, the total heat of transition is lower than expected for fully ordered crystals. Various combinations of two phase structures as suggested by Fig. 3 could be produced for the poly(acryloyloxybenzoic acid)21>. 

Pochan, J. M., Hinman, D. F. and Froix, M. F. Morphological studies on the viscous crystalline phase of poly(diethylsiloxane) including the dynamics of phase formation and the relationship of viscous crystalline structure and crystalline structure. Macromolecules 9, 611 (1976)... 

The potential for novel phase behaviour in rod-coil block copolymers is illustrated by the recent work of Thomas and co-workers on poly(hexyl iso-cyanate)(PHIC)-PS rod-coil diblock copolymers (Chen etal. 1996). PHIC, which adopts a helical conformation in the solid state, has a long persistence length (50-60 A) (Bur and Fetters 1976) and can form lyotropic liquid crystal phases in solution (Aharoni 1980). The polymer studied by Thomas and co-workers has a short PS block attached to a long PHIC block. A number of morphologies were reported—wavy lamellar, zigzag and arrowhead structures—where the rod block is tilted with respect to the layers, and there are different alternations of tilt between domains (Chen et al. 1996) (Fig. 2.37). These structures are analogous to tilted smectic thermotropic liquid crystalline phases (Chen et al. 1996). 

In this section we will discuss the molecular structure of this polymer based on our results mainly from the solid-state 13C NMR, paying particular attention to the phase structure [24]. This polymer has somewhat different character when compared to the crystalline polymers such as polyethylene and poly(tetrameth-ylene) oxide discussed previously. Isotactic polypropylene has a helical molecular chain conformation as the most stable conformation and its amorphous component is in a glassy state at room temperature, while the most stable molecular chain conformation of the polymers examined in the previous sections is planar zig-zag form and their amorphous phase is in the rubbery state at room temperature. This difference will reflect on their phase structure. 

As pointed out above with relation to the data at 87 °C, the Tic of the crystalline-amorphous interphase is appreciably longer than that of the amorphous phase, suggesting the retention of the helical molecular chain conformation in the interphase. We also note that a Tic of 65-70 s for the crystalline phase is significantly shorter than that for other crystalline polymers such as polyethylene and poly-(tetramethylene oxide), whose crystalline structure is comprised of planar zig-zag molecular-chain sequences. In the crystalline region composed of helical molecular chains, there may be a minor molecular motion in the TiC frame, with no influence on the crystalline molecular alignment that is detected by X-ray diffraction analyses. Such a relatively short TiC of the crystalline phase may be a character of the crystalline structure that is formed by helical molecular chain sequences. 

Finally, we have attempted to evaluate the possible impact of an intermediate liquid crystalline phase and the possibility of transfer of helical hand information from the melt to the crystal throughout this process. Assuming that the melt is structured, the melt of chiral but racemic polyolefins would be made of stretches of helical stems that are equally partitioned between left- and right-handed helices. Formation of antichiral structures (such as in a iPP) could be interpreted as indicating a possible transfer of information (but the problem of the sequence of helical hands would still remain). This analysis is, however, ruined by the observation that many of these polymers also form chiral structures (frustrated p phase of iPP, Form III of iPBul). For the achiral poly(5-methyl-pentene-l), the chiral, frustrated phase is actually the more stable one, and can be obtained by melting and recrystallization of a less stable antichiral phase. 

Crystalline cationic poly(3-methylbutene-l) exists in two distinct crystalline phases which are called a and / modifications (165). Both cationic forms are different from the isotactic polymer as judged from their respective X-ray d spacings. The a modification is more stable than the /S form. The repeat distance of an oriented a specimen was found to be 7.8 A which indicates 2 structural units per repeat distance assuming 1,3 enchainment. 

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