Graft copolymers morphology

Figure 2.4. Rubber membrane structure of impact-resistant polystyrene (6% polybutadiene 22% rubber phase volume). This graft-copolymer morphology, containing a fine structure within the discontinuous phase, is brought about by agitation during the early stages of polymerization. (Wagner and Robeson, 1970.)...

Monomer compositional drifts may also occur due to preferential solution of the styrene in the mbber phase or solution of the acrylonitrile in the aqueous phase (72). In emulsion systems, mbber particle size may also influence graft stmcture so that the number of graft chains per unit of mbber particle surface area tends to remain constant (73). Factors affecting the distribution (eg, core-sheU vs "wart-like" morphologies) of the grafted copolymer on the mbber particle surface have been studied in emulsion systems (74). Effects due to preferential solvation of the initiator by the polybutadiene have been described (75,76). 

In addition to graft copolymer attached to the mbber particle surface, the formation of styrene—acrylonitrile copolymer occluded within the mbber particle may occur. The mechanism and extent of occluded polymer formation depends on the manufacturing process. The factors affecting occlusion formation in bulk (77) and emulsion processes (78) have been described. The use of block copolymers of styrene and butadiene in bulk systems can control particle size and give rise to unusual particle morphologies (eg, coil, rod, capsule, cellular) (77). 

It is well known that block copolymers and graft copolymers composed of incompatible sequences form the self-assemblies (the microphase separations). These morphologies of the microphase separation are governed by Molau s law [1] in the solid state. Nowadays, not only the three basic morphologies but also novel morphologies, such as ordered bicontinuous double diamond structure, are reported [2-6]. The applications of the microphase separation are also investigated [7-12]. As one of the applications of the microphase separation of AB diblock copolymers, it is possible to synthesize coreshell type polymer microspheres upon crosslinking the spherical microdomains [13-16]. 

Park et al. [20] reported on the synthesis of poly-(chloroprene-co-isobutyl methacrylate) and its compati-bilizing effect in immiscible polychloroprene-poly(iso-butyl methacrylate) blends. A copolymer of chloroprene rubber (CR) and isobutyl methacrylate (iBMA) poly[CP-Co-(BMA)] and a graft copolymer of iBMA and poly-chloroprene [poly(CR-g-iBMA)] were prepared for comparison. Blends of CR and PiBMA are prepared by the solution casting technique using THF as the solvent. The morphology and glass-transition temperature behavior indicated that the blend is an immiscible one. It was found that both the copolymers can improve the miscibility, but the efficiency is higher in poly(CR-Co-iBMA) than in poly(CR-g-iBMA),... 

Compatibility and various other properties such as morphology, crystalline behavior, structure, mechanical properties of natural rubber-polyethylene blends were investigated by Qin et al. [39]. Polyethylene-b-polyiso-prene acts as a successful compatibilizer here. Mechanical properties of the blends were improved upon the addition of the block copolymer (Table 12). The copolymer locates at the interface, and, thus, reduces the interfacial tension that is reflected in the mechanical properties. As the amount of graft copolymer increases, tensile strength and elongation at break increase and reach a leveling off. 

The comparison of the 2D plot of a graft copolymer with the 2D plot of the precursor PEO shows clearly that the graft copolymer sample does not contain any free PEO. This result was also confirmed by MALDI-TOF mass spectrometry. Next to the requirement of being PEO free, the PEO-g-PVA copolymers showed a good combination of film-forming properties, a fast dissolution, and a low solution viscosity in water. The phase separated morphology, as demonstrated by TEM, DSC, DMTA, and WAXS experiments, provided the PEO-g-PVA copolymers with relatively constant mechanical properties. 

Starch ethers, 4 720 Starch graft copolymers, 4 722 Starch-granule morphology, 26 273 Starch hydrolysates, hydrogenated, 12 39 Starch industry, enzyme use in, 10 252-253... 

Thermoplastic elastomers (TPE), 9 565-566, 24 695-720 applications for, 24 709-717 based on block copolymers, 24 697t based on graft copolymers, ionomers, and structures with core-shell morphologies, 24 699 based on hard polymer/elastomer combinations, 24 699t based on silicone rubber blends, 24 700 commercial production of, 24 705-708 economic aspects of, 24 708-709 elastomer phase in, 24 703 glass-transition and crystal melting temperatures of, 24 702t hard phase in, 24 703-704 health and safety factors related to, 24 717-718... 

As typically observed in the case of non-ionic block and graft copolymers, the immiscibility of the constituent blocks within the copolymers can induce microphase separation beyond even that which normally occurs due to hydrophobic and hydrophilic sites within statistical copolymer PEMs such as Nation. A relatively recent area of PEM research, ionic block and graft copolymers are interesting from the point of view of providing fundamental understanding about the influence of morphology upon proton conduction... 

Figure 2. Morphology of various cross-polybutadiene-in/er-cross-polystyrene sequential IPNs and graft copolymers via transmission electron microscopy. The double bonds in the polybutadiene phase are stained dark with osmium tetroxide. (Reproduced from ref. 15. Copyright 1976 American Chemical Society.)...

Styrene as matrix and polybutadiene as dispersed phase. During this phase inversion the above-mentioned graft copolymers act as polymeric emulsifiers and determine, inter alia, the particle size and particle size distribution of the dispersed polybutadiene phase. This morphology is fixed through another chemical reaction, that is the crosslinking of the polybutadiene phase. Therefore, the reaction mixture at the end of the prepolymerization period (at 30% conversion) does scarcely alter its morphology when it is polymerized to complete conversion, which is done without stirring mostly in bulk in a separate vessel. 

Riess G, Periard J, Banderet A Emulsifying Effect of Block Graft Copolymers - Oil in Oil Emulsions In G. E. Molau (ed) Colloidal and Morphological Behaviour of Block and Graft Copolymers (Proceedings of an American Chemical Society Symposium held at Chicago, Illinois, Sep. 13, 1970)... 

G. Riess, J. Periard, A. Bonderet, Colloidal and Morphological Behavior of Block and Graft Copolymers, Plenum New York, (1971). 

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