Block copolymers mechanical

Bilirubin Block copolymer, mechanical break, <100 pm diameter 10.3 mg/g >10 times, >90% recovered [102]... 

In block copolymers [8, 30], long segments of different homopolymers are covalently bonded to each otlier. A large part of syntliesized compounds are di-block copolymers, which consist only of two blocks, one of monomers A and one of monomers B. Tri- and multi-block assemblies of two types of homopolymer segments can be prepared. Systems witli tliree types of blocks are also of interest, since in ternary systems the mechanical properties and tire material functionality may be tuned separately. 

Block copolymers are closer to blends of homopolymers in properties, but without the latter s tendency to undergo phase separation. As a matter of fact, diblock copolymers can be used as surfactants to bind immiscible homopolymer blends together and thus improve their mechanical properties. Block copolymers are generally prepared by sequential addition of monomers to living polymers, rather than by depending on the improbable rjr2 > 1 criterion in monomers. 

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). 

Gun Propellents. Low sensitivity gun propeUants, often referred to as LOVA (low vulnerabUity ammunition), use RDX or HMX as the principal energy components, and desensitizing binders such as ceUulose acetate butyrate or thermoplastic elastomers (TPE) including poly acetal—polyurethane block copolymers, polystyrene—polyacrjiate copolymers, and glycidyl azide polymers (GAP) to provide the required mechanical... 

Fig. 44. Thermal mechanical behavior of a styrene—butadiene—styrene block copolymer in nitrogen at —180 to 150°C (280).

Butadiene copolymers are mainly prepared to yield mbbers (see Styrene-butadiene rubber). Many commercially significant latex paints are based on styrene—butadiene copolymers (see Coatings Paint). In latex paint the weight ratio S B is usually 60 40 with high conversion. Most of the block copolymers prepared by anionic catalysts, eg, butyUithium, are also elastomers. However, some of these block copolymers are thermoplastic mbbers, which behave like cross-linked mbbers at room temperature but show regular thermoplastic flow at elevated temperatures (45,46). Diblock (styrene—butadiene (SB)) and triblock (styrene—butadiene—styrene (SBS)) copolymers are commercially available. Typically, they are blended with PS to achieve a desirable property, eg, improved clarity/flexibiHty (see Polymerblends) (46). These block copolymers represent a class of new and interesting polymeric materials (47,48). Of particular interest are their morphologies (49—52), solution properties (53,54), and mechanical behavior (55,56). 

Styrene—butadiene block copolymers are made with anionic chain carriers, and low molecular weight PS is made by a cationic mechanism (110). Analytical standards are available for PS prepared by all four mechanisms (see Initiators). 

As shown in the previous section the mechanical and thermal properties of polypropylene are dependent on the isotacticity, the molecular weight and on other structure features. The properties of five commercial materials (all made by the same manufacturer and subjected to the same test methods) which are of approximately the same isotactic content but which differ in molecular weight and in being either homopolymers or block copolymers are compared in Table 11.1. 

When polyols, di-isocyanates and glycols are reacted together as described in the previous section they do in fact tend to produce block copolymers as can be seen from the following reaction mechanism ... 

Brown [46] continued the contact mechanics work on elastomers and interfacial chains in his studies on the effect of interfacial chains on friction. In these studies. Brown used a crosslinked PDMS spherical cap in contact with a layer of PDMS-PS block copolymer. The thickness, and hence the area density, of the PDMS-PS layer was varied. The thickness was varied from 1.2 nm (X = 0.007 chains per nm-) to 9.2 nm (X = 0.055 chains per nm-). It was found that the PDMS layer thickness was less than about 2.4 nm, the frictional force between the PDMS network and the flat surface layer was high, and it was also higher than the frictional force between the PDMS network and bare PS. When the PDMS layer thicknesses was 5.6 nm and above, the frictional force decreased dramatically well below the friction between PDMS and PS. Based on these data Brown [46] concluded that ... 

Creton, C., Kramer, E.J., Hui, C.-Y. and Brown, H.R., Failure mechanisms of polymer interfaces reinforced with block copolymers. Macromolecules, 25, 3075-3088 (1992). Boucher et al., E., Effects of the formation of copolymer on the interfacial adhesion between semicrystalline polymers. Macromolecules, 29, 774-782 (1996). 

As with block copolymers, the important parameters are the surface density and length of the copolymer chains. Toughening of the interface may occurs as a result of pull-out or scission of the connector chains, or of fibril or craze formation in matrix. This last mechanism gives the highest fracture toughness, F, and tends to occur at high surface density of chains. 

New raw materials will be the key to unlocking the opportunities above and to creating the possibility for new sets of adhesive properties. On the horizon are new types of moisture curable systems and a variety of novel block copolymers. The future may find entirely new mechanisms or morphologies for strength development on cooling. 

In nonrigid ionomers, such as elastomers in which the Tg is situated below ambient temperature, even greater changes can be produced in tensile properties by increase of ion content. As one example, it has been found that in K-salts of a block copolymer, based on butyl acrylate and sulfonated polystyrene, both the tensile strength and the toughness show a dramatic increase as the ion content is raised to about 6 mol% [10]. Also, in Zn-salts of a butyl acrylate/acrylic acid polymer, the tensile strength as a function of the acrylic acid content was observed to rise from a low value of about 3 MPa for the acid copolymer to a maximum value of about 15 MPa for the ionomer having acrylic acid content of 5 wt% [II]. Other examples of the influence of ion content on mechanical properties of ionomers are cited in a recent review article [7],... 

The polymers initiated by BP amines were found to contain about one amino end group per molecular chain. It is reasonable to consider that the combination of BP and such polymers will initiate further polymerization of vinyl monomers. We investigated the photopolymerization of MMA with BP-PMMA bearing an anilino end group as the initiation system and found an increase of the molecular weight from GPC and viscometrical measurement [91]. This system can also initiate the photopolymerization of AN to form a block copolymer, which was characterized by GPC, elemental analysis, and IR spectra. The mechanism proposed is as follows ... 

Frounchi and Burford [37] studied the effect of styrene block copolymer as a compatibilizer in isotactic PP-ABS blends. It was found hat in PP-rich blends a marginal improvement in mechanical properties was obtained. However, in acrylo nitrile butadiene styrene (ABS) rich blends no improvement was obtained. The effects of four different block copolymers, SBS, SIS,... 

Table 11 Effect of Different Block Copolymers on the Mechanical Properties of ABS-Rich Blends...

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. 

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