Block copolymer content

Blends with styrenic block copolymers improve the flexibiUty of bitumens and asphalts. The block copolymer content of these blends is usually less than 20% even as Httie as 3% can make significant differences to the properties of asphalt (qv). The block copolymers make the products more flexible, especially at low temperatures, and increase their softening point. They generally decrease the penetration and reduce the tendency to flow at high service temperatures and they also increase the stiffness, tensile strength, ductility, and elastic recovery of the final products. Melt viscosities at processing temperatures remain relatively low so the materials are still easy to apply. As the polymer concentration is increased to about 5%, an interconnected polymer network is formed. At this point the nature of the mixture changes from an asphalt modified by a polymer to a polymer extended with an asphalt. 

PAr/ PVDF PAr-b- PMMA PVDF/PMMA is a miscible blend. Addition of PAr to the PAr/PVDF/PAr-b-PMMA resulted in reduction of PVDF T and an increase of PAr T. These effects were m g enhanced by addition of PAr-b-PMMA. Finer dispersion was obtained for higher block copolymer content. Contact angle measurements, showed that was greatly influenced by the presence of block copolymer. Ahn et al., 1994... 

Fig. 7 Measurements of the relative intensity of third and fifth harmonic for a PDMS/PIB blend with 0.7 block-copolymer content at ft>/2w=0.1Hz. Lines are fits to equation 4/1 = a YQ -I- "GoPo w n = 3and 5...

Table 1 a Results of a droplet size determination for the PDMS/PIB system /t43, , using LAOS measurements and the relation according to Eq. 13 compared to radii from a microscopic analysis / 43,M- In the first series of blends, PDMS/PIB was prepared using manual mixing with a spatula, PDMS/PIB-100 and PDMS/PIB-300 rpm with an electrical stirrer at the designated rotation speed. In the second series the blends differed in their block-copolymer content, as stated in wt% of block-copolymer in the PDMS phase, b Estimation of the interfacial tension F using Eq. 13 based on additional information about the radius from microscopic droplet size determination... 

Figure 10.21 SEM micrographs of fracture surfaces of PET/PP blends compatibilized with SEES, SEP and SEPSEP block copolymers, (a) PET/PP (75/25), (b) PET/PP/SEBS (75/25/10), (c) PET/PP/SEPSEP (75/25/10), (d) PP/SEBS (75/25) (bar length 10 pm).The block copolymer content is expressed in part per hundred (phr). Reprinted from Pracella et al. [93], Copyright 2005, with permission from John Wiley Sons, Inc.

Gaines [13] has reported on dimethylsiloxane-containing block copolymers. Interestingly, if the organic block would not in itself spread, the area of the block polymer was simply proportional to the siloxane content, indicating that the organic blocks did not occupy any surface area. If the organic block was separately spreadable, then it contributed, but nonadditively, to the surface area of the block copolymer. 

It has been reported that block copolymers with appropriately chosen partners and mixing ratios yield materials suitable for use in substrate disks for optical data storage. An example is polyarjiate—polystyrene block copolymer with a PS content between 40 and 60% (225). 

Proportion of Hard Segments. As expected, the modulus of styrenic block copolymers increases with the proportion of the hard polystyrene segments. The tensile behavior of otherwise similar block copolymers with a wide range of polystyrene contents shows a family of stress—strain curves (4,7,8). As the styrene content is increased, the products change from very weak, soft, mbbedike materials to strong elastomers, then to leathery materials, and finally to hard glassy thermoplastics. The latter have been commercialized as clear, high impact polystyrenes under the trade name K-Resin (39) (Phillips Petroleum Co.). Other types of thermoplastic elastomers show similar behavior that is, as the ratio of the hard to soft phase is increased, the product in turn becomes harder. 

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. 

More recently Fina Chemicals have introduced linear SBS materials (Finaclear) in which the butadiene is present both in block form and in a mixed butadiene-styrene block. Thus comparing typical materials with a total styrene content of about 75% by weight, the amount of rubbery segment in the total molecule is somewhat higher. As a result it is claimed that when blended with polystyrene the linear block copolymers give polymers with a higher impact strength but without loss of clarity. 

SBS and SIS can be subsequently hydrogenated to form SEBS and SEPS, respectively. SEBS is obtained from SBS with a higher vinyl content (typically around 30%) in order to avoid crystallization of the mid-block. The properties of all four of these common styrenic block copolymers are displayed in Table 2. 

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 poly(styrene-b-isoprene) (P(S-b-IP)) and poly(-styrene-b-2-vinyl pyridine) (P(S-b-2VP)) block copolymers with narrow molecular weight distributions for blending with the microspheres were also synthesized using the additional anionic polymerization technique. The number-average molecular weights (Mns) and PS contents are also shown in Table 1. 

It is important to recognize that the following analytical methods essentially determine EO-PO ratio ( H NMR, IR, cleavage methods) or even simply alkylene oxide content (compleximetric methods) of the analyte, and as such are not specific quantitative or qualitative methods for poloxamers, since EO-PO copolymers of a different structure (for instance, random copolymers, or PO-EO-PO block copolymers) may respond to the methods in a way indistinguishable from poloxamers. The principal technique that permits definitive identification of a sample as a poloxamer is C NMR, which allows structural details, such as the distribution of EO and PO units along the polymer chain, to be elucidated [10]. 

The presence of flexible PEO and PPO blocks increases the viscosities of block copolymer solutions, this tendency is manifesting itself the stronger the greater is the PEO and PPO content in block copolymers. 

Sutoh and Noda154 succeeded in proving, by synthesizing block copolymers of the structure (Gly-Pro-Pro)n(Gly-Ala-Pro)m-(Gly-Pro-Pro)n, that with increasing imino add content, AS° changes to higher positive values. They do, however, not relate this to lower entropy losses of conformation but to hydrophobic interactions of the proline residues in the helical state. 

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