Styrenic block copolymer properties

Styrenic block copolymers (SBCs) are also widely used in HMA and PSA appHcations. Most hot melt appHed pressure sensitive adhesives are based on triblock copolymers consisting of SIS or SBS combinations (S = styrene, I = isoprene B = butadiene). Pressure sensitive adhesives typically employ low styrene, high molecular weight SIS polymers while hot melt adhesives usually use higher styrene, lower molecular weight SBCs. Resins compatible with the mid-block of an SBC improves tack properties those compatible with the end blocks control melt viscosity and temperature performance. 

Table 9. Properties of Compounded Styrenic Block Copolymers...

Adhesives, Coatings, and Sealants. Eor these appHcations, styrenic block copolymers must be compounded with resins and oils (Table 10) to obtain the desired properties (56—58). Materials compatible with the elastomer segments soften the final product and give tack, whereas materials compatible with the polystyrene segments impart hardness. The latter are usually styrenic resins with relatively high softening points. Materials with low softening points are to be avoided, as are aromatic oils, since they plasticize the polystyrene domains and reduce the upper service temperature of the final products. 

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. 

Where transparency is required, a range of polymers is available. Polystyrene is the least expensive but polymethylmethacrylate has an outstanding high light transmission combined with excellent weathering properties. Also to be considered are the polycarbonates, glass-clear polyamides, SAN, butadiene-styrene block copolymers, MBS polymers, plasticised PVC, ionomers and cellulose esters such as cellulose acetate. 

The properties of styrenic block copolymers are dependent on many factors besides the polymerization process. The styrene end block is typically atactic. Atactic polystyrene has a molecular weight between entanglements (Me) of about 18,000 g/mol. The typical end block molecular weight of styrenic block copolymers is less than Mg. Thus the softening point of these polymers is less than that of pure polystyrene. In fact many of the raw materials in hot melts are in the oligomeric region, where properties still depend on molecular weight (see Fig. 1). 

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. 

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,... 

Vinogradov G.V., Dreval V.E., Malkin A.Y., Yanovskii Yu G., Barancheeva V.V., Borisenkova E.K., Zabugina M.P., Plotnikova E.P., and Sabsai O.Y. Viscoelastic properties of butadiene-styrene block copolymers, Rheol. Acta, 17, 258, 1978. 

The mechanical properties at low strain rates, dynamic mechanical properties, creep-recovery behaviour, thermal expansion and thermal conductivity of foams manufactured from blends of LDPE with an EVA and with an isoprene-styrene block copolymer were studied as a function of the LDPE content in the blends. The experimental results demonstrated important aspects related to the modification of the foam properties by blending. 16 refs. 

In general, block copolymers are heterogeneous (multiphase) polymer systems, because the different blocks from which they are built are incompatible with each other, as for example, in diene/styrene-block copolymers. This incompatibility, however, does not lead to a complete phase separation because the polystyrene segments can aggregate with each other to form hard domains that hold the polydiene segments together. As a result, block copolymers often combine the properties of the relevant homopolymers. This holds in particular for block copolymers of two monomers A and B. 

R.F. Storey, B.J. Chisholm, and M.A. Masse, Morphology and physical properties of poly(styrene-b-isobutylene-b-styrene) block copolymers, Polymer, 37(14) 2925-2938, July 1996. 

Thermoplastic elastomers (TPE s) are characterized by the exceptional property that, without vulcanization, they behave as cross-linked rubbers. They are block-copolymers, in which blocks of the same nature assemble in hard domains, acting as cross-links between the rubbery parts of the chain. These hard domains lose their function when they reach their softening temperature, so that the material can then be processed as a thermoplast. One of the oldest member of the family of TPE s is SBS (styrene-butadiene-styrene block copolymer), but several other TPE s have been developed, i.a. on the basis of polyesters, polyurethanes and polyolefins. In their properties these polymers cover a broad range between conventional rubbers and soft thermoplastics. 

Sulfonation is very useful chemical modification of polymer, as it induces high polarity in the polymer changing its chemical as well as physical properties. Sulfonated polymers are also important precursors for ionomer formation [75]. There are reports of sulfonation of ethylene-propylene diene terpolymer (EPDM) [76, 77], polyarylene-ether-sulfone [78], polyaromatic ether ketone [79], polyether ether ketone (PEEK) [80], styrene-ethylene-butylene-styrene block copolymer, (SEBS) [81]. Poly [bis(3-methyl phenoxy) phosphozene] [82], Sulfonated polymers show a distinct peak at 1176 cm"1 due to stretching vibration of 0=S=0 in the -S03H group. Another peak appears at 881 cm 1 due to stretching vibration of S-OH bond. However, the position of different vibrational bands due to sulfonation depends on the nature of the cations as well as types of solvents [75, 76]. 

Djermouni, B., Ache, H.J. (1980) Effect of casting solvent on the properties of styrene-butadiene-styrene block copolymers studied by positron annihilation techniques . Macromolecules, 13,168. 

Styrenic block copolymers derive their useful properties from their ability to form distinct styrene (hard phase) and diene (rubber phase) domains, with well defined morphologies. To achieve this requires an unusual degree of control over the polymerization. The polymerization must yield discrete blocks of a uniform and controlled size, and the interface between the blocks must be sharp. This is best achieved by so-called living polymerization. For a polymerization to be classified as truly living, it is generally accepted that it must meet several criteria [3] ... 

Albert Einstein said that it is good to make things as simple as possible, but not simpler. Beneath each simple statement about the properties of styrene block copolymers lie volumes of books, thousands of patents and countless pages of paper and electronic files dedicated to describing and understanding these highly useful polymers, and their applications. The task becomes reducing all of this to simple ideas, simple pictures and simple words, but not simpler . 

One simple idea is that styrenic block copolymers are almost never used as a stand-alone 100% neat polymer for any application or use. We tend to think about polymers in terms of this plastic soda bottle is polyester, or this carpet fiber is polyamide, or this house siding is PVC, or this garbage bag film is polyethylene , fully understanding and meaning that virtually 100% of the named object is that polymer. Our brains usefully process the named polymer properties set (as neat polymer) into the desired and required property set for its application. Life is simple in the 100% world. It is intuitive, and what we seem to know makes sense, looking either way properties wise, to why this polymer is used for this application. 

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