Block isoprene-styrene

G-5—G-9 Aromatic Modified Aliphatic Petroleum Resins. Compatibihty with base polymers is an essential aspect of hydrocarbon resins in whatever appHcation they are used. As an example, piperylene—2-methyl-2-butene based resins are substantially inadequate in enhancing the tack of 1,3-butadiene—styrene based random and block copolymers in pressure sensitive adhesive appHcations. The copolymerization of a-methylstyrene with piperylenes effectively enhances the tack properties of styrene—butadiene copolymers and styrene—isoprene copolymers in adhesive appHcations (40,41). Introduction of aromaticity into hydrocarbon resins serves to increase the solubiHty parameter of resins, resulting in improved compatibiHty with base polymers. However, the nature of the aromatic monomer also serves as a handle for molecular weight and softening point control. 

Styrene isoprene block copolymers Styrene butadiene block copolymers Styrene butadiene random copolymers Polyisobutylene Polysiloxanes... 

Block copolymer chemistry and architecture is well described in polymer textbooks and monographs [40]. The block copolymers of PSA interest consist of anionically polymerized styrene-isoprene or styrene-butadiene diblocks usually terminating with a second styrene block to form an SIS or SBS triblock, or terminating at a central nucleus to form a radial or star polymer (SI) . Representative structures are shown in Fig. 5. For most PSA formulations the softer SIS is preferred over SBS. In many respects, SIS may be treated as a thermoplastic, thermoprocessible natural rubber with a somewhat higher modulus due to filler effect of the polystyrene fraction. Two longer reviews [41,42] of styrenic block copolymer PSAs have been published. 

FIGURE 22.5 OTHdC study on the temperature range of the dissociation of the micelle of a styrene-isoprene two-block polymer in n-decane. Column 3.70 fim x 300 cm. (Reprinted with permission from Ref. 14. Copyright 1989 American Chemical Society.)... 

Experimentally, the stretching of block copolymer chains has been addressed in two ways by measuring L as a function of N, and by measuring the components of Rg of the block chains both parallel and perpendicular to the interface. The domain dimensions have been studied most extensively for styrene-isoprene and styrene-butadiene block copolymers X-ray and neutron scattering are the methods of choice. The predicted SSL scaling of L N2/3 has been reported for spheres, cylinders and lamellae [99,102-106], but not in all cases. For example, Bates et al. found N0 37 for styrene-butadiene spheres [100], and Hadziioannou and Skoulios observed N0 79 for styrene-isoprene lamellae [107], In the sphere case, kinetic limitations to equilibration were felt to be an important factor [100],... 

Sequential addition of a second monomer (e.g., styrene,p-terbutyl styrene, p-methyl styrene, indene, -chloro styrene, isoprene, and a-methyl styrene) to make glassy outer-block... 

Cakmak M. and Wang M.D., Structure development in the tubular blown film of PP/EPDM thermoplastic elastomer, Antec 89, 47th Annual Tech. Conference of SPE, New York, May 1, 1989, 1756. Hashimoto T., Todo A., Itoi H., and Kawai H. Domain boundary structure of styrene-isoprene block copolymer films cast from solution. 2. Quantitative estimation of the interfacial thickness of lamellar microphase systems. Macromolecules, 10, 377, 1977. 

Short fiber reinforcement of TPEs has recently opened up a new era in the field of polymer technology. Vajrasthira et al. [22] studied the fiber-matrix interactions in short aramid fiber-reinforced thermoplastic polyurethane (TPU) composites. Campbell and Goettler [23] reported the reinforcement of TPE matrix by Santoweb fibers, whereas Akhtar et al. [24] reported the reinforcement of a TPE matrix by short silk fiber. The reinforcement of thermoplastic co-polyester and TPU by short aramid fiber was reported by Watson and Prances [25]. Roy and coworkers [26-28] studied the rheological, hysteresis, mechanical, and dynamic mechanical behavior of short carbon fiber-filled styrene-isoprene-styrene (SIS) block copolymers and TPEs derived from NR and high-density polyethylene (HOPE) blends. 

Sequential addition of different monomer charges to a living anionic polymerization system is useful for producing well-defined block copolymers. Thermoplastic elastomers of the triblock type are the most important commercial application. For example, a styrene-isoprene-styrene triblock copolymer is synthesized by the sequence... 

Abbreviation for styrene-isoprene-styrene block copolymer, a thermoplastic elastomer. 

Styrenic SBS/SIS (styrene-isoprene-styrene block copolymers) CariflexTR, Kraton... 

Now again, a state of inhomogeneity in polymers, so especially interesting in films and interfaces, occur when discontinuities are built into the main valence chains and networks. Block polymers are the classic embodiments of this. Many periodic distances separating domains in such alternating or rhymthic copolymers have been reported. These indicate existence of phases in laminar domains and, in other cases, of spherical domains.(51) Cases are shown experimentally for styrene/isoprene copolymers and also for styrene/butadiene.(52,53,54)... 

Fig. 49. Zimm plot for a styrene/isoprene block copolymer in methyl isobutyl ketone153)...

Several studies have been published which utilize size exclusion chromatography (SEC) for characterization of the molecular weight distribution of multi-arm structures of polystyrene, polyisoprene, and block copolymers of styrene/ butadiene and styrene/isoprene (1, 2, 8, 17, 25-26). An... 

Kraton 1107 brand elastomer was from Shell Chemical Co., and it is synthesized by coupling the isoprenyl anion ends of a styrene/isoprene (SI) block copolymer to give styrene/isoprene/styrene (SI IS). Proton NMR analysis indicated 84% (wt.) isoprene and 16% (wt.) styrene. 

The effect of blending LDPE with EVA or a styrene-isoprene block copolymer was investigated (178). The properties (thermal expansion coefficient. Young s modulus, thermal conductivity) of the foamed blends usually lie between the limits of the foamed constituents, although the relationship between property and blend content is not always linear. The reasons must he in the microstructure most polymer pairs are immiscible, but some such as PS/polyphenylene oxide (PPO) are miscible. Eor the immiscible blends, the majority phase tends to be continuous, but the form of the minor phase can vary. Blends of EVA and metallocene catalysed ethylene-octene copolymer have different morphologies depending on the EVA content (5). With 25% EVA, the EVA phase appears as fine spherical inclusions in the LDPE matrix. The results of these experiments on polymer films will apply to foams made from the same polymers. 

Statistical, gradient, and block copolymers as well as other polymer architectures (graft, star, comb, hyperbranched) can be synthesized by NMP following the approaches described for ATRP (Secs. 3-15b-4, 3-15b-5) [Hawker et al., 2001]. Block copolymers can be synthesized via NMP using the one-pot sequential or isolated macromonomer methods. The order of addition of monomer is often important, such as styrene first for styrene-isoprene, acrylate first for acrylate-styrene and acrylate-isoprene [Benoit et al., 2000a,b Tang et al., 2003]. Different methods are available to produce block copolymers in which the two blocks are formed by different polymerization mechanisms ... 

Block copolymers of isobuylene with styrene, isoprene, and vinyl ethers have been synthesized, often requiring an appropriate adjustment of reaction conditions for the second stage, as described above for styrene-MVE. Another approach is the use of a telechelic polymer (containing the first block) as the initiator for polymerization of the second monomer (Sec. 5-4b). 

A second route is termed sequential anionic polymerization. More recently, also controlled radical techniques can be applied successfully for the sequential preparation of block copolymers but still with a less narrow molar mass distribution of the segments and the final product. In both cases, one starts with the polymerization of monomer A. After it is finished, monomer B is added and after this monomer is polymerized completely again monomer A is fed into the reaction mixture. This procedure is applied for the production of styrene/buta-diene/styrene and styrene/isoprene/styrene triblock copolymers on industrial scale. It can also be used for the preparation of multiblock copolymers. 

Chlorosulfonated styrene resins and carboxyaminoacid polymers were also found to possess thromboresistant properties by Josefonwicz and coworkers [483]. Studies included investigation of the effect of spacer length between amine and carboxylic groups as well as modification of styrene/isoprene/styrene blocks with chlorosulfonyl isocyanate giving sulfamate and carboxylic functionality [484],... 

The most obvious reaction is simply to add more styrene and convert the isoprene anion to a styryl anion and grow it to a desired size and form the styrene-isoprene-styrene triblock of which we are more familiar in all the theoretical work that has been reported (ji, 7). The last example employs a bifunctional monomer, divinylbenzene, to form miniblocks of divinylbenzene as it reacts with a number of diblocks into what is called a star-block configuration (8). The active anionic sites are now on the divinylbenzene. These materials are then terminated by protonating agents to obtain the final product. The number of arms or diblocks that united into a starblock of this type is controlled by the relative amounts of the diblock to the divinylbenzene. 

Figure 7. Physical properties of styrene-isoprene block polymers.

Almost all isoprene produced is used in the preparation of polymers and copolymers. cis-Polyisoprene, primarily for vehicle tyres, is the largest application, with styrene-isoprene-styrene (SIS) block polymers being a rapidly growing secondary application. Butyl rubber is a significant third application. World demand for isoprene for monomer use in 1992 was (thousand tonnes) polyisoprene, 827 SIS, 95 butyl rubber, 25 and other uses, 10 (Weitz Loser, 1989 Lybarger, 1995). 

The adhesive tie layer can be made up from 82% ethylene-based octene plastomer, 15% styrene modified terpene resin and 3% of a styrene/isoprene/styrene styrenic block copolymer. 

The most important hydrocarbon copolymers are styrene-butadiene rubbers (SBR) produced by free-radical emulsion or anionic polymerization. Anionic polymerization allows the manufacture of styrene-butadiene and styrene-isoprene three-block copolymers. 

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