Polydiene triblock copolymers blocks

The use of lightly crosslinked polymers did result in hydrophilic surfaces (contact angle 50°, c-PI, 0.2 M PhTD). However, the surfaces displayed severe cracking after 5 days. Although qualitatively they appeared to remain hydrophilic, reliable contact angle measurements on these surfaces were impossible. Also, the use of a styrene-butadiene-styrene triblock copolymer thermoplastic elastomer did not show improved permanence of the hydrophilicity over other polydienes treated with PhTD. The block copolymer film was cast from toluene, and transmission electron microscopy showed that the continuous phase was the polybutadiene portion of the copolymer. Both polystyrene and polybutadiene domains are present at the surface. This would probably limit the maximum hydrophilicity obtainable since the RTD reagents are not expected to modify the polystyrene domains. 

Elastomeric Polydiene ABA Triblock Copolymers with Crystalline End Blocks... 

ABA triblock copolymers of the styrene-diene type are well known, and owe their unique properties to their heterophase morphology. This arises from the incompatibility between the polystyrene A blocks and the polydiene B blocks, leading to the formation of a dispersion of very small polystyrene domains within the polydiene matrix. This type of elastic network, held together by the polystyrene "junctions", results in thermoplastic elastomer properties. 

One of the most important discoveries relating to synthesis and physical behavior was made by Dr. Milkovich while at the Shell Development Co. He and his colleagues showed that triblock copolymers containing polystyrene-polydiene-polystyrene blocks in appropriate sizes could behave as a physically cross-linked but linear thermoplastic elastomer. Thus Dr. Milkovich was involved with two very crucial discoveries in this field. Interestingly, he received his M. S. degree at Syracuse with Professor Szwarc and his Ph.D. at Akron with Professor Morton. I was pleased that Dr. Milkovich accepted my invitation to be a plenary speaker at the symposium, along with Professors Szwarc and Morton. 

Block Copolymer Synthesis by Three-Step Sequential Monomer Addition The preparation of block copolymers by sequential addition of monomers using living anionic polymerization and a monofunctional initiator is the most direct method for preparing well-defined block copolymers. Detailed laboratory procedures for anionic synthesis of block copolymers are available [37, 230], Several important aspects of these syntheses can be illustrated by considering the preparation of an important class of block copolymers (Scheme 7.22), the polystyrene-fe-polydiene-( -polystyrene triblock copolymers. 

A typical triblock copolymer may consist of about 150 styrene units at each end of the macromolecule, and some 1000butadiene units in the center. The special physical properties of these block copolymers are due to inherent incompatibility of polystyrene with polybutadiene or polyiso-prene blocks. Within the bulk material there are separations and aggregations of the domains. The polystyrene domains are dispersed in continuous matrixes of the polydienes that are the major components. At ambient temperature, below the Tg of the polystyrene, these domains are rigid and immobilize the ends of the polydiene segments. In effect, they serve both as filler particles or as crosslinks. Above Tg of polystyrene, however, the domains are easily disrupted and the material can be processed as a thermoplastic polymer. The separation into domains is illustrated in Fig. 5.4. 

During the mid-1960 s our attention was drawn to the remarkable properties of the ABA. type of "triblock" copolymers, where the A block is polystyrene and the B block is a poly diene (butadiene or isoprene). These yield products of the "thermoplastic elaatomer" type, since the glassy polystyrene end blocks aggregate into regular and well-formed domains which act as thermoplastic net work junctions for the elastic polydiene chains. 

Such triblock copolymers can be derived by anionic polymerization using dilithium initiators. For the central polydiene block to exhibit a high content in l,4-c units, it is essential that the polymerization be carried out in hydrocarbon solvents (apolar medium) and in absence of any polar additive. Such dilithium initiators are generated from the reaction of butyllithium with an adequate precursor as shown below ... 

In addition to the triblock thermoplastic elastomers, other useful copolymers of styrene with a diene are produced commerically by living anionic polymerization. These include di-and multiblock copolymers, random copolymers, and tapered block copolymers. A tapered (gradient) copolymer has a variation in composition along the polymer chain. For example, S-S/D-D is a tapered block polymer that tapers from a polystyrene block to a styrene-diene random copolymer to polydiene block. (Tapered polymers need not have pure blocks at their ends. One can have a continuously tapered composition from styrene to diene by... 

The ABA triblocks which have been most exploited commercially are of the styrene-diene-styrene type, prepared by sequential polymerization initiated by alkyllithium compounds as shown in Eqs. (99-101) [263, 286]. The behavior of these block copolymers illustrates the special characteristics of block (and graft) copolymers, which are based on the general incompatibility of the different blocks [287]. Thus for a typical thermoplastic elastomer (263), the polystyrene end blocks (-15,000-20,000 MW) aggregate into a separate phase, which forms a microdispersion within the matrix composed of the polydiene chains (50,000-70,000 MW) [288-290]. A schematic representation of this morphology is shown in Fig. 3. This phase separation, which occurs in the melt (or swollen) state, results, at ambient temperatures, in a network of... 

In this paper we describe the preparation and the properties of the title triblock with a low vinyl-1,2 (or 3,4 in the case of polyisoprene) polydiene center block. Two different solvent systems were used as the media of polymerization. In the first system, the polydiene center block was prepared in cyclohexane. Alpha-methylstyrene (AMS) and a polar solvent tetrahydrofuran (THF) were then added. This was followed by a slow and continuous styrene addition to complete the end block preparation. In the second system, AMS itself was used as the solvent with no other solvent added. The second solvent system enabled us to use several different polymerization schemes. The center block could be prepared first to form a tapered or untapered triblock. The end block copolymer also could be prepared first and then the diblock and then coupled to form a tri- or a radial block polymer. Instead of coupling, more styrene could be added to complete the triblock. All these different routes of preparation were used in this work. 

In addition to the relative ratio of the monomers, the arrangement of the units in the chain is important. This arrangement is referred to as the copolymer sequence distribution. In the previous discussion, the assumption was made that the comonomer units were well mixed in the polymer chain. If this is not the case, parts of the chain can reflect properties of the corresponding homopolymer. It is thus possible to produce polymers that have significantly different properties in different parts of the polymer chain. A most dramatic example of this can be found in styrene-butadiene-styrene or styrene-isoprene-styrene thermoplastic elastomers. These triblock polymers behave as cured elastomers at room temperature. The polystyrene blocks have sufficiently different solubility from the polydiene portions that they phase-separate... 

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