Anionic polymerization styrene block copolymers

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. 

Of the amorphous block copolymers, styrenic block copolymers are the vast majority. These are synthesized anionically in solution, with butyl lithium commonly employed as the initiator [4]. There are three processes for this polymerization ... 

Though living anionic polymerization is the most widely used technique for synthesizing many commercially available TPEs based on styrenic block copolymers, living carbocationic polymerization has also been developed in recent years for such purposes [10,11], Polyisobutylene (PlB)-based TPEs, one of the most recently developed classes, are synthesized by living carbocationic polymerization with sequential monomer addition and consists of two basic steps [10] as follows ... 

Anionic polymerization is widely used to prepare polymers with narrow molecular weight distribution. Addition of styrene to the living poly(l,l-dialkylsilabutane)s provided a poly(l,l-dialkylsilyl-/ -styrene) block copolymer (Scheme 11) in 99% yield with MJMn = 1.19 C1997PSA3207, 1995MM7029>. 

Table I shows the Tg values obtained in this work on standard polystyrene samples in most cases, the values obtained from DTA data are slightly higher than those obtained by DSC. Since these data were to be used for detailed comparisons with data obtained by others as well as by ourselves on styrene block copolymers, we first compared our data on anionically polymerized standard polystyrenes with those obtained on other anionically polymerized polystyrenes by other workers also using DTA and DSC techniques. This comparison is shown graphically in Figure 1. In Figure 1, the solid curve is drawn through a combination of our data with that obtained by Wall et al. (25) using a Dupont 900...

The synthesis of styrenic block copolymers (SBCs) has been discussed in a number of books and review articles concerning block copolymers [1] and anionic polymerization [2]. A comprehensive review of the field is beyond the scope of this chapter, the objective of which is to provide an overview of the technology, with particular emphasis on processes currently used for commercial production. 

Since shortly after its discovery by Szwarc et al. [5] in the mid-1950s, living anionic polymerization has been recognized as an ideal route to styrenic block copolymers [6]. To date, living anionic polymerization remains the only commercially important technology for SBC synthesis. The anionic polymerization of styrene and common dienes such as butadiene and isoprene satisfies the criteria outlined above, particularly when carried out in a hydrocarbon solvent and initiated by an appropriate lithium alkyl. 

Monofunctional Initiators. AB, ABA, and multiblock copolymers can be synthesized by initiation of one monomer with a monofunctional initiator like n-butyl lithium. When the first monomer has been reacted, a second monomer can be added and polymerized. This monomer addition sequence can be reversed and repealed if the anion of each monomer sequence can initiate polymerization of the other monomer. The length of each block is determined by the amount of the corresponding monomer which was provided. Styrene-isoprene-styrene block copolymers can be made by this method by polymerizing in benzene solution and adding the styrene first. Addition of a small amount of ether accelerates the slow attack of dienyl lithium on styrene. 

The mapping shown in Fig. 1 includes references to SBR and styrene block copolymers in the PB search. Removing these citations from the database reduced the number to 4297, which can be seen mapped in Fig. 3. the area of high activity is centered on hydroxy terminated PB (HTPB). Low-Mn HTPB can be prepared by a variety of polymerization processes such as radical, anionic, or even using acyclic diene metathesis (ADMET).f The HTPB has a variety of uses as a propellant. " Other uses include reaction with epoxy resins, nylon, urethane, or even in the formulation of adhesives.t" The use of HTPB as an oxygen scavenger in polyamide, polyvinyl alcohol, and multilayer... 

Anionic polymerization is used to produce the styrenic block copolymers and produces a polymer with an extremely narrow block and overall molecular weight distributions. The narrow molecular weight distributions are extremely useful in fundamental studies of polymers, and have led to a great deal of study of anionic polymerization, much more than justified by its commercial importance. In fact, the styrenic-block copolymers are the only polymers produced in large quantities via anionic polymerization. The extremely narrow polydispersity is evident in the following expression for the polydispersity index ... 

Along these lines of thinking block copolymers of styrene and 6-[4-(4-methoxyphenyl)phenoxy]hexylmethacrylate (MPPHM) were synthesized by anionic polymerization. Styrene was polymerized first in benzene using 5-BuLi as the initiator. After completion of polymerization the living PSIi chains were end-capped with diphenylethylene and the solvent was changed to THE Anhydrous liCl was introduced to the reactor, and the temperature was lowered to - 40 °C. At that temperature a solution of purified MPPHM in THE was introduced slowly. After complete reaction of the liquid crystalline monomer, polymerization was terminated with methanol . The procedure is outlined schematically in Scheme 9. 

Styrenic block copolymers are made by anionic living polymerization using sec-butyl lithium as a preferred initiator in non polar solvents such as cyclohexane or toluene.In the normal sequential polymerization, the initiator reacts with a molecule of styrene to form a polystyryol lithium species which then propagates with transfer of the initiator anion to the active chain end. 

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). 

Anionic polymerization, if carried out properly, can be truly a living polymerization (160). Addition of a second monomer to polystyryl anion results in the formation of a block polymer with no detectable free PS. This technique is of considerable importance in the commercial preparation of styrene—butadiene block copolymers, which are used either alone or blended with PS as thermoplastics. 

Commercially, anionic polymerization is limited to three monomers styrene, butadiene, and isoprene [78-79-5], therefore only two useful A—B—A block copolymers, S—B—S and S—I—S, can be produced direcdy. In both cases, the elastomer segments contain double bonds which are reactive and limit the stabhity of the product. To improve stabhity, the polybutadiene mid-segment can be polymerized as a random mixture of two stmctural forms, the 1,4 and 1,2 isomers, by addition of an inert polar material to the polymerization solvent ethers and amines have been suggested for this purpose (46). Upon hydrogenation, these isomers give a copolymer of ethylene and butylene. 

The earliest SIS block copolymers used in PSAs were nominally 15 wt% styrene, with an overall molecular weight on the order of 200,000 Da. The preparation by living anionic polymerization starts with the formation of polystyryl lithium, followed by isoprene addition to form the diblock anion, which is then coupled with a difunctional agent, such as 1,2-dibromoethane to form the triblock (Fig. 5a, path i). Some diblock material is inherently present in the final polymer due to inefficient coupling. The diblock is compatible with the triblock and acts... 

As previously described, all microspheres discussed in this chapter were synthesized from AB type diblock copolymers. Precursor block copolymers, poly(styrene-b-4-vinyl pyridine) (P[S-b-4VP]) diblock copolymers, were synthesized using the additional anionic polymerization technique [13]. The basic properties of the block copolymers were determined elsewhere [24,25] and are listed... 

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. 

Currently, more SBR is produced by copolymerizing the two monomers with anionic or coordination catalysts. The formed copolymer has better mechanical properties and a narrower molecular weight distribution. A random copolymer with ordered sequence can also be made in solution using butyllithium, provided that the two monomers are charged slowly. Block copolymers of butadiene and styrene may be produced in solution using coordination or anionic catalysts. Butadiene polymerizes first until it is consumed, then styrene starts to polymerize. SBR produced by coordinaton catalysts has better tensile strength than that produced by free radical initiators. 

Anionic polymerization of lactams was shown to proceed according to what is called the activated monomer mechanism. With bischloroformates of hydroxy-terminated poly(tetramethyleneglycol) and poly(styrene glycol) as precursors for a polymeric initiator containing N-acyl lactam ends, block copolymers with n-pyrrol-idone and e-caprolactam were obtained by bulk polymerizations in vacuum at 30 and 80 °C, respectively361. ... 

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