Styrenes butyl lithium

The styrene-diene triblocks, the main subject of this section, are made by sequential anionic polymerisation (see Chapter 2). In a typical system cc-butyl-lithium is used to initiate styrene polymerisation in a solvent such as cyclohexane. This is a specific reaction of the type... 

Initiating polymerisation of styrene with sec-butyl-lithium. 

When the styrene has been consumed, to give living polymers of narrow molecular mass distribution, more styrene and more catalyst is added. The styrene adds to the existing chains and also forms new polymer molecules initiated by the additional sec-butyl-lithium. 

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 ... 

There are some indications that the situation described above has been realized, at least partially, in the system styrene-methyl methacrylate polymerized by metallic lithium.29 29b It is known51 that in a 50-50 mixture of styrene and methyl methacrylate radical polymerization yields a product of approximately the same composition as the feed. On the other hand, a product containing only a few per cent of styrene is formed in a polymerization proceeding by an anionic mechanism. Since the polymer obtained in the 50-50 mixture of styrene and methyl methacrylate polymerized with metallic lithium had apparently an intermediate composition, it has been suggested that this is a block polymer obtained in a reaction discussed above. Further evidence favoring this mechanism is provided by the fact that under identical conditions only pure poly-methyl methacrylate is formed if the polymerization is initiated by butyl lithium and not by lithium dispersion. This proves that incorporation of styrene is due to a different initiation and not propagation. 

The Laboratory prepn for amorph styrene involves thermal conditions or the use of butyl-lithium at 50°. Crystalline polystyrene can be... 

The initiation of polymerization of styrene and isoprene in benzene by t-butyl lithium reveals some complexities129) (e.g. zero order kinetics in monomer) not observed in the reaction proceeding in cyclohexane. Further studies of that system are needed. 

The observation of Tsuji et al. 148) concerned with copolymerization of 1- or 2-phenyl butadiene with styrene or butadiene illustrates again the importance of the distinction between the classic, direct monomer addition to the carbanion, and the addition involving coordination with Li4. The living polymer of 1- or 2-phenyl butadiene initiated by sec-butyl lithium forms a block polymer on subsequent addition of styrene or butadiene provided that the reaction proceeds in toluene. However, these block polymers are not formed when the reaction takes place in THF. The relatively unreactive anions derived from phenyl butadienes do not add styrene or butadiene, while the addition eventually takes place in hydrocarbons on coordination of the monomers with Li4. The addition through the coordination route is more facile than the classic one. 

The kinetic model describes the carbanion polymerization of styrene in a hydrocarbon solvent using n-butyl lithium as the initiator. The mechanism is characterized by four steps ... 

Polystyrene was prepared by the anionic polymerisation of styrene in toluene plus THF mixtures (4 1 volume ratio) using n-butyl lithium as initiator. After removing a sample for analysis at this stage, the remainder of the living polystyrene was reacted with a five molar excess of trichloromethylsilane for 15 min and then excess methanol introduced. The methoxy-terminated polystyrene was freeze-dried from dioxan. The method described here essentially follows the route proposed by Laible and Hamann (6). 

The synthetic importance of non-nucleophilic strong bases such as lithium diisopro-pylamide (LDA) is well known but its synthesis involves the use of a transient butyl lithium species. In order to shorten the preparation and make it economically valuable for larger scale experiments an alternate method of synthesis has been developed which also involves a reaction cascade (Scheme 3.14) [92]. The direct reaction of lithium with diisopropylamine does not occur, even with sonication. An electron transfer agent is necessary, and one of the best in this case is isoprene. Styrene is used in the commercial preparation of LDA, but it is inconvenient in that it is transformed to ethylbenzene which is not easily removed. It can also lead to undesired reactions in the presence of some substrates. The advantages of isoprene are essentially that it is a lighter compound (R.M.M. = 68 instead of 104 for styrene) and it is transformed to the less reactive 2-methylbutene, an easily eliminated volatile compound. In the absence of ultrasound, attempts to use this electron carrier proved to be unsatisfactory. In this preparation lithium containing 2 % sodium is necessary, as pure lithium reacts much more slowly. 

Difunctional initiators such as sodium naphthalene are useful for producing ABA, BABAB, CAB AC, and other symmetric block copolymers more efficiently by using fewer cycles of monomer additions. Difunctional initiators can also be prepared by reacting a diene such as /n-diisoprope ny I benzene or l,3-bis(l-phenylethenyl)benzene with 2 equiv of butyl-lithium. Monomer B is polymerized by a difunctional initiator followed by monomer A. A polymerizes at both ends of the B block to form an ABA triblock. BABAB or CABAC block copolymers are syntehsized by the addition of monomer B or C to the ABA living polymer. The use of a difunctional initiator is the only way to synthesize a MMA-styrene-MMA triblock polymer since MMA carbanion does not initiate styrene polymerization (except by using a coupling reaction—Sec. 5-4c). 

Monomer reactivity ratios and copolymer compositions in many anionic copolymerizations are altered by changes in the solvent or counterion. Table 6-12 shows data for styrene-isoprene copolymerization at 25°C by n-butyl lithium [Kelley and Tobolsky, 1959]. As in the case of cationic copolymerization, the effects of solvent and counterion cannot be considered independently of each other. For the tightly bound lithium counterion, there are large effects due to the solvent. In poor solvents the copolymer is rich in the less reactive (based on relative rates of homopolymerization) isoprene because isoprene is preferentially complexed by lithium ion. (The complexing of 1,3-dienes with lithium ion is discussed further in Sec. 8-6b). In good solvents preferential solvation by monomer is much less important and the inherent greater reactivity of styrene exerts itself. The quantitative effect of solvent on copolymer composition is less for the more loosely bound sodium counterion. 

Well developed is the anionic polymerization for the preparation of olefin/di-olefin - block copolymers using the techniques of living polymerization (see Sect. 3.2.1.2). One route makes use of the different reactivities of the two monomers in anionic polymerization with butyllithium as initiator. Thus, when butyl-lithium is added to a mixture of butadiene and styrene, the butadiene is first polymerized almost completely. After its consumption stryrene adds on to the living chain ends, which can be recognized by a color change from almost colorless to yellow to brown (depending on the initiator concentration). Thus, after the styrene has been used up and the chains are finally terminated, one obtains a two-block copolymer of butadiene and styrene ... 

Preparation of the Living" Polystyrene. 18 g of the living polymer was prepared by standard anionic polymerization using n-butyl lithium. The reaction was carried out by the dropwise addition of 20 ml of styrene to 5 ml of the initiator solution in 150 ml of neat THF at -78°C. The styrene drip was adjusted to take approximately 30 min for completion and then the reaction was allowed to stir for two hours before the grafting reaction with mesylated lignin was carried out. The number average molecular weight of the polystyrene, as determined by HPSEC, was 9500 with polydispersity of 1.2. 

This has been studied much less frequently and appears to be a rather more complex reaction. The first results obtained, for the butyl-lithium, styrene reaction in benzene have already been described. In a similar way the addition of butyllithium to 1,1-diphenylethylene shows identical kinetic behaviour in benzene (26). Even the proton extraction reaction with fluorene shows the typical one-sixth order in butyllithium (27). It appears therefore that in benzene solution at least, lithium alkyls react via a small equilibrium concentration of unassociated alkyl. This will of course not be true for reactions with polar molecules for reasons which will be apparent later. No definite information can be obtained on the dissociation process. It is possible that the hexamer dissociates completely on removal of one molecule or that a whole series of penta-mers, tetramers etc. exist in equilibrium. As long as equilibrium is maintained, the hexamer is the major species present and only monomeric butyllithium is reactive, the reaction order will be one-sixth. A plausible... 

Welch, F. J. Effect of Lewis acids and bases on the rate of butyl lithium initiated polymerization of styrene. Read in St. Francisco ACS Meeting. 

Polymeric supports can also be used with advantage to form monofunctional moieties from difunctional (Hies. Leznoff has used this principal in the synthesis of sex attractants on polymer supports (67). Starting from a sheap symmetrical diol he blocked one hydroxyl group by the polymer. Functionalization of cross-linked polymers is mostly performed by chloromethylation (65). A very promising method to introduce functional groups into crosslinked styrene-divinylbenzene copolymers is the direct lithiation with butyllithium in presence of N,N,N, N -tetramethyl-ethylenediamine (TMEDA) (69, 70). Metalation of linear polystyrene with butyl-lithium/TMEDA showed no exchange of benzylic hydrogen and a ratio of attack at m/p-position of 2 1 (71). In the model reaction of cumene with amylsodium, a kinetic control of the reaction path is established. After 3h of treatment with amyl-sodiuni, cumene is metalated 42% in a-, 39% m-, and 19% p-position. After 20h the mixture equilibrates to affort 100% of the thermodynamically more stable a-prod-uct (72). 

Korotkov and Rakova (53) found that butadiene was more active in copolymerization with isoprene with lithium catalyst, although in homopolymerization isoprene is three times faster. Korotkov and Chesnokova (33) studied the copolymerization of butadiene and styrene with n-butyl lithium in benzene. Butadiene polymerized before much of the styrene was consumed. They claimed the formation of block polymers consisting initially of polybutadiene and the polystyrene chain attached. 

Kuntz (33) reported on the copolymerization of butadiene and styrene in n-heptane at 30° using n-butyl lithium. Although styrene homopolymerized six times faster than butadiene, the copolymerization rate was initially the same as that of butadiene homopolymerization and then increased markedly. It was found that about 80% of the styrene remained when 90% of the butadiene was consumed and that the increase in rate coincided with the almost complete consumption of butadiene. With added tetrahydrofuran, the rate of polymerization was faster and about 30% styrene was found in the initial copolymer. 

A diblock copolymer model material with blocks of methylmethacrylate (approximately 25%) and styrene was prepared since this system should be thermally stable. The diblock copolymer was prepared using a technique described by Rempp et al. (9,10) with slight modifications. The following amounts were used methylmethacrylate 50 g (0.5 mol), styrene 150 g (1.44 mol), solvent THF 1,000 mL, and n-butyl-lithium 2.5 10"3 mol (anionic catalyst). Reaction temperature, —55°C. 

The monomers were vacuum distilled three times and dried with CaH2. THF was refluxed over CuCl2 (5 hr), refluxed five times over CaH2 (8 hr), distilled, and finally refluxed over LiAlH4. All treatments were carried out under nitrogen. Before the monomers were added, a drop of styrene was added to the solvent which was titrated with n-butyl lithium until the weakly red, styrylic anion color was stable. 

Nucleophilic addition to styrene is possible only because the intermediate carbanion is stabilized by conjugation into the benzene ring. It needs a more reactive carbanion than the benzyl anion to initiate the polymerization, and an unstabilized nonconjugated organolithium compound like butyl lithium is the answer. 

Butadiene-Styrene Rubber occurs as a synthetic liquid latex or solid rubber produced by the emulsion polymerization of butadiene and styrene, using fatty acid soaps as emulsifiers, and a suitable catalyst, molecular weight regulator (if required), and shortstop. It also occurs as a solid rubber produced by the solution copolymerization of butadiene and styrene in a hexane solution, using butyl lithium as a catalyst. Solvents and volatiles are removed by processing with hot water or by drum drying. 

A reaction vessel was charged with 3.5 ml of styrene diluted with 14 ml of cyclohexane and then treated with 1.25 ml of IM s-butyl lithium and polymerized at 0°C for 2 hours. The polystyryl lithium block obtained had a polydispersity index of 1.1 and a Mn of 1700 daltons. 

The author [2] prepared poly(a-methylstyrene-b-styrene) copolymers using s-butyl lithium and triisobutylaluminum. 

A catalyst combination consisting of the barium salt of tri(ethyleneglycol)ethyl ether, Ba(0CH2CH20CH2CH20CH2CH3)2, with tri-n-octyl aluminum and n-butyl lithium has been used to prepare random poly(styrene-co-butadiene) containing a high butadiene transcontent. These polymers were designed to be co-cured with natural rubber and used as components in automotive tires. 

High trans content copolymers of styrene and butadiene were also obtained by Halasa [4] using the calcium salt of tetrahydrofurfuryl alcohol and n-butyl lithium. 

Dendrimeric rubbery copolymers having a molecular weight of roughly 250,000 daltons and containing siloxane linkages were prepared by the author [6] by copolymerizing 12% styrene and 88% butadiene in combination with of 2-butyl lithium, hexachlorodisiloxane, and A, A, A, A -tetramethyl-1,2-ethanediamine. 

Poly(butadiene-b-a-methylstyrene-b-styrene) was prepared by Tung [4] using sec-butyl-lithium and l,3-di(l-phenylethenyl)benzene. 

Poly(ot-methylstyrene-co-styrene) was previously prepared by Desbois [5] using s-butyl lithium and triisobutylalumimim. 

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