Lithium polydienes

The aggregation of lithium polydienes is disrupted in ethereal solvents and their studies provide information about the conformation of the active centers. The stability of ethereal solutions of polydiene salts is greatly improved at low temperatures, especially in the presence of salts suppressing their dissociation 126). Under these conditions the cis-isomer is the most abundant in equilibrated THF solutions, although... 

An interesting approach to studies of the effects of coordination on the reactivity of lithium polydienes in hydrocarbon solvents was developed by Erussalimski and his colleagues 151 154 The polymerization of lithium polyisoprene in hexane is accelerated by the addition of TMEDA152), the rate levels off at a value of R = [TMEDA]/[li-thium polyisoprene] of 8, its final value giving the absolute rate constant of propagation of the polyisoprene coordinated with TMEDA, namely 0.17 M7l s at 20 °C. 

Finally it should be stressed that the complexation affects the microstructure of poly dienes. As was shown by Langer I56) small amounts of diamines added to hydrocarbon solutions of polymerizing lithium polydienes modify their structure from mainly 1,4 to a high percentage of vinyl unsaturation, e.g., for an equivalent amount of TMEDA at 0 °C 157) the fraction of the vinyl amounts to about 80%. Even more effective is 1,2-dipiperidinoethane, DIPIP. It produces close to 100% of vinyl units when added in equimolar amount to lithium in a polymerization of butadiene carried out at 5 °C 158 159), but it is slightly less effective in the polymerization of isoprene 160>. 

The above mechanism served as a prototype accounting for other similar polymerizations. However, the kinetics of propagation of lithium polydienes revealed a dependence on the polymer concentration lower than 1/2, apparently 1/4 or less order. This prompted the assumption that the lithium polydienyls form higher aggregates than dimers. 

Anionic polymerization of vinyl monomers can be effected with a variety of organometaUic compounds alkyllithium compounds are the most useful class (1,33—35). A variety of simple alkyllithium compounds are available commercially. Most simple alkyllithium compounds are soluble in hydrocarbon solvents such as hexane and cyclohexane and they can be prepared by reaction of the corresponding alkyl chlorides with lithium metal. Methyllithium [917-54-4] and phenyllithium [591-51-5] are available in diethyl ether and cyclohexane—ether solutions, respectively, because they are not soluble in hydrocarbon solvents vinyllithium [917-57-7] and allyllithium [3052-45-7] are also insoluble in hydrocarbon solutions and can only be prepared in ether solutions (38,39). Hydrocarbon-soluble alkyllithium initiators are used directiy to initiate polymerization of styrene and diene monomers quantitatively one unique aspect of hthium-based initiators in hydrocarbon solution is that elastomeric polydienes with high 1,4-microstmcture are obtained (1,24,33—37). Certain alkyllithium compounds can be purified by recrystallization (ethyllithium), sublimation (ethyllithium, /-butyUithium [594-19-4] isopropyllithium [2417-93-8] or distillation (j -butyUithium) (40,41). Unfortunately, / -butyUithium is noncrystaUine and too high boiling to be purified by distiUation (38). Since methyllithium and phenyllithium are crystalline soUds which are insoluble in hydrocarbon solution, they can be precipitated into these solutions and then redissolved in appropriate polar solvents (42,43). OrganometaUic compounds of other alkaU metals are insoluble in hydrocarbon solution and possess negligible vapor pressures as expected for salt-like compounds. 

Aromatic radical anions, such as lithium naphthalene or sodium naphthalene, are efficient difunctional initiators (eqs. 6,7) (3,20,64). However, the necessity of using polar solvents for their formation and use limits their utility for diene polymerization, since the unique abiUty of lithium to provide high 1,4-polydiene microstmcture is lost in polar media (1,33,34,57,63,64). Consequentiy, a significant research challenge has been to discover a hydrocarbon-soluble dilithium initiator which would initiate the polymerization of styrene and diene monomers to form monomodal a, CO-dianionic polymers at rates which are faster or comparable to the rates of polymerization, ie, to form narrow molecular weight distribution polymers (61,65,66). 

The presence of cross-associated species needs to be considered in the interpretation of copolymerization kinetics. It has been found 269) that the reaction of poly(butadie-nyl)lithium with p-divinylbenzene in benzene solution proceeds at a rate which increases markedly with time. Such a result implies that the poly(butadienyl)lithium aggregate is less reactive than the mixed aggregate formed between the butadienyl-and vinylbenzyllithium active centers. Interestingly, no accelerations with increasing reaction time were found with poly(butadienyl)lithium and m-divinylbenzene nor with poly(isoprenyl)lithium and either the m- or p-divinylbenzenes. This general behavior was subsequently verified 270) by a series of size exclusion chromatography measurements on polydiene stars (linked via divinylbenzene) as a function of conversion. 

The crucial point of the procedure is the control of the stoichiometry of the reaction between the living A chains and the DPE derivative, otherwise a mixture of stars is produced. A major problem is the fact that the rate constants for the reaction of the first and second polymeric chain with the DPE derivative are different. This results in bimodal distributions because of the formation of both the monoanion and dianion. In order to overcome this problem polar compounds have to be added, but it is well known that they affect dramatically the microstructure of the polydienes that are formed in the last step. However the addition of lithium sec-butoxide to the living coupled DPE derivative, prior to the addition of the diene monomer, was found to produce monomodal well defined stars with high 1,4 content. Finally another weak point of the method is that, as in the case of the DVB route, the B arms cannot be isolated from the reaction mixture and characterized separately. It is therefore difficult to obtain unambiguous information about the formation of the desired products. 

Polar solvents drastically affect the nature of the polydienes produced by lithium or alkyl lithiums. Generally the m-1,4 stereospecificity is lost. This solvent affect is less pronounced with other alkali metal dependent initiators. 

A variation of the sequential monomer addition technique described in Section 9.2.6(i) is used to make styrene-diene-styrene iriblock thermoplastic rubbers. Styrene is polymerized first, using butyl lithium initiator in a nonpolar solvent. Then, a mixture of styrene and the diene is added to the living polystyryl macroanion. The diene will polymerize first, because styrene anions initiate diene polymerization much faster than the reverse process. After the diene monomer is consumed, polystyrene forms the third block. The combination of Li initiation and a nonpolar solvent produces a high cis-1,4 content in the central polydiene block, as required for thermoplastic elastomer behavior. 

The intensive investigations that followed the discovery ( ) that lithium and its compounds can lead to the polymerization of isoprene to a very high cis-1,4 configuration, close to that of natural rubber, showed that both the type of alkali metal and the nature of the solvent can have a profound effect on the chain structure of polydienes The conclusions reached from these... 

It is fairly well understood that alkyl lithiums form rather stable aggregates in which carbon-lithium bond order is maximized by the utilization of all valence orbitals of lithium.(1) Polystyryl lithium molecules are mostly dimeric in solution.(1.3,4) This has been generally accepted by all the investigators.TlT However, association numbers of two(6) and four(Z T has been reported for polydienes. Two methods were used in determining these values, viz., light scattering measurements (in vacuo) and viscosity measurements. 

The fact that until recently (9,11) there has not been a well established example of a synthetic polydiene containing more of the cis structure than the trans structure, has generally been explained by the greater thermodynamic stability of the trans structure over the cis structure in such compounds. The polymerization of isoprene to a high percentage of the cis structure, and a complete absence of the trans structure by lithium metal, suggests that some unusual mechanism is operating in this polymerization. 

In conclusion, FMC has developed a viable, commercial synthesis of a family of omega-(/-butyldimethylsilyloxy)-l-alkyllithiums that are valuable anionic initiators. A variety of chain lengths are available between the protected hydroxyl ftmction and the carbon-lithium bond. These hydrocarbon soluble initiators afford very high 1,4-microstructure in the polymerization of polydienes, such as... 

Hydrocarbon Solvents One of the most important synthetic and commercial aspects of anionic polymerization is the ability to prepare polydienes [poly(l,3-dienes)] with high 1,4-microstructure using lithium as the counterion in hydrocarbon solutions [3, 156]. The key discovery was reported in 1956 by scientists at the Firestone Tire and Rubber Company that polyisoprene produced by lithium metal-initiated anionic polymerization had a high (>90%) cm-1,4-microstructure similar to natural rubber [47], In general, conjugated 1,3-dienes [CH2=C(R)-CH=CH2] can polymerize to form four constimtional isomeric microstructures as shown below. The stereochemistry of the anionic polymerization of isoprene and... 

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