Molecular weight anionic polymerization

The ratio M IMn approaches unity asymptotically as increases. Narrow molecular weight distributions should thus be obtained in living ionic polymerizations with fast initiation in the absence of depropagation, termination, and chain transfer reactions. Values of polydispersity index (PDI) below 1.1 -1.2 are indeed found for many living polymerizations. Molecular weight-standards for polystyrene, poly-isoprene, poly(a-methylstyrene), and poly (methyl methacrylate) are thus synthesized by living anionic polymerizations. However, the termination reactions in methyl methacrylate polymerizations and depropagation in or-methylstyrene polymerizations tend to broaden the PDI in these systems. 

Compounds of type (72) can be polymerized with radical and anionic initiators. Molecular weights of approximately 5xl0 g/mol have been observed for the homopolymer of Scheme (72) (R = CH3, R = OCH3) [410]. This polymer contained 60 to 69% 3.4 structure units and 31 to 40% 1.4 structure units [411], which were determined from H-NMR data. Anionic polymerization can be initiated by butyllithium, butyl magnesium bromide, and other typical anionic initiators in bulk and in solution [412]. 

My faculty colleagues of the Institute also bring great expertise in the areas of anionic, cationic, and radical polymerization to the transformation of low-molecular-weight hydrocarbons into macromole-... 

The addition polymerization of a vinyl monomer CH2=CHX involves three distinctly different steps. First, the reactive center must be initiated by a suitable reaction to produce a free radical or an anion or cation reaction site. Next, this reactive entity adds consecutive monomer units to propagate the polymer chain. Finally, the active site is capped off, terminating the polymer formation. If one assumes that the polymer produced is truly a high molecular weight substance, the lack of uniformity at the two ends of the chain—arising in one case from the initiation, and in the other from the termination-can be neglected. Accordingly, the overall reaction can be written... 

In ionic polymerizations termination by combination does not occur, since all of the polymer ions have the same charge. In addition, there are solvents such as dioxane and tetrahydrofuran in which chain transfer reactions are unimportant for anionic polymers. Therefore it is possible for these reactions to continue without transfer or termination until all monomer has reacted. Evidence for this comes from the fact that the polymerization can be reactivated if a second batch of monomer is added after the initial reaction has gone to completion. In this case the molecular weight of the polymer increases, since no new growth centers are initiated. Because of this absence of termination, such polymers are called living polymers. 

Polyacetaldehyde, a mbbery polymer with an acetal stmcture, was first discovered in 1936 (49,50). More recentiy, it has been shown that a white, nontacky, and highly elastic polymer can be formed by cationic polymerization using BF in Hquid ethylene (51). At temperatures below —75° C using anionic initiators, such as metal alkyls in a hydrocarbon solvent, a crystalline, isotactic polymer is obtained (52). This polymer also has an acetal [poly(oxymethylene)] stmcture. Molecular weights in the range of 800,000—3,000,000 have been reported. Polyacetaldehyde is unstable and depolymerizes in a few days to acetaldehyde. The methods used for stabilizing polyformaldehyde have not been successful with poly acetaldehyde and the polymer has no practical significance (see Acetalresins). 

A brief review has appeared covering the use of metal-free initiators in living anionic polymerizations of acrylates and a comparison with Du Font s group-transfer polymerization method (149). Tetrabutylammonium thiolates mn room temperature polymerizations to quantitative conversions yielding polymers of narrow molecular weight distributions in dipolar aprotic solvents. Block copolymers are accessible through sequential monomer additions (149—151) and interfacial polymerizations (152,153). 

Many perfluoroaUphatic ethers and tertiary amines have been prepared by electrochemical fluorination (1 6), direct fluorination using elemental fluorine (7—9), or, in a few cases, by fluorination using cobalt trifluoride (10). Examples of lower molecular weight materials are shown in Table 1. In addition to these, there are three commercial classes of perfluoropolyethers prepared by anionic polymerization of hexafluoropropene oxide [428-59-1] (11,12), photooxidation of hexafluoropropene [116-15-4] or tetrafluoroethene [116-14-3] (13,14), or by anionic ring-opening polymeriza tion of tetrafluorooxetane [765-63-9] followed by direct fluorination (15). 

AlkyUithium compounds are primarily used as initiators for polymerizations of styrenes and dienes (52). These initiators are too reactive for alkyl methacrylates and vinylpyridines. / -ButyUithium [109-72-8] is used commercially to initiate anionic homopolymerization and copolymerization of butadiene, isoprene, and styrene with linear and branched stmctures. Because of the high degree of association (hexameric), -butyIUthium-initiated polymerizations are often effected at elevated temperatures (>50° C) to increase the rate of initiation relative to propagation and thus to obtain polymers with narrower molecular weight distributions (53). Hydrocarbon solutions of this initiator are quite stable at room temperature for extended periods of time the rate of decomposition per month is 0.06% at 20°C (39). 

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). 

Polymerization ofiVIasked Disilenes. A novel approach, namely, the anionic polymerization of masked disilenes, has been used to synthesize a number of poly(dialkylsilanes) as well as the first dialkylamino substituted polysilanes (eq. 13) (111,112). The route is capable of providing monodisperse polymers with relatively high molecular weight M = lO" — 10 ), and holds promise of being a good method for the synthesis of alternating and block copolymers. 

The vast majority of commercial apphcations of methacryhc acid and its esters stem from their facile free-radical polymerizabiUty (see Initiators, FREE-RADICAl). Solution, suspension, emulsion, and bulk polymerizations have been used to advantage. Although of much less commercial importance, anionic polymerizations of methacrylates have also been extensively studied. Strictiy anhydrous reaction conditions at low temperatures are required to yield high molecular weight polymers in anionic polymerization. Side reactions of the propagating anion at the ester carbonyl are difficult to avoid and lead to polymer branching and inactivation (38—44). 

It may be shown that M > M. The two are equal only for a monodisperse material, in which all molecules are the same sise. The ratio MI /MI is known as the polydispersity index and is a measure of the breadth of the molecular weight distribution. Values range from about 1.02 for carefully fractionated samples or certain polymers produced by anionic polymerization, to 20 or more for some commercial polyethylenes. 

Polyelectrolyte complex membranes are phase-inversion membranes where polymeric anions and cations react during the gelation. The reaction is suppressed before gelation by incorporating low molecular weight electrolytes or counterions in the solvent system. Both neutral and charged membranes are formed in this manner (14,15). These membranes have not been exploited commercially because of then lack of resistance to chemicals. 

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