Anionic polymerization distribution

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). 

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. 

The block copolymer produced by Bamford s metal carbonyl/halide-terminated polymers photoinitiating systems are, therefore, more versatile than those based on anionic polymerization, since a wide range of monomers may be incorporated into the block. Although the mean block length is controllable through the parameters that normally determine the mean kinetic chain length in a free radical polymerization, the molecular weight distributions are, of course, much broader than with ionic polymerization and the polymers are, therefore, less well defined,... 

As these block copolymers were synthesized using the anionic polymerization technique, their molecular weight distributions were narrow. The microspheres with narrower size distribution are better for well-ordered self-organization. Actually, all block copolymers synthesized for these works formed poly(4-vinyl pyridine) (P4VP) spheres in the PS matrices with narrow size distributions. 

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. 

Some tailor-made homopolymers can serve as starting points for chemical modifications to yield new species. Poly(hydroxyethyl methacrylate) and poly(glyceryl methacrylate) 16), already mentioned, are obtained upon hydrolysis of the OH-protecting groups that allow the anionic polymerization to proceed. Another example is the acid hydrolysis of poly(t-butyl methacrylate), a reaction which proceeds easily to completion, yielding poly(methacrylic acid) of known degree of polymerization and narrow molecular weight distribution 44 45). 

The synthesis of well defined block copolymers exhibiting controlled molecular weight, low compositional heterogeneity and narrow molecular weight distribution is a major success of anionic polymerization techniques 6,7,14-111,112,113). Blocks of unlike chemical nature have a general tendency to undergo microphase separation, thereby producing mesomorphic phases. Block copolymers therefore exhibit unique properties, that prompted numerous studies and applications (e.g. thermoplastic elastomers). 

Polystyrene standards used were narrow molecular weight distribution sample produced by anionic polymerization and available from Pressure Chemical Co. Also sample NBS7C from the National Bureau of Standards was used. The sample of poly n-butyl methacrylate was obtained from Aldrich Chemical. It was produced by free radici polymerization with an Mw of 320,(XK) and an Mn of 73,500 (Cat. No. 18,153-6). 

An important by-product of the development of this approach is that Orthogonal Chromatography provides a direct method of estimating the shape of the chromatogram for extremely narrow molecular weight distributions. This shape function is fundamental information for axial dispersion evaluation and is not otherwise easily obtained. Even commercially available monodisperse standards synthesized by anionic polymerization are too polydisperse. 

Anionic polymerization in suitable systems allows the preparation of polymers with controlled molecular weight, narrow molecular weight distributions and functional termination. The functional termination of a living anionic polymerization with a polymerizable group has been used frequently in the preparation of macromonomers (4). Our research has encompassed the anionic homo and block copolymerizations of D- or hexamethyl cyclotrisiloxane with organolithiums to prepare well defined polymers. As early as 1962 PSX macromonomers were reported in the literature by Greber (5) but the copolymerization of these macromonomers did not become accepted technique until their value was demonstrated by Milkovich and... 

Anionic polymerization Narrow molecular weight distribution Limited chain transfer reactions Predictable molecular weight average Possibility of forming living polymers End groups can be tailored for further reactivity Solvent-sensitive due to the possibility of chain transfer to the solvent Can be slow Sensitive to trace impurities Narrow molecular weight distribution... 

A radical initiator based on the oxidation adduct of an alkyl-9-BBN (47) has been utilized to produce poly(methylmethacrylate) (48) (Fig. 31) from methylmethacrylate monomer by a living anionic polymerization route that does not require the mediation of a metal catalyst. The relatively broad molecular weight distribution (PDI = (MJM ) 2.5) compared with those in living anionic polymerization cases was attributed to the slow initiation of the polymerization.69 A similar radical polymerization route aided by 47 was utilized in the synthesis of functionalized syndiotactic polystyrene (PS) polymers by the copolymerization of styrene.70 The borane groups in the functionalized syndiotactic polystyrenes were transformed into free-radical initiators for the in situ free-radical graft polymerization to prepare s-PS-g-PMMA graft copolymers. 

The polymerization was carried out in THF under the conditions of high vacuum or argon atmosphere with a catalytic amount of alkyllithium as an initiator. Anionic polymerization of 3a with n-BuLi in THF followed by quenching with ethanol afforded polymer 6 in 56 % yield. The molecular weight distribution of the polymer was determined by gel permeation chromatography (GPC), calibrated by polystyrene standards, with chlorofrom as eluent Mn = 6.1xl0"4, Mw/Mn = 1.3. 

Polystyrene/polyethylene oxide dendrimers were prepared by ATRP using tri- and tetra (bromomethyl) benzene as the initiators [207]. Each bromine end-group of the resulting stars was transformed first to two - OH groups and subsequently to potassium alcholate, as shown in Scheme 114. These - OK sites served to initiate the anionic polymerization of EO. The synthesized dendritic copolymers were found to display monomodal and narrow molecular weight distribution. 

Matyjaszewski et al. [281-285] succeeded in the synthesis of poly(St) with a narrow molecular weight distribution, comparable to the living anionic polymerization, in the atom transfer radical polymerization (ATRP) using Cu complex and alkyl halides (Eq. 74) ... 

We use polystyrene-Z>-polybutadiene block copolymers as the starting material with preformed polymer architecture. These polymers are comparatively cheap and easily accessible.1 For the present problems a series of narrowly distributed polystyrene-6-polybutadiene block copolymers with rather different molecular weights were synthesized via anionic polymerization (Figure 10.4, Table 10.1). As a test for the modification of technological products, a commercial triblock copolymer was also used. 

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