Polydispersity, living polymerization

The formation of polymer can be considered as a quasi-living polymerization. After the polymerization is complete, it can be reinitiated with the addition of more monomer to the unquenched polymer. However, the degree of polymerization cannot be predicted by the monomer/initiator molar ratio, the polydispersity is 1.5-2.0, and water, or even carboxylic acids, act as inhibitors and do not terminate the polymerization [10]. 

A potential drawback of all the routes discussed thus far is that there is little control over polydispersity and molecular weight of the resultant polymer. Ringopening metathesis polymerization (ROMP) is a living polymerization method and, in theory, affords materials with low polydispersities and predictable molecular weights. This methodology has been applied to the synthesis of polyacctylcne by Feast [23], and has recently been exploited in the synthesis of PPV. Bicyclic monomer 12 [24] and cyclophane 13 [25) afford well-defined precursor polymers which may be converted into PPV 1 by thermal elimination as described in Scheme 1-4. 

This result is of great interest as it means that tedious fractionation procedures can be avoided The polydispersity of a polymer made by an anionic living polymerization is expected to be narrower than that of a very good fraction arising from a sample obtained by other methods. 

A thiol-terminated PS was used as a sample in the experiment. It was based on a living polymerized carboxyl-terminated PS with M = 93,800 and Mu = 100,400. The polydispersity was Mp( /M = 1.07. The degree of polymerization was about 900 and, thus, its contour length was about 220 nm. The thiol groups were substimted for the carboxylic ends using 1,10-decanedithiol by means of thiolester bonding, anticipating the preferential interaction between... 

Living polymerization of lactones has been successfully performed by catalysis of rare earth metal complexes to obtain Mw/Mn of 1.07-1.08 [8]. The lowest polydispersity index attained so far with the AlEt3/H20 system is 1.13. 

Some transition metal catalysts induce the living polymerization of various acetylenic compounds.68,69 Such polymerizations of phenylacetylene catalyzed by rhodium complexes are used in conjunction with a quantitative initiation and introduction of functional groups at the initiating chain end (Scheme 16).70 The catalyst is prepared from an [RhCl(nbd)]2/Ph2C=C(Ph)Li/PPh3 mixture and proceeds smoothly to give quantitatively the polymer 54 with a low polydispersity ratio. 

Hawker et al. 2001 Hawker and Wooley 2005). Recent developments in living radical polymerization allow the preparation of structurally well-defined block copolymers with low polydispersity. These polymerization methods include atom transfer free radical polymerization (Coessens et al. 2001), nitroxide-mediated polymerization (Hawker et al. 2001), and reversible addition fragmentation chain transfer polymerization (Chiefari et al. 1998). In addition to their ease of use, these approaches are generally more tolerant of various functionalities than anionic polymerization. However, direct polymerization of functional monomers is still problematic because of changes in the polymerization parameters upon monomer modification. As an alternative, functionalities can be incorporated into well-defined polymer backbones after polymerization by coupling a side chain modifier with tethered reactive sites (Shenhar et al. 2004 Carroll et al. 2005 Malkoch et al. 2005). The modification step requires a clean (i.e., free from side products) and quantitative reaction so that each site has the desired chemical structures. Otherwise it affords poor reproducibility of performance between different batches. 

In coi itrast, in living polymerization systems, the polymerization occurs without chain transfer or chain termination, giving greater control over polydispersity of the resultant polymers. Such polymerization systems allow the controlled synthesis of water-soluble polymers and enable precise control over the composition of block copolymers. 

The quasi living polymerization of ethene and norbornene has been reviewed, among other topics in living polymerization of alkenes (19). Specifically, arylimido-aryloxo-vanadium(V) complexes with methylaluminoxane or Et2AlCl as co-catalyst have been used as catalyst systems. The polymers exhibit a low polydispersity and a high molecular weight (20). 

Eq. (17) predicts that, when Pn is 100, the polydispersity is equal to 1.01, so that the polymer is virtually monodisperse. However, such ideal monodisperse polymers have scarcely been synthesized. The lowest values of polydispersity (Mw/Mn = 1.05-1.10) have been attained in homogeneous anionic polymerization 43). Gold 41) calculated the polydispersity of a polymer in the living polymerization with a slow initiation reaction and showed that the value of Pw/Pn increases slightly to a maximum (1.33) with an increase in polymerization time, followed by a decrease toward 1.00. Other factors affecting the molecular weight distribution of living polymer have been discussed in several papers 5S 60). 

The alkylaluminum component combined with V(acac)3 has an influence on the kinetic behavior of the propylene polymerization at —78 °C47 82 83). In the polymerization with V(acac)3 and dialkylaluminum monohalide like Al(i-C4H9)2C1, Al(n-C3H7)2C1, A1(C2HS)2C1 or Al(C2H5)2Br, M of polypropylene increased proportionally to the polymerization time, and the polydispersity (M Mj was as narrow as 1.15 0.05 (see Fig. 9). This is the case of living polymerization. As can be seen from Fig. 9, the rate of increase of Mn, i.e. the rate of propagation of living chains as expressed by lvln/(42 t), is influenced by the kind of aluminum component and decreases in the series... 

---