Acids 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]. 

Lewis acid effects 435 1UPAC recommendations copolymer depiction 335 living polymerization 452 polymer structure 2... 

Phosphoranyl radicals can be involved [77] in RAFT processes [78] (reversible addition fragmentation transfer) used to control free radical polymerizations [79]. We have shown [77] that tetrathiophosphoric acid esters are able to afford controlled/living polymerizations when they are used as RAFT agents. This result can be explained by addition of polymer radicals to the P=S bond followed by the selective p-fragmentation of the ensuing phosphoranyl radicals to release the polymer chain and to regenerate the RAFT agent (Scheme 41). 

Deming TJ (2000) Living polymerization of alpha-amino acid-N-carboxyanhydrides. J Polym Sci Polym Chem 38 3011-3018... 

Brzezinska KR, Deming TJ (2001) Synthesis of ABA triblock copolymers via acyclic diene metathesis polymerization and living polymerization of alpha-amino acid-N-carboxyanhy-drides. Macromolecules 34 4348 354... 

Further experiments were therefore carried out with polar solvents which do not dissolve the polymer. Most striking results were obtained with trichloroacetic acid. The polymerization of acrylonitrile in this solvent was found to proceed under precipitating conditions at all concentrations. In spite of this, the conversion curves were perfectly linear in solutions containing 60 volume per cent monomer or less (18). Moreover, these systems exhibit marked post-polymerization showing the presence of long-lived radicals. 

Fig, 4, Schematic illustration of high-speed living polymerization of methacrylate esters accelerated by steric separation of the aluminum porphyrin nucleophile and bulky Lewis acid. ... 

The major approach to extending the lifetime of propagating species involves reversible conversion of the active centers to dormant species such as covalent esters or halides by using initiation systems with Lewis acids that supply an appropriate nucleophilic counterion. The equilibrium betweem dormant covalent species and active ion pairs and free ions is driven further toward the dormant species by the common ion effect—by adding a salt that supplies the same counterion as supplied by the Lewis acid. Free ions are absent in most systems most of the species present are dormant covalent species with much smaller amounts of active ion pairs. Further, the components of the reaction system are chosen so that there is a dynamic fast equilibrium between active and dormant species, as the rates of deactivation and activation are faster than the propagation and transfer rates. The overall result is a slower but more controlled reaction with the important features of living polymerization (Sec. 3-15). 

Under certain conditions, irreversible chain-breaking reactions are absent and cationic ROPs of cyclic ethers proceed as living polymerizations. These conditions are found for polymerizations initiated with acylium and l,3-dioxolan-2-ylium salts containing very stable counterions such as AsFg, PFg, and SbClg or with very strong acids (fluorosulfonic and... 

Rh complexes are examples of the most effective catalysts for the polymerization of monosubstituted acetylenes, whose mechanism is proposed as insertion type. Since Rh catalysts and their active species for polymerization have tolerance toward polar functional groups, they can widely be applied to the polymerization of both non-polar and polar monomers such as phenylacetylenes, propiolic acid esters, A-propargyl amides, and other acetylenic compounds involving amino, hydroxy, azo, radical groups (see Table 3). It should be noted that, in the case of phenylacetylene as monomer, Rh catalysts generally achieve quantitative yield of the polymer and almost perfect stereoregularity of the polymer main chain (m-transoidal). Some of Rh catalysts can achieve living polymerization of certain acetylenic monomers. The only one defect of Rh catalysts is that they are usually inapplicable to the polymerization of disubstituted acetylenes. Only one exception has been reported which is described below. 

Keywords Anionic polymerization. Living Polymerization, Immortal polymerization, Metalloporphyrin, Lewis acid... 

One-Shot Lewis Acid Promoted Living Polymerization... 

For Lewis acid promoted living polymerization of MMA with (TPP)AlMe (1,X= Me) as initiator, a photoinitiation prior to the addition of the Lewis acid is required. This is because (1) 1 (X=Me) without irradiation does not have the ability to initiate the polymerization even in the presence of Lewis acid, and (2) all-at-once polymerization by direct irradiation of a mixture of MMA, 1 (X=Me), and the Lewis acid results in the formation of a relatively broad MWD PMMA with Mn much higher than expected. In this sense, the procedure using 1 (X= Me) as initiator is not convenient for practical application. In this section, we report on aluminum porphyrins with various axial ligands which were tested as initiators in order to realize a more convenient, one-shot high-speed living polymerization of methyl methacrylate with no need for irradiation with visible light. 

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