Polymerization monomer activation

In cationic polymerization the active species is the ion which is formed by the addition of a proton from the initiator system to a monomer. For vinyl monomers the type of substituents which promote this type of polymerization are those which are electron supplying, like alkyl, 1,1-dialkyl, aryl, and alkoxy. Isobutylene and a-methyl styrene are examples of monomers which have been polymerized via cationic intermediates. 

Two possible reasons may be noted by which just the coordinatively insufficient ions of the low oxidation state are necessary to provide the catalytic activity in olefin polymerization. First, the formation of the transition metal-carbon bond in the case of one-component catalysts seems to be realized through the oxidative addition of olefin to the transition metal ion that should possess the ability for a concurrent increase of degree of oxidation and coordination number (177). Second, a strong enough interaction of the monomer with the propagation center resulting in monomer activation is possible by 7r-back-donation of electrons into the antibonding orbitals of olefin that may take place only with the participation of low-valency ions of the transition metal in the formation of intermediate 71-complexes. 

Unfortunately, the most favorable polymerization conditions (active catalyst, neat monomer) lead rapidly to solidified, high-viscosity reaction mixtures. Highly viscous media can severely inhibit condensation polymerizations, since inefficient removal of the small molecular weight product (in this case, hydrogen) slows approach of the reaction to completion. Raising the temperature to lower the viscosity is counterproductive, since cyclic formation becomes competitive at higher temperatures. 

R A. Monnard et al. from the laboratory of D. W. Deamer also worked on ice/eutectic phases at 255 K. They studied the influence of solutions of inorganic ions (such as Na+, CD, Mg2+, Ca2+ and Fe2+) both on the formation of vesicles and on non-enzymatic polymerization of activated RNA monomers (Monnard et al., 2002). 

The reaction mechanism for the polymerization of a hydroxyalkanoic acid (Eqs. 2-243 through 2-246) is a chain polymerization, often called an activated monomer polymerization. The active site of lipase is its serine a-amino acid unit, which contains a hydroxyl group. The acyl carbon of the hydroxyalkanoic acid undergoes nucleophilic attack by the hydroxyl group of serine to form lipase-activated monomer (Eq. 2-243). Initiation consists of reaction... 

Figures 3-21 and 3-22 show results in the ATRP polymerization of styrene using 1-phenylethyl bromide as the initiator, CuBr as catalyst (activator), and 4,4-di-5-nonyl-2,2 -bipyridine as ligand [Matyjaszewski et al., 1997]. Figure 3-21 shows the decrease in monomer concentration to be first-order in monomer, as required by Eq. 3-223. The linearity over time indicates that the concentration of propagating radicals is constant throughout the polymerization. The first-order dependencies of Rp on monomer, activator, and initiator and the inverse first-order dependence on deactivator have been verified in many ATRP reactions [Davis et al., 1999 Patten and Matyjaszewski, 1998 Wang et al., 1997].

In lipase-catalyzed ROP, it is generally accepted that the monomer activation proceeds via the formation of an acyl-enzyme intermediate by reaction of the Ser residue with the lactone, rendering the carbonyl more prone to nucleophilic attack (Fig. 3) [60-64, 94]. Initiation of the polymerization occurs by deacylation of the acyl-enzyme intermediate by an appropriate nucleophile such as water or an alcohol to produce the corresponding co-hydroxycarboxylic acid or ester. Propagation, on the other hand, occurs by deacylation of the acyl-enzyme intermediate by the terminal hydroxyl group of the growing polymer chain to produce a polymer chain that is elongated by one monomer unit. 

Erom these results, not only the steric bulk of the Lewis acid (monomer activator), but also that of the nucleophilic growing species 2, is important for realizing the Lewis acid assisted, controlled anionic polymerization the basic concept involving a sterically separated nucleophile-electrophile model is thus clearly demonstrated. 

Preliminary results on the kinetics of the polymerization and the efficiency of initiation of the isotactic polymerizations initiated by t-BuMgBr in toluene solution are consistent with the Bateup mechanism proposed for the stereoblock and syndio-tactic-like polymerizations initiated by n-BuMgBr in THF-rich solution — a mechanism which involves initiation and propagation through monomer — active centre complexes (5,8). 

We shall not treat a number of general problems of anionic polymerization such as autosolvation of the ion pairs, cation solvation with the electron-donor chain atoms, the role of the medium etc. Two problems attract our attention monomer activation during chain propagation and the direction of the epoxy ring opening. 

The most evident results have been obtained in the case of monomers having the asymmetric carbon atom in a position with respect to the double bond (Table 3 and 4) on the basis of the optical activity of the polymer obtained and of the non polymerized monomer recovered, it appears that, under the polymerization conditions used, the antipode having the same absolute structure as the asymmetric alkyl group present in the catalyst (104) is polymerized more rapidly, 1.15 to 1.7 times, than the other antipode. 

In our opinion, (XXXVI) with Y=R or (XXXVIII), rather than (XXXIX) or (XL) better explains the relationship found between the absolute structure of the optically active alkyl group present in the organometallic compound used for the preparation of the catalyst and the absolute structure of the preferentially polymerized monomer. 

Enolates. Another class of activators for photoreducible dyes was discovered by Chaberek (24,45). Enolates of diketones such as acetylacetone or dimedone (5,5-dimethyl-l,3-cyclohex-anedione) were shown to be effective reductants for the excited states of MB and to polymerize monomers such as acrylamide. Chaberek, Shepp, and Allen discussed the mechanism of this process in a series of papers (46,47). 

I, 3-diene polymerization. Monomer molecules are included in chiral channels in the matrix crystals, and the polymerization takes place in chiral environment. The y-ray irradiation polymerization of trans- 1,3-pentadiene included in 13 gives an optically active isotactic polymer with a trans-structure. The polymerization of (Z)-2-methyl-1,3-butadiene using 15 as a matrix leads to a polymer having an optical purity of the main-chain chiral centers of 36% [47]. 

It isn t difficult to form addition polymers from monomers containing C=C double bonds many of these compounds polymerize spontaneously unless polymerization is actively inhibited. 

Change in the main monomer activity, e.g. by adding a monomer that is highly reactive to the Surfmer at the end of the polymerization process or by an intrinsic change in the comonomer activity because of concentration effects... 

In addition (chain) polymerization, monomers containing an unsaturated (vinyl) bond polymerize in the presence of an initiator, which generates an active site at the end of the chain. Several chemical reactions take place simultaneously in the course of the polymerization. First, an initiation reaction via photo- or heat-decomposition of the initiator occurs to form the active species, which are either peroxides or azo compounds. The active species react with a monomer to generate the active site (i.e., initiation). 

Polyanhydrides have been modified by incorporating amino acids into im-ide bonds. The imide with the terminal carboxylic acids is activated with acetic anhydride and copolymerized with sebacic acid or CCP. Poly(anhydride-imides) increase the mechanical properties of the polyanhydrides. Degradation of poly(anhydride-imide)s is similar to that of polyanhydrides (i.e., surface erosion). Two different cleavable bonds (anhydride and ester) in the polymer chains have been included in polyanhydrides. Carboxylic acid-terminated e-caprolactone oligomers or carboxylic acid-terminated monomers (e.g., salicylic acid) have been polymerized with activated monomers (e.g., SA). 

Anionic polymerizations, when carried out in aprotic solvents, are characterized by the long lifetime of the carbanionic (or oxanionic) sites l2). When neither spontaneous transfer nor termination reactions are involved, the polymers obtained exhibit sharp molecular weight distributions, and their number average degree of polymerization is determined by the [Monomer]/[Initiator] molar ratio, provided initiation is fast as compared to propagation. However, the major advantage of these methods, as far as synthesis is concerned, is the socalled living character of the polymers 12) After completion of the polymerization the active sites retain their reactivity and can be used for functionalizations at the chain end. 

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