Acrylic monomers, anionic

In dry air and in the presence of polymerisation inhibitors methyl and ethyl 2-cyanoacrylates have a storage life of many months. Whilst they may be polymerised by free-radical methods, anionic polymerisation is of greater significance. A very weak base, such as water, can bring about rapid polymerisation and in practice a trace of moisture on a substrate is enough to allow polymerisation to occur within a few seconds of closing the joint and excluding the air. (As with many acrylic monomers air can inhibit or severely retard polymerisation). 

Alkyl cyanoacrylate monomers have been copolymerized with a variety of monomers, both by radical and anionic initiation. The radical-initiated copolymerization with acrylic monomers was performed with a sufficient amount of an acid stabilizer present to suppress polymerization by anionic means [19]. This investigation has been covered extensively elsewhere. 

Radical copolymerization is used in the manufacturing of random copolymers of acrylamide with vinyl monomers. Anionic copolymers are obtained by copolymerization of acrylamide with acrylic, methacrylic, maleic, fu-maric, styrenesulfonic, 2-acrylamide-2-methylpro-panesulfonic acids and its salts, etc., as well as by hydrolysis and sulfomethylation of polyacrylamide Cationic copolymers are obtained by copolymerization of acrylamide with jV-dialkylaminoalkyl acrylates and methacrylates, l,2-dimethyl-5-vinylpyridinum sulfate, etc. or by postreactions of polyacrylamide (the Mannich reaction and Hofmann degradation). Nonionic copolymers are obtained by copolymerization of acrylamide with acrylates, methacrylates, styrene derivatives, acrylonitrile, etc. Copolymerization methods are the same as the polymerization of acrylamide. 

Recently it has been shown that anionic functionalization techniques can be applied to the synthesis of macromonomers — macromolecular monomers — i.e. linear polymers fitted at chain end with a polymerizable unsaturation, most commonly styrene or methacrylic ester 69 71). These species in turn provide easy access to graft copolymers upon radical copolymerization with vinylic or acrylic monomers. 

These TMS-carbamate-mediated NCA polymerizations resemble to some extent the group-transfer polymerization (GTP) of acrylic monomers initiated by organo-silicon compounds [40]. Unlike GTPs that typically require Lewis acid activators or nucelophilic catalysts to facilitate the polymerization [41], TMS-carbamate-mediated NCA polymerizations do not appear to require any additional catalysts or activators. However, it is still unclear whether the TMS transfer proceeds through an anionic process as in GTP [41] or through a concerted process as illustrated in Scheme 14. 

However, the practical, direct synthesis of functionalized linear polyolefins via coordination copolymerization olefins with polar monomers (CH2 = CHX) remains a challenging and industrially important goal. In the mid-1990s Brookhart et al. [25, 27] reported that cationic (a-diimine)palladium complexes with weakly coordinating anions catalyze the copolymerization of ethylene with alkylacrylates to afford hyperbranched copolymers with the acrylate functions located almost exclusively at the chain ends, via a chain-walking mechanism that has been meticulously studied and elucidated by Brookhart and his collaborators at DuPont [25, 27], Indeed, this seminal work demonstrated for the first time that the insertion of acrylate monomers into certain late transition metal alkyl species is a surprisingly facile process. It spawned almost a decade of intense research by several groups to understand and advance this new science and to attempt to exploit it commercially [30-33, 61]. 

Another approach is based on the copolymerisation of a mixture of two acrylic monomers. One is of the anionic type (or cationic) and the other one is poly-hydroxylated (Fig. 4.3). The latter is used to ensure the hydrophilic character necessary for the stationary phase. A limitation of these resins is their variable swelling, which depends on the composition of the mobile phase. They are normally used for medium pressure chromatography and certain biochemical applications. 

It was previously mentioned that PDADMAC (Cat-Floe) was the first commercial flocculant approved for potable water [26]. Since then, PDADMAC has been continuously used for coagulation/flocculation both in potable water and waste water treatment. A good example of the performance of PDADMAC in the coagulation of colloidal solids is the reduction of turbidity in fresh water of 150 mg L 1 of Ca(OH)2. A reduction of 82% in turbidity is observed with the addition of only 2 mg L 1 of branched PDADMAC [217]. In addition, PDADMAC and copolymers of DADMAC are reported to be effective in the removal of hard-to-elimi-nate impurities in the water treatment industry. Emulsified impurities from streams of a petroleum refinery waste water and an automotive oily effluent water have been removed by the use of water soluble copolymers consisting essentially of DADMAC and small amounts of anionic acrylic monomers [89]. 

Ballard et al. [64] found that bulky dialkyl aluminum phenolate additives would improve the anionic polymerization of acrylic monomers. They called their method Screened Anionic Polymerization (Scheme 28). 

Catalysts of the Ziegler type have been used widely in the anionic polymerization of 1-olefins, diolefins, and a few polar monomers which can proceed by an anionic mechanism. Polar monomers normally deactivate the system and cannot be copolymerized with olefins. However, it has been found that the living chains from an anionic polymerization can be converted to free radicals in the presence of peroxides to form block polymers with vinyl and acrylic monomers. Vinylpyridines, acrylic esters, acrylonitrile, and styrene are converted to block polymers in good yield. Binary and ternary mixtures of 4-vinylpyridine, acrylonitrile, and styrene, are particularly effective. Peroxides are effective at temperatures well below those normally required for free radical polymerizations. A tentative mechanism for the reaction is given. 

In the present paper we pay special attention to block polymers with polypropylene and polyethylene as the initial anionic block. However, both crystalline and amorphous block polymers of ethylene and propylene, butadiene, and several other olefins and dienes have been made by the AFR technique. The second or free radical block has been made from 4-vinylpyridine, 2-methyl-5-vinylpyridine, and mixtures with other monomers, as well as a number of acrylic monomers. Vinyl chloride, vinylidine chloride, vinyl acetate, and several related monomers have not been successfully copolymerized. 

The favorable effect of trialkylaluminium on the anionic polymerization of acrylic monomers induced by organolithium compounds prompted a DFT theoretical and 6Li,13C NMR study on the interaction between AlEt3 and ethyl lithioisobutyrate (EIBLi) in toluene at — 20 °C. Monomers, dimers and tetramers of 1 1 or 1 2 enolate and AlEt3 aggregates were identified (Scheme 67)286. 

The surfactants used in the emulsion polymerization of acrylic monomers are classified as anionic, cationic, or nonionic. Anionic surfactants, such as salts of alkyl sulfates and alkylarene sulfates and phosphates, or nonionic surfactants, such as alkyl or aryl polyoxyethylenes, are most common (87,98—101). Mixed anionic—nonionic surfactant systems are also widely utilized (102—105). 

Acrylate monomers do not generally polymerize by a cationic mechanism. However, the anionic polymerization of acrylic monomers to stereoregular or block copolymers is well known. These polymerizations are conducted in organic solvents, primarily using organometallic compounds as initiators. 

This method for the preparation of poly(styrene-fc-tBuA) is based upon the procedure described by Jerome et al. Teyssie and co-workers demonstrated that the addition of LiCl can be effective in the living anionic polymerization of the acrylic monomers, because a p,-type complex" is formed between LiCl and the growing site. This complex prevents the occurrence of side-reactions at the propagating site, thus markedly narrowing the molecular weight distribution. 

A disadvantage recognized at the outset was the expected difficulty of copolymerizing vinyl ethers (which undergo ready cationic polymerization) with acrylic monomers which are polymerized using radical or anionic Initiators but which resist cationic Initiation (Scheme Ill). 

Another approach for obtaining these stationary phases is based on the copolymerization of a mixture of two acrylic monomers. One is anionic (or cationic), according to the nature of the phase desired, and the other is polyhydroxylated (Figure 4.5), in order to ensure the hydrophilic character of the stationary phase. There is, however, an inconvenience with these resins as their rate of swelling depends upon the... 

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