Polymerization ester mechanism

It appeared to us that the only reasonable non-ionic reaction product of an acid and an olefin would be an ester, and for this reason we put forward the idea that this is the active species in the pseudo-cationic polymerizations. Of course, the idea of an ester in this role has a respectable ancestry which has been discussed in this new context [6]. The ester mechanism of polymerization will be discussed in sub-section 3.3. It must be understood that our conclusion concerning the non-ionic nature of the chain-carriers in the pseudocationic polymerizations is quite independent of our view that the chain-carriers are esters this is at present merely an hypothesis to explain our factual conclusion. 

In accordance with the two ester mechanism, the first step in the polymerization of ethylene in the presence of phosphoric acid is the formation of an ethyl phosphate (Ipatieff and Pines, 70). It was found that rapid absorption of ethylene took place when orthophosphoric acid was treated with etyhlene at 180° under an initial pressure of 50 atmos-... 

Polymaric plasticizars can ba mada by (1) Internal plasticization whoroby a monomor is copolymorizod with on which tends to yield soft polymers by itself (2) Mechanical mixing of a polymerizable monomer with a polymer, followed by polymerization (3) Mechanical blending of two compatible polymers. In many cases It Is necessary to combine the polymeric plasticizer with a liquid plasticizer because the compatibility of polymers with each other is generally limited. From the industrial polymeric plasticizers, especially polyesters of low degree of polymerization and several copolymers of butadiene with acrylonitrile, acrylic add esters and fumaric add esters were studied. These polymeric plasticizers are characterized by good compatibility and improved cold resistance of the final product. 

Muller AHE. Present view of the anionic polymerization of methyl methacrylate and related esters in polar solvents. In McGrath JE, editor. Anionic Polymerization Kinetics, Mechanisms, and Synthesis. ACS Symposium Series. Volume 166. Washington (DC) American Chemical Society 1981. p 441-461. 

Most UV/EB adhesives are based on an addition polymerization curing mechanism. Materials consist of acrylic acid esters of various forms or combinations of acrylates with aliphatic or aromatic epoxies, urethanes, polyesters, or polyethers. 

The reaction mechanism for isobutylene formation is derived from the general mechanism of Grassie and co-workers [8]. Polyisobutyl acrylate degradation produces more simple saturated esters than the other homologous polymeric esters. 

Under acidic conditions, furfuryl alcohol polymerizes to black polymers, which eventually become crosslinked and insoluble in the reaction medium. The reaction can be very violent and extreme care must be taken when furfuryl alcohol is mixed with any strong Lewis acid or Brn nstad acid. Copolymer resins are formed with phenoHc compounds, formaldehyde and/or other aldehydes. In dilute aqueous acid, the predominant reaction is a ring opening hydrolysis to form levulinic acid [123-76-2] (52). In acidic alcohoHc media, levulinic esters are formed. The mechanism for this unusual reaction in which the hydroxymethyl group of furfuryl alcohol is converted to the terminal methyl group of levulinic acid has recendy been elucidated (53). 

To a large extent, the properties of acryUc ester polymers depend on the nature of the alcohol radical and the molecular weight of the polymer. As is typical of polymeric systems, the mechanical properties of acryUc polymers improve as molecular weight is increased however, beyond a critical molecular weight, which often is about 100,000 to 200,000 for amorphous polymers, the improvement is slight and levels off asymptotically. 

Bulk Polymerization. The bulk polymerization of acryUc monomers is characterized by a rapid acceleration in the rate and the formation of a cross-linked insoluble network polymer at low conversion (90,91). Such network polymers are thought to form by a chain-transfer mechanism involving abstraction of the hydrogen alpha to the ester carbonyl in a polymer chain followed by growth of a branch radical. Ultimately, two of these branch radicals combine (91). Commercially, the bulk polymerization of acryUc monomers is of limited importance. 

Although the anionic polymerization mechanism is the predominant one for the cyanoacryhc esters, the monomer will polymerize free-radically under prolonged exposure to heat or light. To extend the usable shelf life, free-radical stabilizers such as quinones or hindered phenols are a necessary part of the adhesive formulation. 

Blocked isocyanates are particularly helpful in dual cure mechanisms. In one instance, UV light first polymerizes an acrylate polymer containing hydroxyl groups. The system also contains a malonate ester-blocked isocyanate. The one-component system is heated, which starts the polymerization of the acrylate. Higher temperatures unblock the isocyanate, permitting the cure of the urethane to proceed [15]. 

Because they are acrylic monomers, alkyl cyanoacrylate esters still require the addition of radical polymerization inhibitors, such as hydroquinone or hindered phenols, to prevent radically induced polymerization over time [3j. Since basic initiation of alkyl cyanoacrylate monomers is the predominant polymerization mechanism, large quantities of free radical inhibitors can be added, with little or no effect on adhesive performance. 

The furfuryl esters of acrylic and methacrylic acid polymerize via a free-radical mechanism without apparent retardation problems arising from the presence of the furan ring. Early reports on these systems described hard insoluble polymers formed in bulk polymerizations and the cross-linking ability of as little as 2% of furfuryl acrylate in the solution polymerization of methylacrylate121. ... 

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