Homopolymerizations methacrylate

AlkyUithium compounds are primarily used as initiators for polymerizations of styrenes and dienes (52). These initiators are too reactive for alkyl methacrylates and vinylpyridines. / -ButyUithium [109-72-8] is used commercially to initiate anionic homopolymerization and copolymerization of butadiene, isoprene, and styrene with linear and branched stmctures. Because of the high degree of association (hexameric), -butyIUthium-initiated polymerizations are often effected at elevated temperatures (>50° C) to increase the rate of initiation relative to propagation and thus to obtain polymers with narrower molecular weight distributions (53). Hydrocarbon solutions of this initiator are quite stable at room temperature for extended periods of time the rate of decomposition per month is 0.06% at 20°C (39). 

Vinyhdene chloride copolymerizes randomly with methyl acrylate and nearly so with other acrylates. Very severe composition drift occurs, however, in copolymerizations with vinyl chloride or methacrylates. Several methods have been developed to produce homogeneous copolymers regardless of the reactivity ratio (43). These methods are appHcable mainly to emulsion and suspension processes where adequate stirring can be maintained. Copolymerization rates of VDC with small amounts of a second monomer are normally lower than its rate of homopolymerization. The kinetics of the copolymerization of VDC and VC have been studied (45—48). 

During mutual graft copolymerization, homopolymerization always occurs. This is one of the most important problems associated with this technique. When this technique is applied to radiation-sensitive monomers such as acrylic acid, methacrylic acid, polyfunctional acrylates, and their esters, homopolymer is formed more rapidly than the graft. With the low-molecular weight acrylate esters, particularly ethyl acrylate, the homopolymer problem is evidenced not so much by high yields as by erratic and irreproducible grafting. 

Several radical copolymerizations of vinyl 2-furoate with well-known monomers (50 50) were also studied. Complete inhibition was obtained with vinyl acetate, very strong retardation with styrene, vinyl chloride and acrylonitrile methyl methacrylate homopolymerized without appreciable decrease in rate. It is evident that the degree of retardation that vinyl 2-furoate imposes upon the other monomer depends on the stability of the latter s free radical. With styrene and vinyl chloride the small amounts of fairly low molecular-weight products contained units from vinyl 2-furoate which had entered the chain both through the vinyl bond and through the ring (infrared band at 1640 cm-1). 

For less polar monomers, the most extensively studied homopolymerizations are vinyl esters (e.g. VAc), acrylate and methacrylate esters and S. Most of these studies have focused wholly on the polymerization kinetics and only a few have examined the mierostructures of the polymers formed. Most of the early rate data in this area should be treated with caution because of the difficulties associated in separating effects of solvent on p, k and initiation rate and efficiency. 

Monomers not amenable to direct homopolymerization using a particular reagent can sometimes be copolymcrizcd. For example, NMP often fails with methacrylates (e.g. MMA, BMA), yet copolymerizalions of these monomers with S are possible even when the monomer mix is predominantly composed of the methacrylate monomer,15j This is attributed to the facility of cross propagation and the relatively low steady state concentration of propagating radicals with a terminal MMA (Section 7.4.3.1). MMA can also be copolymerized with S or acrylates at low temperature (60 C).111 Under these conditions, only deactivation of propagating radicals with a terminal MMA unit is reversible, deactivation of chains with a terminal S or acrylate unit is irreversible. Molecular weights should then be controlled by the reactivity ratios and the comonomer concentration rather than by the nitroxide/alkoxyamine concentration. 

Only fragmented data are available on polymerization of other methacrylates. Propagation constants and the respective Arrhenius parameters for the homopolymerization of various methacrylates initiated by sodium metallo-organics were reported recently +3,56) and are given in Table 2. 

Sutterlin 22.), Figures 4,5, and 6, styrene and methyl methacrylate (MMA) homopolymerizations in a batch reactor at 80 °C with various amounts of added surfactant. 

Two free radical-initiated polymerizations are used in turn as examples the homopolymerization of methyl methaK rylate and the copolymerization of styrene n-butyl methacrylate. 

In this paper the GPC interpretation underlying the kinetic model of methyl methacrylate polymerization previously publMied and by now shown to be useful is detailed and updated. It provides a prime example of the conventional experimental use of GPC in homopolymerization studio. 

Homopolymerization of ethyl 4-vinyl-a-cyano-p-phenylcinnamate with AIBN in benzene gave a soluble polymer of inherent viscosity 0.2 djf,/g. There was no evidence for involvement of the tetra-substituted double bond in the polymerization. Copolymerizations with styrene and methyl methacrylate were also successful. 

Homopolymerization of monomer I or its copolymerization with 2-hydro-xyethyl methacrylate or 3-hydroxypropyl methacrylate gave the frist series of... 

Auto-acceleration was observed in the homopolymerization of methacrylic acid solutions over limited concentration ranges in methanol and in water. Perhaps under such conditions swelling of the polymer favors monomer diffusion leading to a larger amount of pre-oriented structures III. Alternatively, a monomer-solvent complex may arise which favors a pre-oriented structure and thus, may be responsible for the onset of a matrix effect (9). 

The product involves a combination of homopolymerization and graft polymerization of a monomer such as methyl methacrylate to wood. 

Covalent bonding of acrylic or methacrylic monomer to the template leads to multifunctional monomers (multimonomers).If monomer units are connected by covalent bonds within the frame of the template and polymerization proceeds according to the zip mechanism , a product with ladder-type structure can he expected. The structure of products obtained depends on the competition between the reactions proceeding on the template and the reaction between groups belonging to different macromolecules (templates). Template homopolymerization in this case can he represented by the scheme given in Figure 9.1. 

If one combines all of this information, one can develop a scheme to account for all of these observations. There is a competition for initiator in the reaction of SBS with methyl methacrylate some is used to initiate the homopolymerization of the monomer and some is used to remove an allylic hydrogen from the SBS chain. Once both of these sites are initiated, they will both compete for monomer. In the other three cases the initiator can once again initiate both the polymer and the monomer. For these monomers the reactivity of the... 

In connection with the cause of the field influences on the cationic homopolymerization, it is interesting to study how free radical polymerizations are affected by an electric field. Table 1 shows that both the polymer yield and the degree of polymerization were not affected at all by the field, though the intensity was much higher than that applied to cationic systems. The situation was the same for free radical polymerizations of styrene by benzoylperoxide (72), and of methyl methacrylate by benzoylperoxide and azobisisobutyronitiile (77). 

A similar approach was used in Ref. 103) to obtain the fat-soluble derivatives of heparin by its copolymerization with butyl methacrylate or vinyllaurate and to get high-molecular products with a molecular mass of over 200000 by homopolymerization of the unsaturated heparin derivative. The products were used as thromboresistant... 

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