Methyl methacrylate termination

It was suggested (66) that anionic polymerization of methyl methacrylate terminated by isomerization of the carbanion into a carboxylate ion by migration of a methyl carbonium ion. However, the authors later stated (73) that the methyl methacrylate used was not sufficiently well purified. Schreiber (59) pointed out that methyl methacrylate reacts with phenyl lithium in the following manner ... 

Like other overnight discoveries, the present success of living-radical polymerization is built on the work of pioneers in the field who laid the groundwork for what was to come. The first indication that a terminated polymer prepared by a free-radical polymerization could chain extend was reported by Braun [2] in 1981. Thus, a purified oligomeric methyl methacrylate, terminated with a primary radical from... 

If more than one monomer species is present in the reaction medium, a copolymer or an interpolymer can result from the polymerization reaction. Whether, however, the reaction products will consist of copolymers or just mixtures of homopolymers or of both depends largely upon the reactivity of the monomers. A useful and a simplifying assumption in kinetic analyses of free-radical copolymerizations is that the reactivity of polymer radicals is governed entirely by the terminal monomer units. " For instance, a growing polymer radical, containing a methyl methacrylate terminal unit, is considered, in terms of reactivity, as a poly(methyl methacrylate) radical. This assumption, not always adequate, can be used to predict satisfactorily the behavior of many mixtures of monomers. Based on this assumption, the copolymerization of a pair of monomers involves four distinct growth reactions and two types of polymer radicals. 

Other workers have reported the preparation of methyl methacrylate-styrene and methyl methacrylate-vinyl chloride block copolymers by a two stage free radical polymerization. First they prepared telomers of styrene (or vinyl chloride) and poly(methyl methacrylate) terminated by carbon tetrachloride. Then they heated the telomers of the desired monomers in the presence of bis-(ephedrine) copper to prepare sequential ABAB block copolymers(87). Poly(methyl methacrylate-b-acrylonitrile) was prepared by heating (CO)5Mn(CF2)2 terminated poly(methyl methacrylate) and acrylonitrile at 100 C(88) ... 

Apart from the nse of a polymerizable alkoxysilane, silica/polystyrene composite particles with a raspberry-like morphology have been elaborated in the presence of a methyl methacrylate-terminated polyethylene glycol macromonomer. This macromonomer is mainly hydrophilic due to the presence of ethylene oxide repeat units (n 23), which are able to form hydrogen bonds with the silanol groups of silica and adsorb on its snrface. In addition, this molecnle contains a methacrylate functionality able to copoljmerize with styrene thus... 

In the radical polymerization of methyl methacrylate, termination by combination (also called coupling) is demanding because it requires that each carbon atom forming the resulting bond be tetrasubstituted. Thus, the relative importance of the two processes varies with temperature since their activation energies are appreciably different ... 

In general it is found that both types of termination take place in any particular system but to different extents. For instance it is found that polystyrene terminates principally by combination whereas poly(methyl methacrylate) terminates almost exclusively by disproportionation at high temperatures and by both mechanisms at lower temperatures. 

Combination and disproportionation are competitive processes and do not occur to the same extent for all polymers. For example, at 60°C termination is virtually 100% by combination for polyacrylonitrile and 100% by disproportionation for poly (vinyl acetate). For polystyrene and poly (methyl methacrylate), both reactions contribute to termination, although each in different proportions. Each of the rate constants for termination individually follows the Arrhenius equation, so the relative amounts of termination by the two modes is given by... 

Bulk Polymerization. This is the method of choice for the manufacture of poly(methyl methacrylate) sheets, rods, and tubes, and molding and extmsion compounds. In methyl methacrylate bulk polymerization, an auto acceleration is observed beginning at 20—50% conversion. At this point, there is also a corresponding increase in the molecular weight of the polymer formed. This acceleration, which continues up to high conversion, is known as the Trommsdorff effect, and is attributed to the increase in viscosity of the mixture to such an extent that the diffusion rate, and therefore the termination reaction of the growing radicals, is reduced. This reduced termination rate ultimately results in a polymerization rate that is limited only by the diffusion rate of the monomer. Detailed kinetic data on the bulk polymerization of methyl methacrylate can be found in Reference 42. 

The auto-acceleration effect appears most marked with polymers that are insoluble in their monomers. In these circumstances the radical end becomes entrapped in the polymer and termination reactions become very difficult. It has been suggested that, in thermodynamic terms, methyl methacrylate is a relatively poor solvent for poly(methyl methacrylate) because it causes radicals to coil while in solution. The termination reaction is then determined by the rate at which the radical ends come to the surface of the coil and hence become available for mutual termination. 

In contrast to /3-PCPY, ICPY did not initiate copolymerization of MMA with styrene [39] and AN with styrene [40]. However, it accelerated radical polymerization by increasing the rate of initiation in the former case and decreasing the rate of termination in the latter case. The studies on photocopolymerization of MMA with styrene in the presence of ICPY has also been reported [41], /8-PCPY also initiated radical copolymerization of 4-vinylpyridine with methyl methacrylate [42]. However, the ylide retarded the polymerization of N-vinylpyrrolidone, initiated by AIBN at 60°C in benzene [44]. (See also Table 2.)... 

Which mechanism of termination will be preferably applied depends largely on the monomer used. Thus, methyl methacrylate chains terminate to a large extent by disproportionation, whereas styrene chains tend to termination by combination. The ratios of termination rate constants 8 = ktJkic (for disproportionation, td, combination,, c) are 5 == 0 and 5 = 2 for styrene [95] and methyl methacrylate [96], respectively. In the case of styrene, however, the values of 8 reported in the literature are at variance. Berger and Meyerhoff [97] found 8 = 0.2, at 52°C. Therefore, it is possible that a fraction of styrene terminates by disproportionation. 

Formation of block polymers is not limited to hydrocarbon monomers only. For example, living polystyrene initiates polymerization of methyl methacrylate and a block polymer of polystyrene and of polymethyl methacrylate results.34 However, methyl methacrylate represents a class of monomers which may be named a suicide monomer. Its polymerization can be initiated by carbanions or by an electron transfer process, the propagation reaction is rapid but eventually termination takes place. Presumably, the reactive carbanion interacts with the methyl group of the ester according to the following reaction... 

Yamashita and co-workers have also determined the reactivity ratios of styryl terminated PDMS macromonomers (M,) with styrene (M2) and methyl methacrylate (M2)123>. They have determined (r2) and (r2) as 1.1 and 0.60 respectively. These values... 

Siloxane-(methyl methacrylate) networks showing high oxygen permeabilities were prepared by gamma-irradiation of tx,(o-methacryloyl terminated tetramethyl-disiloxanes and methyl methacrylate 325). Due to the utilization of very low molecular weight disiloxane modifier, no phase separation was observed in the networks produced. DSC studies showed only one Tg around 120 °C. These materials were evaluated... 

Although the low temperature polymerization of methyl methacrylate in polar solvents such as THF was believed to proceed without termination, a more exhaustive investigation55) revealed some slow termination processes resulting from the formation of a, not yet specified agent, supposedly produced in the initiation step. Since the nature of the terminating agent is still unknown it is premature to discuss here the proposed schemes of this termination process. 

Both termination mechanisms have been shown to occur experimentally, the method being to examine the polymer molecules formed for fragments of initiator. In such a way polystyrene has been found to terminate mainly by combination and poly(methyl methacrylate) entirely by disproportionation at temperatures above 60 °C. 

II. B polyethylene glycol, ethylene oxide, polystyrene, diisocyanates (urethanes), polyvinylchloride, chloroprene, THF, diglycolide, dilac-tide, <5-valerolactone, substituted e-caprolactones, 4-vinyl anisole, styrene, methyl methacrylate, and vinyl acetate. In addition to these species, many copolymers have been prepared from oligomers of PCL. In particular, a variety of polyester-urethanes have been synthesized from hydroxy-terminated PCL, some of which have achieved commercial status (9). Graft copolymers with acrylic acid, acrylonitrile, and styrene have been prepared using PCL as the backbone polymer (60). 

Torkelson and coworkers [274,275] have developed kinetic models to describe the formation of gels in free-radical pol5nnerization. They have incorporated diffusion limitations into the kinetic coefficient for radical termination and have compared their simulations to experimental results on methyl methacrylate polymerization. A basic kinetic model with initiation, propagation, and termination steps, including the diffusion hmitations, was found to describe the gelation effect, or time for gel formation, of several samples sets of experimental data. 

The above explanation of autoacceleration phenomena is supported by the manifold increase in the initial polymerization rate for methyl methacrylate which may be brought about by the addition of poly-(methyl methacrylate) or other polymers to the monomer.It finds further support in the suppression, or virtual elimination, of autoacceleration which has been observed when the molecular weight of the polymer is reduced by incorporating a chain transfer agent (see Sec. 2f), such as butyl mercaptan, with the monomer.Not only are the much shorter radical chains intrinsically more mobile, but the lower molecular weight of the polymer formed results in a viscosity at a given conversion which is lower by as much as several orders of magnitude. Both factors facilitate diffusion of the active centers and, hence, tend to eliminate the autoacceleration. Final and conclusive proof of the correctness of this explanation comes from measurements of the absolute values of individual rate constants (see p. 160), which show that the termination constant does indeed decrease a hundredfold or more in the autoacceleration phase of the polymerization, whereas kp remains constant within experimental error. 

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