Kinetics and mechanism of polymerization of methyl methacrylate initiated by stibonium ylide

Homopolymerization of methyl methacrylate (MMA) was carried out in the presence of triphenylstibonium 1,2,3,4-tetraphenyl-cyclopentadienylide as an initiator in dioxane at 65°C±0·l°C. The system follows non-ideal radical kinetics (R _p ∝ [M]^1·4 [I]^0·44 @#@) due to primary radical termination as well as degradative chain-transfer reaction. The overall activation energy and average value ofk ₂ ^p /k _t were 64 kJmol⁻¹ and 0.173 × 10⁻³ 1 mol⁻¹ s⁻¹ respectively     

Kinetic study of the alternating copolymerization of butadiene and methyl methacrylate

A kinetic investigation of the alternating copolymerization of butadiene and methyl methacrylate with the use of a system of ethylaluminum dichloride and vanadyl chloride as a catalyst was undertaken. The relation between the polymer yield and the molar fraction of methyl methacrylate in the feed was examined by continuous variation of butadiene and methyl methacrylate, the concentrations of total monomer, ethylaluminum dichloride, and vanadyl chloride being kept constant. This continuous variation method revealed that the polymer yield attains its maximum value with a monomer feed containing less than the 0.5 molar fraction of methyl methacrylate. This value of the molar fraction of methyl methacrylate affording the maximum polymer yield decreased on increasing the total monomer concentration but was not changed on varying the concentration of ethylaluminum dichloride. The number of active species estimated from the relation between yield and molecular weight of the polymer was almost constant, regardless of the molar fraction of methyl methacrylate in the feed. Consequently, it can be said that the maximum polymer yield depends mainly on the propagation reaction, not on the initiation reaction or the termination reaction. Three types of the mechanism have been discussed for this alternating copolymerization: polymerization via alternating addition of butadiene and methyl methacrylate complexed with ethylaluminum dichloride by the Lewis-Mayo scheme; polymerization via the ternary intermediate of butadiene, methyl methacrylate, and ethylaluminum dichloride; polymerization via the complex formation of butadiene and methyl methacrylate complexed with ethylaluminum dichloride occurring only at the growing polymer radical. From the kinetic results obtained, it was shown that the first and third schemes are excluded, and polymerization by way of the ternary intermediate is compatible with the data.     

Kinetic study of high-conversion copolymerization of butyl acrylate with methyl methacrylate in solution

Butyl acrylate (BA) and methyl methacrylate (MMA) have been copolymerized in a 3 mol/L benzene solution using 2,2′-azobis(isobutyronitrile) (AIBN) as initiator over a wide composition and conversion range. The overall copolymerization parameter k_p/k_t^1/2 and the composition of the copolymer formed have been measured as a function of conversion. Theoretical values of the coupled parameter k_p/k_t^1/2 calculated from the implicit penultimate unit model and those of cumulative copolymer composition, determined from the Mayo—Lewis terminal model, have been correlated with those experimentally obtained. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 1961–1965, 1997     

Photopolymerization of methyl methacrylate initiated by sulphur dioxide

In catalytic concentrations (10^?5?10^?4 mol l^?1) sulphur dioxide induces polymerization of MMA, particularly on photoactivation. The effective initiating species appears to be the monomer-SO₂ complex rather than free SO₂. A mechanism involving biradical initiation by decomposition of the initiating species, linear propagation in two directions, and significant termination of growing chains by chain transfer with initiating species has been suggested. The initiator transfer constant is 1.6 at 40°.     

Graft copolymerization of methyl methacrylate to poly(vinyl alcohol) initiated by ferric ion-hydrogen peroxide system

The reaction occurring on treatment of samples of poly(vinyl alcohol) previously oxidized by sodium hypochlorite with ferric ion and hydrogen peroxide was studied. The graft copolymerization taking place on adding methyl methacrylate to the above system was also studied. Early in the reaction there was a period during which hydrogen peroxide was greatly reduced by the poly(vinyl alcohol), and this corresponded with a rapid cleavage reaction of the main chain of the polymer. Moreover, it was found that the reaction was quantitatively proportional to the formation of carbonyl groups in the sample. On the other hand, very few grafts were scarcely formed during this period; they formed by a mild reaction which took place immediately after this period. It seems that this behavior is quite different from that observed with the ceric ion initiating system. It is presumed that the formation of grafts is due to radicals formed by the cleavage of the main chain, and that the structure of the copolymer so formed is something like a block polymer.     

Emulsion copolymerization of styrene and methyl methacrylate

Chain transfer constants to monomer have been measured by an emulsion copolymerization technique at 44°C. The monomer transfer constant (ratio of transfer to propagation rate constants) is 1.9 × 10^?5 for styrene polymerization and 0.4 × 10^?5 for the methyl methacrylate reaction. Cross-transfer reactions are important in this system; the sum of the cross-transfer constants is 5.8 × 10^?5. Reactivity ratios measured in emulsion were r₁ (styrene) = 0.44, r₂ = 0.46. Those in bulk polymerizations were r₁ = 0.45, r₂ = 0.48. These sets of values are not significantly different. Monomer feed compcsition in the polymerizing particles is the same as in the monomer droplets in emulsion copolymerization, despite the higher water solubility of methyl methacrylate. The equilibrium monomer concentration in the particles in interval-2 emulsion polymerization was constant and independent of monomer feed composition for feeds containing 0.25–1.0 mole fraction styrene. Radical concentration is estimated to go through a minimum with increasing methyl methacrylate content in the feed. Rates of copolymerization can be calculated a priori when the concentrations of monomers in the polymer particles are known.     

Catalytic chain transfer copolymerization of methyl methacrylate and methyl acrylate

Bis(aqua)bis((difluoroboryl)dimethylglyoximate)cobalt(II) (COBF) has proven to be a very effective catalytic chain transfer agent in the copolymerization of MA and MMA. The chain transfer activity depends on the fraction of MMA in the monomer feed and the total radical concentration. The polymerization can be described by a model that combines features of catalytic chain transfer for MMA homopolymerization and cobalt mediated controlled radical polymerization of MA. According to the model part of the COBF is covalently bonded to MA‐ended polymeric radicals and cannot take part in the chain transfer step. The model can also account for the observed inhibition time that occurs at high chain transfer agent concentration and low fraction of MMA in the monomer feed.     

Kinetic studies of nonaqueous polymerization of methyl methacrylate initiated by ferric laurate–n-hexyl amine system

The polymerization of methyl methacrylate was studied in carbon tetrachloride medium with ferric laurate, a metal soap, in combination with n-hexyl amine as the initiator system at 60°C. The rate of polymerization was found to be linear with the monomer concentration and proportional to the square root of both ferric ion and amine concentration. A reaction scheme involving initial complex formation between ferric ion and amine and subsequent reaction of the complex with the solvent molecule to produce free radicals responsible for initiation of polymerization has been postulated to account for the observed results.     

Kinetic study of free-radical copolymerization of ethyl α-benzoyloxymethylacrylate with methyl methacrylate in benzene

From a phenomenological point of view, the Mayo-Lewis terminal model can describe both copolymer composition and the variation of copolymerization rate for the ethyl α-benzoyloxymethylacrylate/methyl methacrylate/benzene/2,2′-azoisobutyronitrile system.     

Polymerization of coordinated monomers. XIX. Kinetic study of the alternating copolymerization of methyl methacrylate with styrene by boron trichloride

Alternating copolymerizations of methyl methacrylate with styrene in the presence of boron trichloride at 0°C in 1,2-dichloroethane were carried out by using benzoyl peroxide as an initiator. Conversion increased proportionally with polymerization time, whereas the degree of polymerization was constant irrespective of time. The rate depended linearly on the square root of the concentration of benzoyl peroxide. The equilibrium constants for the formation of the ternary molecular complex composed of methyl methacrylate, styrene, and boron trichloride in 1,2-dichloroethane at ?20, ?10, and +4°C were determined by ¹H-NMR spectroscopy. The concentrations of the ternary molecular complex in the polymerization mixtures were evaluated from the equilibrium constant of the formation. The rate of the alternating copolymerization was proportional to the first order of the concentration of the ternary molecular complex. The distribution of methyl methacrylate-centered triads in the alternating copolymer was different from that of styrene-centered triads. These results can be explained by a mechanism involving the homopolymerization of a ternary molecular complex.     

Dispersion copolymerization of methyl methacrylate and n-butyl acrylate

In the dispersion copolymerization of methyl methacrylate (MMA) and n-butyl acrylate (BA), the particle size increases with an increasing MMA fraction in the comonomer. The power dependence of the particle size on the initiator concentration also increases with an increasing MMA concentration. Similar to what can be found in the homopolymerizations, two populations can be observed in the molecular weight distributions of the copolymers. Core–shell structured particles with a poly(methyl methacrylate)-rich core and a poly(n-butyl acrylate)-rich shell result from the copolymerizations because of the significantly different reactivity ratios. The reaction rates of the dispersion copolymerization are lower than those of the homopolymerization of BA and close to or lower than those of the homopolymerization of MMA, depending on the ratio of the monomers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2105–2112, 2007     

Graft copolymerization of methyl methacrylate onto curdlan

Graft copolymerization of methyl methacrylate onto curdlan was first investigated. In the graft copolymerization initiated by ammonium persulfate (APS) in DMSO under a homogeneous condition, the resulting graft copolymers had low molecular weights and low grafting percentages. However, the initiation by APS in water gave graft copolymers having relatively higher molecular weight ( ) and higher grafting percentage (548%) than those copolymers obtained by the homogeneous condition. When the graft copolymerization was carried out by cerium (IV) ammonium nitrate-HNO₃ initiation, the graft copolymer had the highest grafting percentage of 1620% without degradation of the curdlan backbone. The resulting graft copolymers were soluble in DMSO. The graft copolymers obtained by the cerium salt had narrow molecular weight distributions () compared with those by the APS catalyst in DMSO or water. The graft copolymers decomposed with sulfuric acid to isolate PMMAs, which molecular weights were larger than that of the corresponding homo-PMMAs. The structure of the grafted copolymers was characterized by IR, ¹³C NMR, DSC, and SEM. It was found that the graft copolymers exhibited the glass transition temperature (T_g), though curdlan had no T_g. As the grafting percentage increased, the T_g increased to reach 270°C, which was higher than the decomposition temperature of curdlan. The surface image of the grafted copolymers observed by SEM, showed smoothless compared with that of curdlan. It was also revealed that the graft copolymers having the grafting percentage of 1620% swelled in common organic solvents up to 4.5 times of the weight of the dry graft copolymer to form gels. © 1996 John Wiley & Sons, Inc.     

Ultrasonically initiated emulsion polymerization of methyl methacrylate

The ultrasonically initiated emulsion polymerization of methyl methacrylate (MMA) was investigated. Experimental results show that sodium dodecyl sulfonate (SDS) surfactant plays a very important role in obtaining a high polymer yield, because in the absence of SDS, monomer conversion is near zero. Thus, the surfactant serves as an initiator and as interfacial modifier in this system (MMA/H₂O), and the monomer conversion increases significantly with increasing SDS concentration. An increase in the reactor temperature also leads to an increase in the monomer conversion. An appropriate increase in the N₂ purging rate also leads to higher conversion. The conversion of MMA decreases with increasing monomer concentration because of the higher viscosity of the system. With the experimental results, optimized reaction conditions were obtained. Accordingly, a high monomer conversion of about 67% and a high molecular weight of several millions can be obtained in a period of about 30 min. Furthermore, transmission electron micrographs show that the latex particles prepared are nanosized, indicating a promising technique for preparing nanoscale latex particles with a small amount of surfactant. In conclusion, a promising technique for ultrasonically initiated emulsion polymerization has been successfully performed. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3356–3364, 2001     

Reversible addition-fragmentation chain transfer copolymerization of methyl methacrylate and methyl acrylate

Pseudo-living radical copolymerization of methyl methacrylate and methyl acrylate under reversible addition-fragmentation chain transfer in a mass in the presence of reversible chain transfer agents of different nature was implemented. A comparison of physical and mechanical properties of narrowly dispersed copolymers was performed as well as copolymers obtained by uncontrolled radical polymerization.     

Graft copolymerization of 2-hydroxyethyl methacrylate and methyl methacrylate onto hide powder

Graft copolymerization of 2-hydroxyethyl methacrylate(HEMA) and mixtures of HEMA with methyl methacrylate (MMA) onto hide powder was attempted using ceric ammonium nitrate as initiator, with a view to optimize the conditions for graft copolymerization. Percent grafting and grafting efficiency were calculated for various variables such as monomer concentration, initator concentration and mole ratio of HEMA to MMA. R_p, R_g and R_h (rates of polymerization, grafting and homopolymerization respectively) were also evaluated. It was observed that R_p increased linearly with increasing concentration of MMA except at very low concentrations of the monomer. An explanation is given for the effect of variables on extent of grafting and grafting efficiency.     

Photo-induced graft copolymerization of methyl methacrylate on cellulose

Graft copolymerization initiated by ultraviolet light irradiation at 40°C in a hard glass vessel under nitrogen was examined. The graft copolymerization was observed to occur easily after some induction period without any use of photosensitizer, though it was found the per cent grafting and the grafting efficiency were markedly affected by the quantities of cellulose and monomer. In the system without cellulose, homopolymerization of methyl methacrylate hardly took place, but the use of cellulose caused the formation of homopolymer too, and a grafting efficiency in the range of 60–80% generally resulted. Ferric chloride or sodium anthraquinone-2,7-disulfonate (AQ) acted on the polymerization reaction as photosensitizers to reduce its induction period. Though ferric chloride acted to develop both the per cent grafting and the number of grafts, not the same effects were observed with AQ. Oxalic acid, which was employed with the object of eliminating very small amount of metals contained in cellulose, was found to act favorably in the formation of grafts, much like ferric chloride.