Monomers peroxides

Acrylamide, 2-methyl-5-vinylpyridine and /V-vinylpyrrolidone can be polymerized under similar conditions, and also after decomposition of a monomer-peroxide complex. On the other hand, styrene, methyl methacrylate, isoprene, methyl acrylate, vinyl acetate and ascorbic acid do not polymerize under these conditions. Complex formation between persulphate and these monomer donors is more favourable energetically [165]. The complex is more stable, it is not decomposed into initiating radicals and polymerization does not occur. 

It is particularly typical of grafting amine-containing monomers peroxides cause oxidation of amino groups, which leads to a loss of commercial value of a grafted product. It should be remembered that most of the azo compounds are unsuitable as initiators not only because of half-life (tq.s) but also because cyanoalkyl radicals formed are inactive in abstraction reactions of hydrogen from chains. An exception is phenylazo-compounds (33) being a source of phenyl radicals that are most active in hydrogen abstraction reactions (Table 10.3). 

Modern GPPS is produced by continuous bulk and solution processes developed in the mid-1950s by major PS producers, BASF, Dow Chemical, Monsanto, Union Carbide, and others. In the modern continuous GPPS process, as the one shown in Figure 13.6, styrene monomer is continuously fed to a packed column (normally alumina, silica gel, or clay) to remove moisture, impurities, and inhibitor, blended with recycled styrene monomer, peroxide initiator (normally dialkyl or diacyl peroxides, such as di-fert-butyl peroxide, dicumyl peroxide, or fert-butyl peroxibenzoate utilized at low concentrations [I] <0.5% w/w in the feed), chain transfer agent (normally aliphatic... 

Polymerization takes place, in the following manner in the presence of suitable peroxide catalyst these compounds polymerize with themselves (homopolymerizatiOn) in aqueous emulsion. When the reaction is complete, the emulsified polymer may be used directly or the emulsion coagulated to yield the solid polymer (312). A typical polymerization mixture is total monomer (2-vinylthiazole), 100 sodium stearate, 5 potassium persulfate, 0.3 laurylmercaptan, 0.4 to 0.7 and water, 200 parts. 

Organic peroxides are used extensively for the curing of unsaturated polyester resins and the polymerization of monomers having vinyl unsaturation. The —O—O— bond is split into free radicals which can initiate polymerization or cross-linking of various monomers or polymers. 

Poly (methyl Acrylate). The monomer used for preparing poly(methyl acrylate) is produced by the oxidation of propylene. The resin is made by free-radical polymerization initiated by peroxide or azo catalysts and has the following formula ... 

Figure 6.3 Log-log plots of Rp versus concentration which verify the order of the kinetics with respect to the constituent varied, (a) Monomer (methyl methacrylate) concentration varied at constant initiator concentration. [Data from T. Sugimura and Y. Minoura, J. Polym. Sci. A-l 2735 (1966).] (b) Initiator concentration varied AIBN in methy methacrylate (o), benzoyl peroxide in styrene ( ), and benzoyl peroxide in methyl methacrylate ( ). (From P. J. Flory, Principles of Polymer Chemistry, copyright 1953 by Cornell University, used with permission.)...

Tetrahydrofurfuryl acrylate and methacrylate reactive unsaturated monomers, are readily polymerized and easily cross-linked by exposure to heat, peroxide catalysts, or uv radiation. 

The effectiveness of phenoHc inhibitors is dependent on the presence of oxygen and the monomers must be stored under air rather than an inert atmosphere. Temperatures must be kept low to minimise formation of peroxides and other products. Moisture may cause mst-initiated polymerization. 

Usually, free-radical initiators such as azo compounds or peroxides are used to initiate the polymerization of acrylic monomers. Photochemical (72—74) and radiation-initiated (75) polymerizations are also well known. At a constant temperature, the initial rate of the bulk or solution radical polymerization of acrylic monomers is first order with respect to monomer concentration and one-half order with respect to the initiator concentration. Rate data for polymerization of several common acrylic monomers initiated with 2,2 -azobisisobutyronittile (AIBN) [78-67-1] have been determined and are shown in Table 6. The table also includes heats of polymerization and volume percent shrinkage data. 

The type of initiator utilized for a solution polymerization depends on several factors, including the solubiUty of the initiator, the rate of decomposition of the initiator, and the intended use of the polymeric product. The amount of initiator used may vary from a few hundredths to several percent of the monomer weight. As the amount of initiator is decreased, the molecular weight of the polymer is increased as a result of initiating fewer polymer chains per unit weight of monomer, and thus the initiator concentration is often used to control molecular weight. Organic peroxides, hydroperoxides, and azo compounds are the initiators of choice for the preparations of most acryUc solution polymers and copolymers. 

Initiators, usually from 0.02 to 2.0 wt % of the monomer of organic peroxides or azo compounds, are dissolved in the reaction solvents and fed separately to the kettie. Since oxygen is often an inhibitor of acryUc polymerizations, its presence is undesirable. When the polymerization is carried out below reflux temperatures, low oxygen levels are obtained by an initial purge with an inert gas such as carbon dioxide or nitrogen. A blanket of the inert gas is then maintained over the polymerization mixture. The duration of the polymerization is usually 24 h (95). 

Initiators of suspension polymerization are organic peroxides or azo compounds that are soluble in the monomer phase but insoluble in the water phase. The amount of initiator influences both the polymerization rate and the molecular weight of the product (95). 

Anaerobic stmctural adhesives are typically formulated from acryhc monomers such as methyl methacrylate [80-62-6] C Hg02, and methacrylic acid [79-41-4] (see Acrylic ester polymers). Very often, cross-linking agents such as dimethacrylates are also added. A peroxide, such as cumene... 

When initiator is first added the reaction medium remains clear while particles 10 to 20 nm in diameter are formed. As the reaction proceeds the particle size increases, giving the reaction medium a white milky appearance. When a thermal initiator, such as AIBN or benzoyl peroxide, is used the reaction is autocatalytic. This contrasts sharply with normal homogeneous polymerizations in which the rate of polymerization decreases monotonicaHy with time. Studies show that three propagation reactions occur simultaneously to account for the anomalous auto acceleration (17). These are chain growth in the continuous monomer phase chain growth of radicals that have precipitated from solution onto the particle surface and chain growth of radicals within the polymer particles (13,18). 

High molecular weight polymers or gums are made from cyclotrisdoxane monomer and base catalyst. In order to achieve a good peroxide-curable gum, vinyl groups are added at 0.1 to 0.6% by copolymerization with methylvinylcyclosiloxanes. Gum polymers have a degree of polymerization (DP) of about 5000 and are useful for manufacture of fluorosiUcone mbber. In order to achieve the gum state, the polymerization must be conducted in a kineticaHy controlled manner because of the rapid depolymerization rate of fluorosiUcone. The expected thermodynamic end point of such a process is the conversion of cyclotrisdoxane to polymer and then rapid reversion of the polymer to cyclotetrasdoxane [429-67 ]. Careful control of the monomer purity, reaction time, reaction temperature, and method for quenching the base catalyst are essential for rehable gum production. 

Wheieas the BPO—DMA ledox system works well for curing of unsaturated polyester blends, it is not a very effective system for initiating vinyl monomer polymerizations, and therefore it generally is not used in such appHcations (34). However, combinations of amines (eg, DMA) and acyl sulfonyl peroxides (eg, ACSP) are very effective initiator systems at 0°C for high conversion suspension polymerizations of vinyl chloride (35). BPO has also been used in combination with ferrous ammonium sulfate to initiate emulsion polymerizations of vinyl monomers via a redox reaction (36). 

Because high temperatures are required to decompose diaLkyl peroxides at useful rates, P-scission of the resulting alkoxy radicals is more rapid and more extensive than for most other peroxide types. When methyl radicals are produced from alkoxy radicals, the diaLkyl peroxide precursors are very good initiators for cross-linking, grafting, and degradation reactions. When higher alkyl radicals such as ethyl radicals are produced, the diaLkyl peroxides are useful in vinyl monomer polymerizations. 

Ketone Peroxides. These materials are mixtures of compounds with hydroperoxy groups and are composed primarily of the two stmctures shown in Table 2. Ketone peroxides are marketed as solutions in inert solvents such as dimethyl phthalate. They are primarily employed in room-temperature-initiated curing of unsaturated polyester resin compositions (usually containing styrene monomer) using transition-metal promoters such as cobalt naphthenate. Ketone peroxides contain the hydroperoxy (—OOH) group and thus are susceptible to the same ha2ards as hydroperoxides. 

The aqueous phase into which the monomer mix is dispersed is also prepared in a separate tank before transferring to the copolymerization ketde. It contains a catalyst, such as benzoyl peroxide [94-36-0], to initiate and sustain the polymerization reaction, and chemicals that aid in stabilizing the emulsion after the desired degree of dispersion is achieved. Careful adherence to predeterrnined reaction time and temperature profiles for each copolymer formulation is necessary to assure good physical durabiHty of the final ion-exchange product. 

Unsaturated polyester resins prepared by condensation polymerization constitute the largest industrial use for maleic anhydride. Typically, maleic anhydride is esterified with ethylene glycol [107-21-1] and a vinyl monomer or styrene is added along with an initiator such as a peroxide to produce a three-dimensional macromolecule with rigidity, insolubiUty, and mechanical strength. 

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