Free radical polymerization initiation phase

In 1981 we reported (2, 3) the first examples of free radical polymerizations under phase transfer conditions. Utilizing potassium persulfate and a phase transfer catalyst (e.g. a crown ether or quaternary ammonium salt), we found the solution polymerization of acrylic monomers to be much more facile than when common organic-soluble initiators were used. Somewhat earlier, Voronkov and coworkers had reported (4) that the 1 2 potassium persulfate/18-crown-6 complex could be used to polymerize styrene and methyl methacrylate in methanol. These relatively inefficient polymerizations were apparently conducted under homogeneous conditions, although exact details were somewhat unclear. We subsequently described (5) the... 

In conclusion, several examples of free radical polymerizations under phase transfer conditions have been described in the literature since the initial reports in 1981. In all of these cases it is apparent that transfer of an active species from one phase to a second phase is intimately involved in the initiation step of the polymerization. However, it is also clear that these are complex reactions mechanistically, and one general kinetic scheme may not be sufficient to describe them all. The extent of phase transfer and the exact species transferred will depend to a large extent upon the nature of the two phases, upon the... 

Macroporosity of styrene—DVB copolymers arises from the presence of certain diluents in the initial homogeneous solution of the comonomers these do not participate in free radical polymerization but phase-separate from the growing polymer. Three types of diluents have generally been recognized (i) precipitating media for linear polystyrene, (ii) good solvents for polystyrene, and (iii) linear polystyrene or other polymers. 

Polymerization begins in the aqueous phase with the decomposition of the initiator. The free radicals produced initiate polymerization by reacting with the monomers dissolved in the water. The resulting polymer radicals grow very slowly because of the low concentration of monomer, but as they grow they acquire surface active properties and eventually enter micelles. There is a possibility that they become adsorbed at the oil-water interface of the monomer... 

The effects of increasing the concentration of initiator (i.e., increased conversion, decreased M , and broader PDi) and of reducing the reaction temperature (i.e., decreased conversion, increased M , and narrower PDi) for the polymerizations in ambient-temperature ionic liquids are the same as observed in conventional solvents. May et al. have reported similar results and in addition used NMR to investigate the stereochemistry of the PMMA produced in [BMIM][PFgj. They found that the stereochemistry was almost identical to that for PMMA produced by free radical polymerization in conventional solvents [43]. The homopolymerization and copolymerization of several other monomers were also reported. Similarly to the findings of Noda and Watanabe, the polymer was in many cases not soluble in the ionic liquid and thus phase-separated [43, 44]. 

Phase-transfer techniques are widely used for the preparation of polymers. For example, potassium fluoride is used to produce poly(etherketone)s under phase-transfer conditions (Scheme 10.18). Use of this reagent allows the chloroaro-matics to be used as starting material as opposed to the more expensive flu-oroaromatics that are usually employed [23]. This method is suitable for the synthesis of high molecular weight semicrystalline poly(ether ketone)s, although the presence of excess potassium fluoride in the reaction mixture can lead to degradation reactions. The use of a phase transfer catalyst can allow the use of water-soluble radical initiators, such as potassium peroxomonosulfate used to promote the free-radical polymerization of acrylonitrile [24],... 

Rasmussen and co-workers. Chapter 10, have shown that many free-radical polymerizations can be conducted in two-phase systems using potassium persulfate and either crown ethers or quaternary ammonium salts as initiators. When transferred to the organic phase persulfate performs far more efficiently as an initiator than conventional materials such as azobisisobutyronitrile or benzoyl peroxide. In vinyl polymerizations using PTC-persulfate initiation one can exercise precise control over reaction rates, even at low temperatures. Mechanistic aspects of these complicated systems have been worked out for this highly useful and economical method of initiation of free-radical polymerizations. 

A critical survey of the literature on free radical polymerizations in the presence of phase transfer agents indicates that the majority of these reactions are initiated by transfer of an active species (monomer or initiator) from one phase to another, although the exact details of this phase transfer may be influenced by the nature of the phase transfer catalyst and reaction medium. Initial kinetic studies of the solution polymerization of methyl methacrylate utilizing solid potassium persulfate and Aliquat 336 yield the experimental rate law ... 

Until recently, the most detailed kinetic investigations of phase transfer free radical polymerizations were those of Jayakrishnan and Shah (11, 12). Both of these studies have been conducted in two phase aqueous/organic solvent mixtures with either potassium or ammonium persulfate as the initiator, and have corroborated our earlier conclusions (2, 3)... 

Because the size of the emulsion droplets dictates the diameter of the resulting capsules, it is possible to use miniemulsions to make nanocapsules. To cite a recent example, Carlos Co and his group developed relatively monodisperse 200-nm capsules by interfacial free-radical polymerization (Scott et al. 2005). Dibutyl maleate in hexadecane was dispersed in a miniemulsion of poly(ethylene glycol)-1000 (PEG-1000) divinyl ether in an aqueous phase. They generated the miniemulsion by sonication and used an interfacially active initiator, 2,2 -azobis(A-octyl-2-methyl-propionamidine) dihydrochloride, to initiate the reaction, coupled with UV irradiation. 

Taylor in 1925 demonstrated that hydrogen atoms generated by the mercury sensitized photodecomposition of hydrogen gas add to ethylene to form ethyl radicals, which were proposed to react with H2 to give the observed ethane and another hydrogen atom. Evidence that polymerization could occur by free radical reactions was found by Taylor and Jones in 1930, by the observation that ethyl radicals formed by the gas phase pyrolysis of diethylmercury or tetraethyllead initiated the polymerization of ethylene, and this process was extended to the solution phase by Cramer. The mechanism of equation (37) (with participation by a third body) was presented for the reaction, - which is in accord with current views, and the mechanism of equation (38) was shown for disproportionation. Staudinger in 1932 wrote a mechanism for free radical polymerization of styrene,but just as did Rice and Rice (equation 32), showed the radical attack on the most substituted carbon (anti-Markovnikov attack). The correct orientation was shown by Flory in 1937. In 1935, O.K. Rice and Sickman reported that ethylene polymerization was also induced by methyl radicals generated from thermolysis of azomethane. 

The sample used to study the relationship between the volume phase transition and the frictional property is poly( /V-isopropylacrylamide) gel which shows a small discontinuous volume phase transition at 33.6 °C. The sample gel is prepared by free radical polymerization 7.8 g of re-crystallized N-iso-propylacrylamide (main constituent, Kodak), 0.133 g lV,iV -methylenebis-acrylamide (cross-linker, Bio-Rad), 240 ml tetramethylenediamine (accelerator, Bio-Rad), and 40 mg ammonium persulfate (initiator, Mallinckrodt) are dissolved in distilled water (100 ml) at 0°C. The gel mold is immersed in the pre-gel solution and then degassed for 40 min at 0°C. The temperature is raised to 20.0 °C after this treatment to initiate the gelation reaction. The sample gel thus obtained is homogeneous and transparent, at least by visual inspection. 

Gramain and Frere [82] observed that the free radical polymerization of co-meth-acryloyl terminated PEO macromonomers in the aqueous phase deviates from the solution polymerization. Polymerizations initiated by KPS in water were much faster than those that proceeded in the solution. Low molecular weight polymers were formed in the aqueous systems (ca. up to 20 macromonomer units were incorporated into polymer molecules). 

Free-Radical Polymerization in Emulsion. In suspension polymerization, the particle size is fixed by the size of the monomer droplet which contains the initiator. Emulsion polymerization differs from suspension polymerization in that the initiator is dissolved in the aqueous phase and the polymer particle grows during polymerization. Free radicals are generated in the water and diffuse to the monomer-water interface. The length of the polymer chain formed, or equivalently the molecular weight, depends on the rate of free radical arrival and termination. S. Katz,... 

If surfactant is added to a suspension polymerization system, a number of phenomena may occur. If the surfactant is added in small amounts (below the critical micelle concentration or CMC), the reduction in interfacial tension between the organic and aqueous phases will result in smaller monomer droplets, but it has hardly any other effect. If surfactant is added above the CMC, and an oil-soluble initiator is used, the process is commonly termed a microsuspension polymerization. Due to the reduced interfacial tension, the droplet diameter (and hence bead diameter) is reduced to approximately 10-40 pm. Little polymerization takes place in the aqueous phase or in particles generated from surfactant micelles because of the hydrophobic nature of the initiator. However, some smaller particles initiated from surfactant micelles may be found. The kinetics are still essentially those of a bulk free radical polymerization. Microsuspension polymerization is used to produce pressure-sensitive adhesives for repositionable notes. 

Barrere and Landfester [184] prepared a hybrid miniemulsion in which isophorone diisocyanate was condensation polymerized with dodecanediol to form polyurethane at the same time that the polystyrene or polyBA was free radical polymerized. Unlike previous work, the polyurethane was not prepared in organic solvent in advance. Therefore, in this one-pot synthesis, polyaddition and free radical polymerization both take place in the same particle. HD was used as the costabihzer. After miniemulsification, the polycondensation was allowed to take place, and then a free radical initiator was added to polymerize the styrenic or acrylic monomer. Molecular weight distributions were bimodal the PU had a substantially lower molecular weight than the polyacrylate. Neither intra- nor interparticle phase separation could be detected by TEM the particles appeared to be homogeneous. No measurements of grafting were made, but since there was no unsaturation in the PU, none was expected. 

Claverie et al. [325] have polymerized norbornene via ROMP using a conventional emulsion polymerization route. In this case the catalyst was water-soluble. Particle nucleation was found to be primarily via homogenous nuclea-tion, and each particle in the final latex was made up of an agglomeration of smaller particles. This is probably due to the fact that, unlike in free radical polymerization with water-soluble initiators, the catalyst never entered the polymer particle. Homogeneous nucleation can lead to a less controllable process than droplet nucleation (miniemulsion polymerization). This system would not work for less strained monomers, and so, in order to use a more active (and strongly hydrophobic) catalyst, Claverie employed a modified miniemulsion process. The hydrophobic catalyst was dissolved in toluene, and subsequently, a miniemulsion was created. Monomer was added to swell the toluene droplets. Reaction rates and monomer conversion were low, presumably because of the proximity of the catalyst to the aqueous phase due to the small droplet size. 

Radiation-induced polymerization, which generally occurs in liquid or solid phase, is essentially conventional chain growth polymerization of a monomer, which is initiated by the initiators formed by the irradiation of the monomer i.e., ion radicals. An ion radical (cation radical or anion radical) initiates polymerization by free radical and ionic polymerization of the respective ion. In principle, therefore, radiation polymerization could proceed via free radical polymerization, anionic polymerization, and cationic polymerization of the monomer that created the initiator. However, which polymerization dominates in an actual polymerization depends on the reactivity of double bond and the concentration of impurity because ionic polymerization, particularly cationic polymerization, is extremely sensitive to the trace amount of water and other impurities. 

The model for the reaction system will be considered in detail in Section II. However, it is convenient to note here that, in principle, the free radicals that initiate the polymerization may be generated cither within the external phase (external initiation) or within the reaction loci themselves (internal initiation). Whereas very brief reference will be made at the conclusion of this chapter to reaction systems of the latter type, the concern here will be almost exclusively with reaction systems of the former type. Insofar as the initiating radicals are generated exclusively within the external phase (and therefore have to be by some means acquired by the loci by absorption from the external phase), we have a farther important distinction between homogeneous and compartmentalized reactions. In the latter case, the processes that lead to the generation of the initiatit radicals are physically isolated from the propagation, termination, and transfer reactions. One minor consequence of this is that transfer-to-initiator reactions may be virtually eliminated in the latter case. 

Radical polymerization can be carried out under homogenous as well as heterogenous conditions. This difference is classified based on whether the initial mixture and/or final product are homogenous or heterogenous. Some homogenous mixtures become heterogenous as polymerization proceeds as a result of insolubility of the resulting polymer in the reaction media. There are many other specialized processes that are used to synthesize materials via free-radical polymerization. These include interfacial polymerization, gas phase reactions ( popcorn polymerization ), as well as the use of specialized media like supercritical fluids. Current research efforts include the study of such... 

Ethylene is compressed to 2,700 bar and a free-radical initiator, e.g., trace amounts of oxygen or a peroxide, is injected into the feed stream to promote the free-radical polymerization. The polyethylene polymer that is formed remains dissolved in the supercritical ethylene phase at the operating temperature, which ranges from 140 to 250°C. The heat of reaction is removed by through-wall heat transfer when the tubular reactor is used and by regulating the rate of addition of initiator when the autoclave reactor is used. 

This paper focuses on heterophase free radical polymerizations. It is limited to processes where multiple phases, distinguished by the insolubility of reagents, exists at the onset of the reaction. It therefore does not consider precipitation polymerization [1], which occurs when the polymer is insoluble in the monomer and precipitates out from an initially homogeneous solution. It also does not address emulsifier-free polymerization or dispersion polymerization. This rather general nomenclature is now accepted as applying to specific systems where the heterophase nature is produced at the onset of the reaction by homogeneous nucleation of oligomers or polymer chains which have exceeded their solubility limit [2]. 

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