Radical polymerization reactions

Let us for the moment disregard chain transfer reactions. Radical polymerization then consists of three component reactions initiation, propagation of the polymer chains, and termination of chain growth. The rate of primary radical formation, v, by decomposition of the initiator I, may be written ... 

Fig. 2 Reactions - radical polymerization [1] - a dash symbolizes a chemical bond involving two...

A MECHANISM FOR THE REACTION ] Radical Polymerization of Ethene (Ethylene) 484... 

Cyanoacrylate esters readily polymerize by several different mechanisms. Anionic polymerization is the most common and the most important method with respect to their use as adhesives. Typically this process is initiated by the nucleophilic contaminants found on the surfaces being bonded. The other routes by which cyanoacrylates polymerize or copolymerize involve radically initiated and photochemically initiated reactions. Radical polymerization or copolymerization of cyanoacrylates usually does... 

Polymerization reactions. There are two broad types of polymerization reactions, those which involve a termination step and those which do not. An example that involves a termination step is free-radical polymerization of an alkene molecule. The polymerization requires a free radical from an initiator compound such as a peroxide. The initiator breaks down to form a free radical (e.g., CH3 or OH), which attaches to a molecule of alkene and in so doing generates another free radical. Consider the polymerization of vinyl chloride from a free-radical initiator R. An initiation step first occurs ... 

Dimerization in concentrated sulfuric acid occurs mainly with those alkenes that form tertiary carbocations In some cases reaction conditions can be developed that favor the formation of higher molecular weight polymers Because these reactions proceed by way of carbocation intermediates the process is referred to as cationic polymerization We made special mention m Section 5 1 of the enormous volume of ethylene and propene production in the petrochemical industry The accompanying box summarizes the principal uses of these alkenes Most of the ethylene is converted to polyethylene, a high molecular weight polymer of ethylene Polyethylene cannot be prepared by cationic polymerization but is the simplest example of a polymer that is produced on a large scale by free radical polymerization... 

The three-step mechanism for free-radical polymerization represented by reactions (6.A)-(6.C) does not tell the whole story. Another type of free-radical reaction, called chain transfer, may also occur. This is unfortunate in the sense that it complicates the neat picture presented until now. On the other hand, this additional reaction can be turned into an asset in actual polymer practice. One of the consequences of chain transfer reactions is a lowering of the kinetic chain length and hence the molecular weight of the polymer without necessarily affecting the rate of polymerization. 

Among other possible reactions, these free radicals can initiate ordinary free-radical polymerization. The Ziegler-Natta systems are thus seen to encompass several mechanisms for the initiation of polymerization. Neither ionic nor free-radical mechanisms account for stereoregularity, however, so we must look further for the mechanism whereby the Ziegler-Natta systems produce this interesting effect. 

Since the principal hazard of contamination of acrolein is base-catalyzed polymerization, a "buffer" solution to shortstop such a polymerization is often employed for emergency addition to a reacting tank. A typical composition of this solution is 78% acetic acid, 15% water, and 7% hydroquinone. The acetic acid is the primary active ingredient. Water is added to depress the freezing point and to increase the solubiUty of hydroquinone. Hydroquinone (HQ) prevents free-radical polymerization. Such polymerization is not expected to be a safety hazard, but there is no reason to exclude HQ from the formulation. Sodium acetate may be included as well to stop polymerization by very strong acids. There is, however, a temperature rise when it is added to acrolein due to catalysis of the acetic acid-acrolein addition reaction. 

Replacement of Labile Chlorines. When PVC is manufactured, competing reactions to the normal head-to-tail free-radical polymerization can sometimes take place. These side reactions are few ia number yet their presence ia the finished resin can be devastating. These abnormal stmctures have weakened carbon—chlorine bonds and are more susceptible to certain displacement reactions than are the normal PVC carbon—chlorine bonds. Carboxylate and mercaptide salts of certain metals, particularly organotin, zinc, cadmium, and antimony, attack these labile chlorine sites and replace them with a more thermally stable C—O or C—S bound ligand. These electrophilic metal centers can readily coordinate with the electronegative polarized chlorine atoms found at sites similar to stmctures (3—6). 

Other nonpolymeric radical-initiated processes include oxidation, autoxidation of hydrocarbons, chlorination, bromination, and other additions to double bonds. The same types of initiators are generally used for initiating polymerization and nonpolymerization reactions. Radical reactions are extensively discussed in the chemical Hterature (3—15). 

There are many chemical methods for generating radicals reported in the hterature that do not involve conventional initiators. Specific examples are included in References 64—79. Most of these radical-generating systems carmot broadly compete with the use of conventional initiators in industrial polymer apphcations owing to cost or efficiency considerations. However, some systems may be weU-suited for initiating specific radical reactions or polymerizations, eg, grafting of monomers to cellulose using ceric ion (80). 

Polymerization of methacrylates is also possible via what is known as group-transfer polymerization. Although only limited commercial use has been made of this technique, it does provide a route to block copolymers that is not available from ordinary free-radical polymerizations. In a prototypical group-transfer polymerization the fluoride-ion-catalyzed reaction of a methacrylate (or acrylate) in the presence of a silyl ketene acetal gives a high molecular weight polymer (45—50). 

Polyethylene (PE) is a genetic name for a large family of semicrystalline polymers used mostiy as commodity plastics. PE resins are linear polymers with ethylene molecules as the main building block they are produced either in radical polymerization reactions at high pressures or in catalytic polymerization reactions. Most PE molecules contain branches in thek chains. In very general terms, PE stmcture can be represented by the following formula ... 

The radicals are destroyed and are not available to take part in the desired radical reactions, eg, polymerizations. Thus, transition-metal ion concentrations of metal—hydroperoxide initiating systems are optimized to maximize radical generation. 

The minimum polydispersity index from a free-radical polymerization is 1.5 if termination is by combination, or 2.0 if chains ate terminated by disproportionation and/or transfer. Changes in concentrations and temperature during the reaction can lead to much greater polydispersities, however. These concepts of polymerization reaction engineering have been introduced in more detail elsewhere (6). 

Polymerization Processes. Free-radical polymerization is carried out in a variety of ways. One of the practical problems that must be dealt with is mnaway reactions which can result from auto acceleration, an increase in rate of polymerization caused by diffusion-limited termination (reduced... 

Photopolymerization. In many cases polymerization is initiated by ittadiation of a sensitizer with ultraviolet or visible light. The excited state of the sensitizer may dissociate directiy to form active free radicals, or it may first undergo a bimoleculat electron-transfer reaction, the products of which initiate polymerization (14). TriphenylaLkylborate salts of polymethines such as (23) ate photoinitiators of free-radical polymerization. The sensitivity of these salts throughout the entire visible spectral region is the result of an intra-ion pair electron-transfer reaction (101). 

In the manufacture of highly resident flexible foams and thermoset RIM elastomers, graft or polymer polyols are used. Graft polyols are dispersions of free-radical-polymerized mixtures of acrylonitrile and styrene partially grafted to a polyol. Polymer polyols are available from BASF, Dow, and Union Carbide. In situ polyaddition reaction of isocyanates with amines in a polyol substrate produces PHD (polyhamstoff dispersion) polyols, which are marketed by Bayer (21). In addition, blending of polyether polyols with diethanolamine, followed by reaction with TDI, also affords a urethane/urea dispersion. The polymer or PHD-type polyols increase the load bearing properties and stiffness of flexible foams. Interreactive dispersion polyols are also used in RIM appHcations where elastomers of high modulus, low thermal coefficient of expansion, and improved paintabiUty are needed. 

The most important chemical reaction of vinyl acetate is free-radical polymerization (13,14). The reaction is summarized as follows ... 

Polymerization Reactions. The polymerization of butadiene with itself and with other monomers represents its largest commercial use. The commercially most important polymers are styrene—butadiene mbber (SBR), polybutadiene (BR), styrene—butadiene latex (SBL), acrylonittile—butadiene—styrene polymer (ABS), and nittile mbber (NR). The reaction mechanisms are free-radical, anionic, cationic, or coordinate, depending on the nature of the initiators or catalysts (194—196). 

There are two very active special fields of phase-transfer appHcations that transcend classes (/) and 2) metal—organic reactions both with and without added bases, and polymer chemistry. Certain chemical modifications of side groups, polycondensations, and radical polymerizations can be influenced favorably by PTC. 

Calcium Chelates (Salicylates). Several successhil dental cements which use the formation of a calcium chelate system (96) were developed based on the reaction of calcium hydroxide [1305-62-0] and various phenohc esters of sahcyhc acid [69-72-7]. The calcium sahcylate [824-35-1] system offers certain advantages over the more widely used zinc oxide—eugenol system. These products are completely bland, antibacterial (97), facihtate the formation of reparative dentin, and do not retard the free-radical polymerization reaction of acryhc monomer systems. The principal deficiencies of this type of cement are its relatively high solubihty, relatively low strength, and low modulus. Less soluble and higher strength calcium-based cements based on dimer and trimer acid have been reported (82). 

Photopolymerization reactions are widely used for printing and photoresist appHcations (55). Spectral sensitization of cationic polymerization has utilized electron transfer from heteroaromatics, ketones, or dyes to initiators like iodonium or sulfonium salts (60). However, sensitized free-radical polymerization has been the main technology of choice (55). Spectral sensitizers over the wavelength region 300—700 nm are effective. AcryUc monomer polymerization, for example, is sensitized by xanthene, thiazine, acridine, cyanine, and merocyanine dyes. The required free-radical formation via these dyes may be achieved by hydrogen atom-transfer, electron-transfer, or exciplex formation with other initiator components of the photopolymer system. 

Additive Polyimides. Rhc ne-Poulenc s Kin el molding compound and Kerimid impregnating resin (115), Mitsubishi s BT Resins (116), and Toshiba s Imidaloy Resin (117) are based on bismaleimide (4) technology. Maleic anhydride reacts with a diamine to produce a diimide oligomer (7). Eurther reaction with additional diamine (Michael addition) yields polyaminohismaleimide prepolymer with terminal maleic anhydride double bonds. Cure is achieved by free-radical polymerization through the terminal double bonds. 

Grignard reagents from, 5, 106 reactions, 5, 104 6, 274, 292 reactivity, 6, 292 synthesis, 6, 297 Thiazoles, imino-reactivity, 6, 250 Thiazoles, isopropenyl-radical polymerization, 6, 278 Thiazoles, mercapto-industrial uses, 6, 330 reactions, 5, 102 synthesis, 6, 298-299 tautomerism, 6, 247, 248, 269, 289 Thiazoles, methyl-... 

The reaction between benzoyl peroxide and A,A-dimethylaniline has been the subject of many examinations over the years. The following mechanism of initiation is fairly well accepted in the polymerization of styrene. It seems likely that a similar mechanism is followed for other free-radical polymerizations (Scheme 5). 

Polyethylene is the simplest of so-called high polymers. The reaction for low density polyethylene (LDPE) follows the classical free radical polymerization steps of initiator decomposition, initiation, propagation, and termination. The reaction is... 

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