Polymerization, free-radical addition vinyl

Kinetics. Monomer can be converted into polymer by any chemical reaction which creates a new covalent bond. Most of this review will concern polymerization of vinyl monomers by free radical addition polymerization. However, some attention will be given to cationic polymerization of epoxy functional materials. No extensive review of polymerization processes and kinetics will be given here, but some of the fundamental notions will be described. For reviews, see (4a-d). 

The reaction engineering aspects of these polymerizations are similar. Excellent heat transfer makes them suitable for vinyl addition polymerizations. Free radical catalysis is mostly used, but cationic catalysis is used for non-aqueous dispersion polymerization (e.g., of isobutene). High conversions are generally possible, and the resulting polymer, either as a latex or as beads, is directly suitable for some applications (e.g., paints, gel-permeation chromatography beads, expanded polystyrene). Most of these polymerizations are run in the batch mode, but continuous emulsion polymerization is common. 

Free radical polymerization offers a convenient approach toward the design and synthesis of special polymers for almost every area. In a free radical addition polymerization, the growing chain end bears an unpaired electron. A free radical is usually formed by the decomposition of a relatively unstable material called initiator. The free radical is capable of reacting to open the double bond of a vinyl monomer and add to it, with an electron remaining unpaired. The energy of activation for the propagation is 2-5 kcal/mol that indicates an extremely fast reaction (for condensation reaction this is 30 to 60 kcal/mol). Thus, in a very short time (usually a few seconds or less) many more monomers add successively... 

Generalized methods of initiating the polymerization of these monomers have recently been reviewed in detail [9], and were also mentioned briefly earlier in this Chapter. As with vinyl monomers initiation can be efficient and rapid, with the production of a fixed number of active centres. Propagation appears to be much slower, however, and rates of polymerization are comparable to those in free radical addition polymerizations. Techniques such as dilatometry, spectrophotometry etc. are therefore convenient for kinetic investigation of this type of cationic reaction. 

Theoretical Aspects. Ultraviolet light-cured inks are cured by free radical-initiated vinyl addition polymerization. The photochemical initiation of vinyl polymerization has been the subject of many investigations dating back more than 30 years, to the first systematic studies of polymerization kinetics. Photochemical initiation offered a reproducible source of radicals that is not dependent upon temperature as is the thermal decomposition of free radical initiators. However, despite these early studies of its mechanism and kinetics, only recently has photochemical initiation become of practical interest, mainly because of the recent development of ultraviolet lamps suitable for production curing of printing inks and coatings. 

Poly(vinyl acetate) (PVA) and ethylene-vinyl acetate (EVA) copolymer adhesives have much in common, yet represent extremes in the degree of sophistication of their production processes. Both products are stable suspensions in water of a film-forming polymer, the particles of which are generally spherical. They are made by emulsion polymerization, which uses a free-radical addition mechanism to polymerize the monomer in the presence of water and stabilizers. Vinyl acetate is the sole or major monomeric raw material. 

Basic acrylate chemistry. The basic acrylic monomers or oligomers contain unsaturated double bonds (vinyl groups), and consequently cure by addition polymerization involving a free-radical reaction. Free-radical-producing compounds such as peroxides, peracetic acids, and sulfones are added to acrylic resins to initiate polymerization. Free-radical polymerization of acrylics may also be induced by exposure to U V or visible light. These UV-curing adhesives, most of which are based on acrylic or modified acrylic... 

Allyl esters, unsaturated polyesters, as well as some of what are known as vinyl or acrylic esters are cured by free radical addition polymerization. In the case of allyl esters, the monomers, themselves, are cross-linked. On the other hand, unsaturated polyesters are copolymerized with monomers such as styrene or methyl methacrylate. Since the unsaturated polyesters have many main-chain double bonds and the structure of a cross-linked network is fixed after quite low conversions, only a few double bonds actually react. These unconverted double bonds can then react later with atmospheric agents, and so produce poor weathering properties of the crosslinked networks. In addition, the polymerization produces many free chain ends that contribute nothing or even disadvantageously to the mechanical properties. The newly developed vinyl or acrylic esters avoid both of these problems in that the monomers capable of cross-linking only have unsaturated double bonds at the molecular ends (see also Section 26.4. S). 

Polyvinyl Chloride (PVC). Polyvinyl chloride polymers (PVC), generally referred to as vinyl resins, are prepared by the polymerization of vinyl chloride in a free radical addition polymerization reaction. Vinyl chloride monomer is prepared by reacting ethylene with chlorine to form 1,2-dichloroethane. The 1,2 dichloroethane is then cracked to give vinyl chloride. The polymerization reaction is depicted in Fig. 2.41. 

One or more pairs of double bonds such as >C=C< and >C=0 can form polymers by conversion of their double bonds into saturated linkages for example, vinyl chloride can undergo free-radical addition polymerization to form polyvinyl chloride. 

The preparation of polymer colloids is both a science and an art. It is a science in which the kinetic principles of free radical-initiated vinyl addition polymerization are superimposed on the heterogeneous polymer latex system. It is an art in that the preparer uses a recipe which comprises monomer, water, emulsifier, initiator, and other ingredients, and the quality of the latex obtained depends upon small variations in the polymerization parameters as well as the skill of the preparer. The purpose of this paper is to review the different types of polymer latexes and the mechanisms proposed for their preparation, and to give examples of the preparation of different types. 

Vinyl stearate (7) was one of the first materials to be investigated for its polymerization behaviour, either on the water surface [23] or in LB multilayers [24]. Polymerization on the water surface yields highly rigid monolayers that are incapable of LB deposition. The monomer deposits X-type, and can be polymerized with UV or y-irradiation by way of a free-radical addition mechanism to produce the polymer (8). This mechanism is common for many such materials, and great care must be taken to avoid quenching of the radical intermediates by impurities, particularly oxygen. It is therefore usually necessary to carry out the polymerization in an inert atmosphere. 

Commercially, suspension polymerization has been hmited to the free-radical addition of water-insoluble liquid monomers. With a volatile monomer such as vinyl chloride, moderate pressures are required to maintain it in the hquid state. It is possible, however, to perform inverse suspension polymerizations with a hydrophilic monomer or an aqueous solution of a water-soluble monomer suspended in a hydrophobic continuous phase. 

As with suspension polymerization, commerdal emulsion polymerization has pretty much been restricted to the free-radical addition of water-insoluble, liquid monomers (with volatile monomers such as butadiene and vinyl chloride, moderate pressures are required to keep them in the liquid phase). Inverse emulsion polymerizations, with a hydrophylic monomer phase dispersed in a continuous hydrophobic phase, are possible, however. 

Another type of isomerism that can occur is that caused by different orientations of monomer addition at the active centre during vinyl polymerization. This problem has been discussed in the case of free-radical addition with respect to active centre formation (Section 2.2.2) and the propagation reaction (Section 2.2.3). The normal orientations that are found with vinyl monomers are the head-to-tail configurations... 

The addition polymerization of a vinyl monomer CH2=CHX involves three distinctly different steps. First, the reactive center must be initiated by a suitable reaction to produce a free radical or an anion or cation reaction site. Next, this reactive entity adds consecutive monomer units to propagate the polymer chain. Finally, the active site is capped off, terminating the polymer formation. If one assumes that the polymer produced is truly a high molecular weight substance, the lack of uniformity at the two ends of the chain—arising in one case from the initiation, and in the other from the termination-can be neglected. Accordingly, the overall reaction can be written... 

For most vinyl polymers, head-to-tail addition is the dominant mode of addition. Variations from this generalization become more common for polymerizations which are carried out at higher temperatures. Head-to-head addition is also somewhat more abundant in the case of halogenated monomers such as vinyl chloride. The preponderance of head-to-tail additions is understood to arise from a combination of resonance and steric effects. In many cases the ionic or free-radical reaction center occurs at the substituted carbon due to the possibility of resonance stabilization or electron delocalization through the substituent group. Head-to-tail attachment is also sterically favored, since the substituent groups on successive repeat units are separated by a methylene... 

Cationic Polymerization. For decades cationic polymerization has been used commercially to polymerize isobutylene and alkyl vinyl ethers, which do not respond to free-radical or anionic addition (see Elastomers, synthetic-BUTYLRUBBEr). More recently, development has led to the point where living cationic chains can be made, with many of the advantages described above for anionic polymerization (27,28). 

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