Radical polymerization monomers used

Owing to their liquid or semisolid nature, monomers are easy to process into polymers. For radical polymerization the use of solid AIBN for liquid monomers at room temperature and liquid MEKP for semisolid monomers or a mixture of liquid and semisolid monomers with some heating is convenient. During the course of curing at 85- 100°C for 22 h the problem of surface inhibition of free radicals by oxygen from the air can be avoided by inert-gas blanketing. 

There have been efforts to enhance stereoselectivity in radical polymerization by using fluoroalcohols or Lewis acids that complex with monomers such as MMA and vinyl acetate [Isobe et al., 2000, 2001a Okamoto et al., 2002], In almost all instances the effects are nil or very small. For example, the use of perfluoro-t-butyl alcohol as solvent instead of toluene changes (rr) from 0.89 to 0.91 in the polymerization of MMA at —78°C. An exception is in the polymerization of acrylamide in the presence of some rare-earth Lewis acids such as ytterbium triflate. The polymer is atactic at 0°C, (m) = 0.46, in the absence of the Lewis acid, but significantly isotactic, (m) — 0.80, in the presence of the Lewis acid. The reason for this effect is unclear. More highly isoselective polymerization occurs in some radical polymerizations of MMA (Sec. 8-14b). 

Monomers, (III) and (IV), having pendant tri ary I methane groups were prepared by Herron et al. (3) and then free radically polymerized and used as hole transport polymers. 

Styrene and butadiene also form copolymers known as high impact polystyrene, or rubber-modified polystyrene, when the content of butadiene is 10%. This type of material has excellent mechanical properties, and it is widely used in practice for the manufacturing of numerous objects, including parts for household appliances, furniture, etc. Rubber-modified polystyrene is commonly used as wood replacement and also for packaging. The synthesis of this material typically is done by dissolving polybutadiene in styrene monomer, followed by free radical polymerization achieved using a peroxide catalyst. This procedure leads to block or graft type copolymers. 

As discussed so far in this section, the helical polymethacrylates are synthesized predominantly using anionic polymerization techniques. However, recently, more versatile, inexpensive, and experimentally simple free-radical polymerization has been proved to be an alternative, effective way to prepare helical polymethacrylates from some monomers. Although the stereochemical control of radical polymerization is generally more difficult compared with that in other types of polymerization,69 an efficient method would make it possible to synthesize helical, optically active polymers having functional side chains by direct radical polymerization without using protective groups. In the radical polymerization of bulky methacrylates, helix-sense selection is governed by the chirality of a monomer itself or an additive. 

In another extension for copolymerizations involving several monomers, Tobita has studied the full multivariate distribution of chain length and compositions for multi-component free radical polymerization by using generating functions [141, 142],... 

Electroluminescent Materials. Radical polymerization is used in the preparation of electroluminescent materials that are composed of alternate copolymer-izates of hole transfer monomers and electron transfer monomers [27]. 

A parallel development was initiated by the first publications from Sawamoto and Matyjaszweski. They reported independently on the transition-metal-catalyzed polymerization of various vinyl monomers (14,15). The technique, which was termed atom transfer radical polymerization (ATRP), uses an activated alkyl halide as initiator, and a transition-metal complex in its lower oxidation state as the catalyst. Similar to the nitroxide-mediated polymerization, ATRP is based on the reversible termination of growing radicals. ATRP was developed as an extension of atom transfer radical addition (ATRA), the so-called Kharasch reaction (16). ATRP turned out to be a versatile technique for the controlled polymerization of styrene derivatives, acrylates, methacrylates, etc. Because of the use of activated alkyl halides as initiators, the introduction of functional endgroups in the polymer chain turned out to be easy (17-22). Although many different transition metals have been used in ATRP, by far the most frequently used metal is copper. Nitrogen-based ligands, eg substituted bipyridines (14), alkyl pyridinimine (Schiff s base) (23), and multidentate tertiary alkyl amines (24), are used to solubilize the metal salt and to adjust its redox potential in order to match the requirements for an ATRP catalyst. In conjunction with copper, the most powerful ligand at present is probably tris[2-(dimethylamino)ethyl)]amine (Mee-TREN) (25). 

Since the preparation of the first identified block copolymer by Melville [26 ] a large variety of A-B and A-B-A block copolymers were prepared by free-radical polymerization by using as well macroinitiators with active chain ends, either peroxide or azo groups, as polyinitiators, for example polyazoesters [20]. These techniques are stiU used at present for the preparation of different types of polyelectrolyte block copolymers, because charge-carrying monomers are in general not directly polymerizable by ionic techniques. 

Williams RJJ. Statistics of free-radical polymerizations revisited using a fragment approach, 1. Bifunctional monomers. Macromolecules 1988 21 2568-2571. 

Acrylic latexes are high MW acrylic (co)polymer particles dispersed in water. Synthetic latexes are prepared by a radical polymerization mechanism using an emulsion polymerization technique. The emulsion polymerization is carried out in water using monomer(s), surfactant (emulsifier) and water-soluble initiator. In a typical manufacturing process, an initiator and a separate emulsion of monomer(s) in water are slowly added to a reaction vessel containing water and emulsifier, at a predetermined rate. Polymerization of monomers occurs within tiny pockets formed by aggregation of emulsifier molecules, called micelles, resulting in formation... 

Early, in situ radical polymerization was used for the synthesis of poly(methyl methacrylate) (PMMA)-CNT composites [82]. In situ polymerization was performed using the radical initiator 2,2-azobisisobutyronitrile(AIBN). In this reaction, p-bonds in CNTs were initiated by AIBN, and therefore nanotubes could participate in PMMA polymerization to form a strong interface between the CNT and the PMMA matrix. PA6/CNT composites have been prepared by in situ polymerization of e-caprolactam in the presence of pristine and carboxylated CNTs. The e-caprolactam monomer was found to form an electron-transfer complex with CNTs and result in a homogeneous, polymerizable solution. The final composites can be spun into PA6/CNT fibers (Fig. 7) with excellent mechanical and electrical properties [83].This method is also suitable for the fabrication of thermosetting polymer composites with nanofillers. Bauhofer et al. [84] dispersed CNTs in an epoxy solution system based on a bisphenol-A epoxy resin and an amine hardener During nanocomposite curing, electric fields were used to induce the formation of aligned conductive nanotube networks. Recently, the in situ polymerization method... 

The elastomer produced in greatest amount is styrene-butadiene rubber (SBR) Annually just under 10 lb of SBR IS produced in the United States and al most all of it IS used in automobile tires As its name suggests SBR is prepared from styrene and 1 3 buta diene It is an example of a copolymer a polymer as sembled from two or more different monomers Free radical polymerization of a mixture of styrene and 1 3 butadiene gives SBR... 

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 ... 

On the basis of these observations, criticize or defend the following proposition Regardless of the monomer used, zero-order Markov (Bernoulli) statistics apply to all free radical, anionic, and cationic polymerizations, but not to Ziegler-Natta catalyzed systems. 

The presence of stable free radicals in the final polycondensate is supported by the observation that traces of (11) have a strong inhibiting effect on the thermal polymerization of a number of vinyl monomers. Radical polymerization was inhibited to a larger extent by a furfural resin than by typical polymerization inhibitors (34). Thermal degradative methods have been used to study the stmcture of furfural resinifted to an insoluble and infusible state, leading to proposed stmctural features (35). 

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. 

Emulsion Adhesives. The most widely used emulsion-based adhesive is that based upon poly(vinyl acetate)—poly(vinyl alcohol) copolymers formed by free-radical polymerization in an emulsion system. Poly(vinyl alcohol) is typically formed by hydrolysis of the poly(vinyl acetate). The properties of the emulsion are derived from the polymer employed in the polymerization as weU as from the system used to emulsify the polymer in water. The emulsion is stabilized by a combination of a surfactant plus a coUoid protection system. The protective coUoids are similar to those used paint (qv) to stabilize latex. For poly(vinyl acetate), the protective coUoids are isolated from natural gums and ceUulosic resins (carboxymethylceUulose or hydroxyethjdceUulose). The hydroHzed polymer may also be used. The physical properties of the poly(vinyl acetate) polymer can be modified by changing the co-monomer used in the polymerization. Any material which is free-radically active and participates in an emulsion polymerization can be employed. Plasticizers (qv), tackifiers, viscosity modifiers, solvents (added to coalesce the emulsion particles), fillers, humectants, and other materials are often added to the adhesive to meet specifications for the intended appHcation. Because the presence of foam in the bond line could decrease performance of the adhesion joint, agents that control the amount of air entrapped in an adhesive bond must be added. Biocides are also necessary many of the materials that are used to stabilize poly(vinyl acetate) emulsions are natural products. Poly(vinyl acetate) adhesives known as "white glue" or "carpenter s glue" are available under a number of different trade names. AppHcations are found mosdy in the area of adhesion to paper and wood (see Vinyl polymers). 

Acrylonitrile and its comonomers can be polymerized by any of the weU-known free-radical methods. Bulk polymerization is the most fundamental of these, but its commercial use is limited by its autocatalytic nature. Aqueous dispersion polymerization is the most common commercial method, whereas solution polymerization is used ia cases where the spinning dope can be prepared directly from the polymerization reaction product. Emulsion polymerization is used primarily for modacryhc compositions where a high level of a water-iasoluble monomer is used or where the monomer mixture is relatively slow reacting. 

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