Latex free radical polymerization

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). 

An emulsion polymerization reaction follows three conventional steps, namely, initiation, propagation, and termination. These steps can be described by the conventional reactions that are valid for any free radical polymerization. Smith and Ewart [10] proposed that a forming latex particle in an ideal emulsion polymeriza-... 

Free-radical polymerization of alkenes has been carried out in aqueous conditions.115 Aqueous emulsion and suspension polymerization is carried out today on a large scale by free-radical routes. Polymer latexes can be obtained as products (i.e., stable aqueous dispersions... 

Polymer colloids involve dispersions containing polymer particles having sizes greater than about 1 nm. If dispersed in aqueous solution, such a polymer dispersion is called a latex. These are usually synthetic polymer particles formed by free radical polymerization [784], Many kinds of polymerization systems exist, involving almost all of the possible kinds of colloidal dispersion, including emulsion polymerization, hence the more general term heterophase polymerization is sometimes used. Several reviews are available [785-789]. Emulsion polymerization provides a convenient means of controlling the polymerization of monomers and is used to make, for example, synthetic rubber which is mostly a co-polymer of butadiene and styrene. 

So far we have discovered very few polymerization techniques for making macromolecules with narrow molar mass distributions and for preparing di-and triblock copolymers. These types of polymers are usually made by anionic or cationic techniques, which require special equipment, ultrapure reagents, and low temperatures. In contrast, most of the commodity polymers in the world such as LDPE, poly(methyl methacrylate), polystyrene, poly(vinyl chloride), vinyl latexes, and so on are prepared by free radical chain polymerization. Free radical polymerizations are relatively safe and easy to perform, even on very large scales, tolerate a wide variety of solvents, including water, and are suitable for a large number of monomers. However, most free radical polymerizations are unsuitable for preparing block copolymers or polymers with narrow molar mass distributions. 

Emulsion polymerization—Free-radical polymerization carried out in micelles suspended in water. Ingredients include a surfactant (detergent) to form the micelles, a monomer that is not very soluble in water, and an initiator. The product consists of small particles of polymer suspended in water called a latex. ... 

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. 

As a result of the advances in catalyst discovery for aqueous ethylene polymerization, silica-polyethylene nancomposites have been prepared with structures that vary with changing catalyst structure and silica composition." It is likely that many more advances in the area of high-tech composites with potential biological and nanotechnology applications will be made in the next few years through aqueous polymerization processes. In addition to free radical polymerizations and catalytic polymerizations, it should be noted that oxidative polymerizations can also be performed in aqueous media to yield conducting polymers. Recently, this has been used to prepare polypyrrole-coated latex particles that are expected to be interesting synthetic mimics for micrometeorites. 

The theory also has relevance to the so-called seeded " emulsion polymerization reactioas- In these reactions, polymerization is initial in the presence of a seed latex under conditions such that new particles are unlikely to form. The loci for the compartmentalized free-radical polymerization that occurs are therefore provided principally by the particles of the initial seed latex. Such reactions are of interest for the preparation of latices whose particles have, for instance, a core-shell" structure. They are also of great interest for investigating the fondamentals of compartmentalized free-radical polymerization processes. In this latter connection it is important to note that, in principle, measurements of conversion as a function of time during nonsteady-state polymerizations in seeded systems offer the possibility of access to certain fundamental properties of reaction systems not otherwise available. As in the case of free-radical polymerization reactions that occur in homogeneous media, investigation of the reaction during the nonsteady state can provide information of a fundamental nature not available through measurements made on the same reaction system in the steady state. 

Overall, it is clear that significant hydrolysis of silanes in waterborne formulations occurs when the hindered silanes are used as monomers in emulsion polymerization. Si NMR spectroscopy on latex solids also reveals that a significant amount of hindered vinyl silane monomer forms condensates with itself, so that not all of the vinyl groups are incorporated into the backbone of the growing polymer through free-radical polymerization. 

Aqueous dispersions of poly(vinyl acetate) and vinyl acetate-ethylene copolymers, homo- and copolymers of acrylic monomers, and styrene-butadiene copolymers are the most important types of polymer latexes today. Applications include paints, coatings, adhesives, paper manufacturing, leather manufacturing, textiles and other industries. In addition to emulsion polymerization, other aqueous free-radical polymerizations are applied on a large scale. In suspension polymerization a water-irnrniscible olefinic monomer is also polymerized. However, by contrast to emulsion polymerization a monomer-soluble initiator is employed, and usually no surfactant is added. Polymerization occurs in the monomer droplets, with kinetics similar to bulk polymerization. The particles obtained are much larger (>15 pm) than in emulsion polymerization, and they do not form stable latexes but precipitate during polymerization (Scheme 7.2). 

In 1993, Perez et al. reported norbornene polymerization in aqueous emulsion at 70 °C using PdCl2 as a catalyst precursor [92, 93]. A stable latex consisting of low-molecular-weight oligomeric material (degree of polymerization DP ca. 10) was obtained with low catalyst activities (70 TO h ). Very small latex particles of 10 to 20 nm diameter were reported. In the free radical polymerization of olefinic monomers such small particles are only obtained by microemulsion polymeriza-... 

Emulsion polymerization is the process of choice for the commercial production of many polymers used for coating and adhesive applications, especially for those products that can be used in latex form. Emulsion polymerization uses free-radical polymerization mechanisms with unsaturated monomers. The heterogeneous nature of the reaction mixture, however, has a significant influence on the chemical and physical reaction mechanisms and on the nature of the final product. 

Most early thermoplastics, e.g., PVC or PS, were obtained in the free radical polymerization, initiated either by heat or by sunlight. The first systematic studies of the free radical chemistry commenced 80 years later [Ostromislensky, 1911, 1915, 1916]. Fikentscher empirically determined which one of the 30-or-so monomers liked or disliked to copolymerize with each other. The advantage of latex-blending was also established. The theory of the free radical copolymerization was finally developed in the 1940 s [Alfrey et al, 1952]. 

There are many unique polymerization processes which share a conunon heritage with emulsion polymerization, but which often are unrecognized as such. It is the purpose of this review to describe some of these emulsion polymerization-like processes and their products. Some further definition is in order unconventional emulsion polymerizations can be described as those processes whereby the product is a polymer latex that physically resembles latex from emulsion polymerization and cannot be grouped into any other recognized form of heterogeneous polymerization. In many cases the reasons why a process is not recognized as an emulsion polymerization is that the polymerization is not via a free-radical process. This review (hscusses four distinct types of polymerization processes, all of which have examples that produce latex particles and in many ways can be described as unconventional emulsion polymerizations. These are free-radical polymerization, ionic polymerization, transition metal catalyzed polymerization and enzyme-catalyzed polymerization. The precise systems discussed in this review are described in Table 23.1. 

The conversion of n bonds into a bonds is exothermic and leads to enthalpies of polymerization in the approximate range -60 to — lOOkJ moI for the monomers most often used in free-radical polymerizations. Clearly the heat evolved during polymerization must be removed and, although this is not a significant problem on the laboratory scale, heat transfer requirements cannot be ignored when considering large-scale production of latexes. 

Emulsion polymerization involves the emulsification of monomers in an aqueous phase, and stabilization of the droplets by a surfactant. Usually, a water-soluble initiator is used to start the free-radical polymerization. The final product is a dispersion of submicrometer polymer particles, which is called latex. The locus of polymerization is the micelle. Typical applications are paints, coatings, adhesives, paper coatings and carpet backings. The latex particles can have different structures (see Fig. 2). Excellent text books on the applications and structure-property relationships exist [11-15]. Besides a full description of the kinetics and mechanism of emulsion polymerization [16], a textbook adapted for use as material for people entering the field is also available [17]. 

Most studies have dealt either with the free radical polymerization of hydrophobic monomers—e.g., styrene [56-89], methyl methacrylate (MMA) [68,73,74,84,86,90-93] or derivatives [2,94,97], and butyl acrylate (BA) [98-100]—within the oily core of O/W microemulsions or with the polymerization of water-soluble monomers such as acrylamide (AM) within the aqueous core of W/O microemulsions [101-123]. In the latter case, the monomer is a powder that has to first be dissolved in water (1 1 mass ratio) so that the resulting polymer particles are swollen by water, in contrast with O/W latex particles, where the polymer is in the bulk state. The polymerization can be initiated thermally, photochemically, or under )>-radiolysis. The possibility of using a coulometric initiation for acrylamide polymerization in AOT systems was also reported [120]. Besides the conventional dilatometric and gravimetric techniques, the polymerization kinetics was monitored by Raman spectroscopy [73,74], pulsed UV laser source [72,78], the rotating sector technique [105,106], calorimetry, and internal reflectance spectroscopy [95]. 

The concept of copolymerizing with a functional comonomer that is soluble in the continuous phase can virtually be extended to any vinyl functional monomer, provided that under such conditions the copolymerization parameters will allow a copolymerization to occur. The functionalities available using hydrophobic monomers with functional monomers in direct miniemulsions are summarized in Table 15.1. Latexes with a double functionality were prepared via a free-radical polymerization of divinylbenzene in miniemulsion [49, 50] after polymerization, the remaining vinyl bond might be reacted with a thiol-functionalized PEG via the thiol-ene chemistry [49]. 

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