Organic monomers

Photoinitiation. Since photolysis of polysdanes generates sdyl radicals, which can add to carbon—carbon double bonds, these polymers have been used for the free-radical polymerization of unsaturated organic monomers (135,136). Though about one-tenth as efficient as other organic photoinitiators, polysdanes are nevertheless quite insensitive to oxygen effects, which somewhat compensates for their lower efficiency. 

Emulsion Polymerization. When the U.S. supply of natural mbber from the Far East was cut off in World War II, the emulsion polymerization process was developed to produce synthetic mbber. In this complex process, the organic monomer is emulsified with soap in an aqueous continuous phase. Because of the much smaller (<0.1 jira) dispersed particles than in suspension polymerization and the stabilizing action of the soap, a proper emulsion is stable, so agitation is not as critical. In classical emulsion polymerization, a water-soluble initiator is used. This, together with the small particle size, gives rise to very different kinetics (6,21—23). 

Ammonium sulfate is also recovered as a by-product in large amounts during the coking of coal, nickel refining, and organic monomer synthesis, particularly during production of caprolactam (qv). About four metric tons of ammonium sulfate are produced per ton of caprolactam which is an intermediate in the production of nylon. 

Radiopaque materials are used to determine the location of aspirated dentures and fragments (205,206). Opacifying additives include barium sulfate, barium fluoride, barium or bismuth glasses, and brominated organic monomers and polymers. The incorporation of these additives into the resin base or tooth can adversely affect physical properties. Radiopaque materials meeting the requirement for ANSI/ADA specifications for denture-base polymer have been described (207). 

TFIIA and TFIIB bind to both TBP and DNA Flomeodomain proteins are involved in the development of many eucaryotic organisms Monomers of homeodomain proteins bind to DNA through a heltx-turn-helix motif In vivo specificity of homeodomain... 

The interest in this area may be seen to stem from the biological area where the phenomenon is well known and accounts for the regularity in the structure of natural proteins and polynucleotides. Such polymers are efficiently synthesized by enzymes which arc capable of organizing monomer units within regularly structured molecular-scale spaces and exploiting weak forces such as hydrogen bonds and Van der Waal forces to control the polymerization process.. 

Detailed information on the copolymerization of cyclic trifluoropropylmethyl-siloxane trimer and octamethylcyclotetrasiloxane is also very limited in the open literature26 27 . Recently, preparation of various amine terminated (dimethyl-tri-fluoropropyl,methyl)siloxane oligomers with varying molecular weights and backbone compositions has been reported 69115 ll7). Table 11 shows various properties of the oligomers produced as a function of composition. These types of modification play very important roles in determining the solubility characteristics and hence the compatibility of resultant polysiloxanes with other conventional organic monomers... 

Dendrimers can be constructed from chemical species other than purely organic monomers. For example, they can be built up from metal branching centres such as ruthenium or osmium with multidentate ligands. The resulting molecules are known as metallodendrimers. Such molecules can retain their structure by a variety of mechanisms, including complexation, hydrogen bonding and ionic interactions. 

Bisphenol A, whose official chemical name is 2,2-bis(4-hydroxyphenyl)propane, is a difunctional monomer with two reactive hydroxyl groups, as shown in Fig. 20,2. It polymerizes svith dicarbonyl organic monomers, such as phosgene or diphenyl carbonate, which are illustrated in Fig. 20.3. During polymerization, shown in Fig. 20.4, the hydroxyl groups of the bisphenol A deprotonate in the presence of a base. After deprotonation, the oxygen atoms on the bisphenol A residue form ester bonds with the dicarbonyl compounds. The polymerization process terminates when a monohydric phenol reacts with the growing chain end. 

Pekala R.W., Alviso C.T., Kong F.M., Hulsey S.S. Aerogels derived from multifunctional organic monomers. J. Nn-Cryst Solids 1992 145 90-8. 

The lack of isomerisation indicates that a non-ionic process is involved. The reaction does not continue to give a polymerisation of ethylene, because in contrast to the tertiary C-Cl bond which is broken, the primary C-Cl bond which is formed is too strong to be activated sufficiently by the A1C13. For the polymerisations involving an organic (monomer) halide and a metal halide, such as ZnBr2, it seems reasonable to represent the insertion also as occurring via a 6-membered cyclic transition state (II) ... 

The hybridizing component can also be formed directly on the surface of a pristine or modified nanocarbon using molecular precursors, such as organic monomers, metal salts or metal organic complexes. Depending on the desired compound, in situ deposition can be carried out either in solution, such as via direct network formation via in situ polymerization, chemical reduction, electro- or electroless deposition, and sol-gel processes, or from the gas phase using chemical deposition (i.e. CVD or ALD) or physical deposition (i.e. laser ablation, electron beam deposition, thermal evaporation, or sputtering). 

Acidogenesis. The soluble organic monomers produced in the hydrolysis step are decomposed by means of acidogenic bacteria to produce acetate, VFA, CO2 and H2. 

The initiator is present in the water phase, and this is where the initiating radicals are produced. The rate of radical production if, is typically of the order of 1013 radicals L-1 s-1. (The symbol p is often used instead of Rj in emulsion polymerization terminology.) The locus of polymerization is now of prime concern. The site of polymerization is not the monomer droplets since the initiators employed are insoluble in the organic monomer. Such initiators are referred to as oil-insoluble initiators. This situation distinguishes emulsion polymerization from suspension polymerization. Oil-soluble initiators are used in suspension polymerization and reaction occurs in the monomer droplets. The absence of polymerization in the monomer droplets in emulsion polymerization has been experimentally verified. If one halts an emulsion polymerization at an appropriate point before complete conversion is achieved, the monomer droplets can be separated and analyzed. An insignificant amount (approximately <0.1%) of polymer is found in the monomer droplets in such experiments. Polymerization takes place almost exclusively in the micelles. Monomer droplets do not compete effectively with micelles in capturing radicals produced in solution because of the much smaller total surface area of the droplets. 

Although to-date the emphasis has been on plasma polymerized films produced from hydrocarbon based systems, this trend in more recent times has swung towards fluorocarbons in an attempt to produce polymers of similar properties to conventionally prepared linear fluoropolymers. However, it will become clear from the account to follow that in many respects plasma polymerized fluorocarbons differ significantly from their linear counterparts. It is to the plasma polymerization of organic monomers containing solely carbon and fluorine therefore that we shall devote our attention in this section with only brief references to hydrocarbon and fluorohydrocarbon polymers for comparison purposes. 

There are many liquids capable of rapidly generating a solid product, when their droplets dispersed in an inert gas are contacted with a vapor coreactant. Such compounds include metal alkoxides, halides, and oxyhalides that react with water, hydrogen sulfide, etc., and organic monomers that can undergo either addition or condensation polymerization in the presence of appropriate initiators. The resulting powders consist of spherical particles, the size distribution of which depends on the method and conditions of droplet generation. 

Both evaporation/condensation and nebulization equipments have been employed to generate droplets of reactive organic monomers, which could undergo the polymerization to powders when exposed to an initiator vapor. 

Figure 3.10—Formation of bonded organosilanes at the interface of silica gel. Representation of organic monomers and polymers at the surface of silica gel. The arrangement Si-O-Si C is more stable than Si O C. This reaction leads to a carbon content of 4 or 5%. Other reactions can also be used (hydrosilylation in particular). When a monolayer of hydrocarbons is bonded to the surface of silica, they orient in a particular manner at the interface due to their lipophilic and hydrophilic character.

In emulsion polymerization the organic monomer is emulsified with soap in an aqueous continuous phase. 

Vanadiaxerogels are especially interesting for their redox properties, which promote the catalytical activity of enzymes such as glucose oxydase [644] or induce the oxidative polymerization of organic monomers, such as aniline, pyrrol, and thiophene [873],... 

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