Polymerizations of Monomers

In general, copolymerization provides an additional variable by which the properties of a polymer can be tuned. Copolymerization of aniline with ring substituted aniline derivatives has been well studied as a 

Water-soluble moiety Self-doping moiety 

In a subsequent study, Ruckenstein etal. prepared densely grafted copolymer poly(aniline-2-sulfonic acid-co-aniline) [114]. Water solubility of the copolymer increased with the molar ratio of aniline-2-sulfonic acid to aniline in the polymerization mixture. Also, in this study it was suggested that aggregation occurred due to intramolecular and intermolecular self-doping of the copolymer poly(aniline-2-sulfonic 

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Organic peroxides are used extensively for the curing of unsaturated polyester resins and the polymerization of monomers having vinyl unsaturation. The —O—O— bond is split into free radicals which can initiate polymerization or cross-linking of various monomers or polymers. 

Rayon is unique among the mass produced man-made fibers because it is the only one to use a natural polymer (cellulose) directly. Polyesters, nylons, polyolefins, and acryflcs all come indirectly from vegetation they come from the polymerization of monomers obtained from reserves of fossil fuels, which in turn were formed by the incomplete biodegradation of vegetation that grew millions of years ago. The extraction of these nonrenewable reserves and the resulting return to the atmosphere of the carbon dioxide from which they were made is one of the most important environmental issues of current times. CeUulosic fibers therefore have much to recommend them provided that the processes used to make them have minimal environmental impact. 

Acrylamide—acrylic polymers are made by free-radical polymerization of monomers containing the acryHc stmcture, where R is —H or —CH and is —NH2 or a substituted amide or the alkoxy group of an ester. 

The polymerization of monomers to form hydrocarbon resins is typically carried out by either the direct addition of catalyst to a hydrocarbon fraction or by the addition of feed to a solvent—catalyst slurry or solution. Most commercial manufacturers use a continuous polymerization process as opposed to a batch process. Reactor temperatures are typically in the range of 0—120°C. 

Further deprotonation, dehydration, and polymerization of monomers and dimers may yield ringlike stmctures of hydroxy—aluminum complexes (10). Coalescence of ring compounds into layers by further growth results in the formation of crystalline aluminum hydroxide at pH 6, the point of minimum aqueous solubiUty. 

Mechanisms. Because of its considerable industrial importance as well as its intrinsic interest, emulsion polymerization of vinyl acetate in the presence of surfactants has been extensively studied (75—77). The Smith-Ewart theory, which describes emulsion polymerization of monomers such as styrene, does not apply to vinyl acetate. Reasons for this are the substantial water solubiUty of vinyl acetate monomer, and the different reactivities of the vinyl acetate and styrene radicals the chain transfer to monomer is much higher for vinyl acetate. The kinetics of the polymerization of vinyl acetate has been studied and mechanisms have been proposed (78—82). 

Unlike most elastomeric polymers, which are made by direct polymerization of monomers or comonomers, chlorosulfonated polyethylene, as the name implies, is made by chemical modification of a preformed thermoplastic polymer. The chlorination and chlorosulfonation reactions are usually carried out simultaneously but may be carried out ia stages. 

Bis-maleimide resins composed of BMI and diamines have been reported in the early 1960s in the patent literature. Since that time, a number of patents have appeared describing improvements in their properties and uses [3]. Although many bis-maleimide resins are commercially developed, relatively few reports of their use as adhesives are to be found in scientific journals [4-10]. Improvements of maleimide resins are mirrored in the improvements of thermosetting polyimides. For example, the method of in situ polymerization of monomer reactants (PMR method) was developed [6]. 

Group of plastics composed of resins formulated by addition polymerization of monomers containing allyl groups (e.g., diallyl phthalate). 

Group of plastics composed of resins generated from the polymerization of monomers consisting of a carbon and a halogen or halogens. 

Two different methods have been used for the incorporation of the activating ogliomer (or monomer) in the seed particles. The first method involves the application of a small organic chemical, such as chloroundecane or dibutyl phthalate, which is incorporated into the particles in the first swelling step. In the second method, an ogliomer compound is formed by polymerization of monomers that are absorbed inside the seed particles. 

The creation of active sites as well as the graft polymerization of monomers may be carried out by using radiation procedures or free-radical initiators. This review is not devoted to the consideration of polymerization mechanisms on the surfaces of porous solids. Such information is presented in a number of excellent reviews [66-68]. However, it is necessary to focus attention on those peculiarities of polymerization that result in the formation of chromatographic sorbents. In spite of numerous publications devoted to problems of composite materials produced by means of polymerization techniques, articles concerning chromatographic sorbents are scarce. As mentioned above, there are two principle processes of sorbent preparation by graft polymerization radiation-induced polymerization or polymerization by radical initiators. We will also pay attention to advantages and deficiencies of the methods. 

However, the polymerization of monomers in the gaseous phase by first procedure (1) mentioned above leads to the formation of considerable amounts of homopolymers. It is caused by low molecular weight radicals H and OH , not bounded chemically with the solid support [70, 73], In this case the subsequent... 

Currently, graft post-polymerization of monomers in the gaseous phase (2) is the more widely used process because it has at least two basic advantages. First, side processes of homopolymerization are minimized which reduces the consumption of monomers and makes unnecessary additional treatment of the modified materials with solvents. Second, this method is universal and allows the grafting to the surfaces (such as silica) to be carried out with low radiation yields of active sites as compared to the monomers. 

Chromatographic Packings Prepared by Graft Polymerization of Monomers... 

This section describes polymerizations of monomer(s) where the initiating radicals are formed from the monomer(s) by a purely thermal reaction (/.e. no other reagents are involved). The adjectives, thermal, self-initialed and spontaneous, are used interchangeably to describe these polymerizations which have been reported for many monomers and monomer combinations. While homopolymerizations of this class typically require above ambient temperatures, copolymerizations involving certain electron-acceptor-electron-donor monomer pairs can occur at or below ambient temperature. 

With appropriate choice of reaction conditions, hyperbranched polymers can be formed by sclf-condcnsing vinyl polymerization of monomers that additionally contain the appropriate initiator (NMP, ATRP), when the compounds are called inimers, or RAFT agent functionality. Monomers used in this process include 340,716 341717 and 34204 (for NMP), 108714,714 and 344 and related monomers720 723 (for ATRP) and 343408 (for RAFT). Careful control of reaction conditions is required to avoid network formation. 

Emulsifiers are used in many technical applications. Emulsions of the oil-in-water and the water-in-oil type are produced on a large scale in the cosmetic industry. Other fields of employment are polymerization of monomers in emulsions and emulsification of oily and aqueous solutions in lubricants and cutting oils. In enhanced oil recovery dispersing of crude oil to emulsions or even microemulsions is the decisive step. 

Reactive radical ions, cations and anions are frequent intermediates in organic electrode reactions and they can serve as polymerization initiators, e.g. for vinylic polymerization. The idea of electrochemically induced polymerization of monomers has been occasionally pursued and the principle has in fact been demonstrated for a number of polymers But it appears that apart from special cases with anionic initiation the heterogeneous initiation is unfavorable and thus not competitive for the production of bulk polymers A further adverse effect is the coating of electrodes... 

Successive polymerization of monomers starting from a difunctional initiator... 

Nearly all polymerization processes and products require a post-reaction process to remove and reduce to an acceptable level residual monomer(s), solvent or diluent. End use properties can be adversely affected by high levels of residuals through toxicity, odor, or poor physical properties. In the cases of residual solvent or diluent, a separation process involving the evaporation of the volatile components (devolatilization) can be used. Devolatilization can be used for residual monomer removal, but completing the polymerization of monomer is an attractive alternative when applicable. Polymerization finishing is usually accomplished with an increase in temperature to kick-off a finishing initiator or the addition of an initiator. (D For the dispersion... 

C13-0113. One of Ihe problems encountered in Ihe polymerization of monomers lhat contain two different... 

Dopachrome also undergoes a nonenzymatic reaction to form dihidroxyindole (DHI), the precursor of DHI-eumelanins. For the formation of phaeomelanins, dopaquinone is first transformed in cysteinil-DOPA and then in cysteinyl-dopaquinone which suffers a nonenzymatic polymerization. The polymerization of monomers and the association of melanins with proteins is not yet completely elucidated and may involve other intermediates. ... 

One of the ways to synthesize specialty polymers with certain desirable functional groups is by the polymerization of monomers with the desirable functional groups. However there are often a number of difficulties associated with polymerization of these... 

Synthesis. Graft copolymer was formed in aqueous solution by ceric-ion-initiated, radical polymerization of monomer on starch. Polymerization was conducted in an inert, atmosphere. Details of the synthesis procedure may be found in references 41 to 43 In recovering the polymer product, freeze drying was used with care since freeze drying produces a more dissolvable and useful product but can degrade polymers with molecular weights of 1 million or more. Poly(starch-g-(1-amidoethylene)) Poly(starch-g-(1-amidoethylene))... 

Very undesirable structural irregularities are 0-0 bonds that may be introduced into the polymer during its storage and/or during the polymerization of monomers not sufficiently deprived from oxygen. 

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