Divinyl monomer

Vinyl polymers cross-linked with divinyl monomers, for example, polystyrene polymerized in the presence of divinyl benzene. 

In the multistep swelling and polymerization method, polymerization time, temperature, and initiator concentration have marginal effects only. The ratio of monovinyl to divinyl monomer in the polymerization mixture, along with the composition of the porogenic systems, is known to be the most important factor in controlling the ultimate macroporous structure. The average molecular... 

The arm-first synthesis of star microgels by initiating polymerization or copolymerization of a divinyl monomer such as diviny lbenzene or a bis-maleimide with a polystyryl alkoxyamine was pioneered by Solomon and coworkers.692 693 The general approach had previously been used in anionic polymerization. The method has now been exploited in conjunction with NMP,692 6 ATRP69 700 and RAFT.449 701 702 The product contains dormant functionality in the core. This can be used as a core for subsequent polymerization of a monoene monomer to yield a mikto-arm star (NMP ATRP704). 

In this paper, the pseudo-kinetic rate constant method in which the kinetic treatment of a multicomponent polymerization reduces to that of a hcmopolymerization is extensively applied for the statistical copolymerization of vinyl/divinyl monomers and applications to the pre- and post-gelation periods are illustrated. 

Crosslihkinq Density Distribution. Let us consider the statistical copolymerization of vinyl/divinyl monomers without chain transfer to polymer for simplicity. In this case the crosslinking density p is defined as follows. 

For this low mole fraction of divinyl monomer (f2o 1-52 xlO ) the effect of cyclization should not be significant, and the calculated results for weight fraction of gel agree with experimental data satisfactorily. But to accurately calculate the structural properties of the gel such as crosslinking density, it will be necessary to consider the effect of cyclization. 

In the case of vinyl/divinyl copolymerization, the subscript 1 is used to designate mono-vinyl monomer, 2 is used for divinyl monomer. f Q indicates the initial mole fraction of divinyl monomer in the monomer mixture, instantaneous mole fraction of monomer i bound in the polymer chain. 

In principle, polymers equivalent to those obtained from vinyl and divinyl monomers may be synthesized by this method. The product in the above example possesses the same chain structure as polyethylene. The polymerization process, notwithstanding the likelihood of a metal alkyl intermediate, should conform satisfactorily to stepwise condensation. However, the product, and those obtained by Friedel-Crafts condensation as well, lack the recurrent functional groups which generally characterize condensation polymers. 

Divinyl monomers such as divinylbenzene, divinyl adipate, and ethylene dimethacrylate, in which the reaction of one double bond does not alter greatly the reactivity of the other, polymerize to highly cross-linked structures. 

Copolymers prepared from a vinyl monomer and a small proportion of a divinyl monomer are closely related to cross-linked polymers. They will be considered in the final section of the present chapter, where the application of the critical conditions set forth above will be discussed in greater detail. 

If an inert good solvent is used in solution polymerization, the gel thus obtained will have a supercoiled (expanded) structure (Gel B). Gel B swells in good solvents much more than Gel A which is synthesized in bulk. If the amount of the crosslinking divinyl monomer in the reaction mixture is increased while the amount of solvent remains constant, highly crosslinked networks are formed that cannot absorb all solvent molecules present in the reaction mixture and a heterogeneous structure results (Gel C). A part of the solvent separates from the gel phase during polymerization and the formed Gel C consists of two continuous phases, a gel and a solvent phase. If the amount of solvent is further increased, a... 

Fig. 2. Formation of various structures in radical crosslinking copolymerization of monovinyl -divinyl monomers with or without using a solvent (diluent).

During the past 25 years, Funke and co-workers have extensively studied the emulsion polymerization of divinyl monomers alone including 1,4-DVB and ethylene glycol dimethacrylate (EDM A) under various reaction conditions. They found that the intraparticle crosslinking changes drastically the classical picture of emulsion polymerization. 

In EP of bifunctional vinyl monomers, the reaction rate increases with the emulsifier concentration because the number of particles increases. However, in the crosslinking EP of divinyl monomers, the reaction rate is inversely proportional to the emulsifier concentration. This unusual behavior is due to nucleation taking place in both micelles and monomer droplets. In monomer droplets, the kinetics resembles that of bulk polymerization and therefore the reaction rates... 

Radical polymerizations have three important reaction steps in common chain initiation, chain propagation, and chain termination. For the termination of chain radicals several mechanisms are possible. Since the lifetime of a radical is usually less than 1 s, radicals are continuously generated and terminated. Each propagating radical can add a finite number of monomers between its initiation and termination. If a divinyl monomer is in the monomer mixture, the reaction kinetics changes drastically. In this case, a dead polymer chain may grow again as a macroradical, when its pendant vinyl groups react with radicals, and the size of the macromolecule increases until it extends over the whole available volume. 

The divinyl monomers can thus be found in macromolecules as units which bear pendant vinyl groups or which are involved in cycles, crosslinks or multiple crosslinks. Since the number of crosslinks necessary for the onset of macrogelation is very low [64], pendant vinyl groups in RCC are mainly consumed in cycles and multiple crosslinks. Therefore, the reaction rate of pendant vinyl groups is a very sensitive indicator for the formation of cycles and multiple crosslinks in finite species [100,147,157-160]. 

The conversion of pendant vinyl groups, x3, may be defined as the fraction of divinyl monomer units with both vinyl groups reacted... 

Among the divinyl monomers, 1,4-DVB and EDM A are the most extensively studied monomers for microgel formation by anionic polymerization. Com-... 

Star-shaped macromolecules have also been synthesized by using the monofunctional "living" precursor as an Initiator for the polymerization of a small amount of a divinyl monomer. A small crosslinked nodule is formed, which is connected with the p chains that have contributed to Its Initiation. It turns out that fluctuations on the value of p within a sample remain rather small, and consequently the star polymers obtained by this method can also be considered as tailor-made polymers. Recently star molecules with deuterium labeled central nodule have been synthesized according to the... 

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