Polymerization heterogeneous bulk

Bulk Polymerization. The bulk polymerization of acrylonitrile is complex. Even after many investigations into the kinetics of the polymerization, it is stiU not completely understood. The complexity arises because the polymer precipitates from the reaction mixture barely swollen by its monomer. The heterogeneity has led to kinetics that deviate from the normal and which can be interpreted in several ways. 

In heterogeneous polymerizations in bulk, the formed polymer is insoluble in its monomer and the polyreaction is performed below the softening point of the polymer. On an industrial scale, this type of process is especially utilized for chain polymerizations, for example, the radical polymerization of liquid vinyl chloride, the polymerization of liquid propylene with Ziegler-Natta or with metallocene catalysts, and the polymerization of molten trioxane. 

Polymer in solution Any (e.g., a condensation product or another polymer phase) Heterogeneous bulk or solution polymerization Salt precipitating from a condensation reaction. Prepolymerized rubber precipitating from a solution of polystyrene in styrene monomer... 

Tt is well known that the presence of precipitated polymer can influence the course of polymerization. In bulk acrylonitrile polymerization the effects are most dramatic and have been the subject of many studies. The literature on this subject has been reviewed by Bamford et al. (4) by Thomas (29), and by Peebles (23). Under conditions where the system becomes heterogeneous owing to precipitation of small particles of polymer, a protracted acceleration period is observed at the start of polymerization, and the final rate is found to depend on the 0.8 power of the concentration of free radical initiator. Unusual post-polymerization effects are observed in photoinitiated polymerization of acrylonitrile, owing to the presence of trapped radicals which can be detected by electron spin resonance. None of the detailed mechanisms proposed to... 

Monomers, such as styrene which are good solvents for their polymers do not retard the bulk polymerization rate. However, this rate does not increase in a viscous good solvent medium that is present toward the end of the polymerization. Heterogeneous solution polymerization in nonvlscous poor solvents (1 ) and in viscous poor solvents is faster than rates observed in good solvents. 

Heterogeneous systems comprising (a) heterogeneous bulk polymerizations, (b) heterogeneous solution polymerizations, (c) suspension systems, (d) emulsion systems, (e) dispersion polymerization, (0 gas phase polymerization, and (g) interfacial polymerizations. 

Polyfvinyl chloride) (PVC) is produced by mass, suspension, and emulsion processes. Mass polymerization is an exatiiple of a heterogeneous bulk system. PVC is virtually insoluble in vinyl chloride because the polymer is about 35% more dense than the monomer under normal polymerization conditions. Vinyl chloride, however, is quite soluble in polymer. The two phases in PVC polymerizations are pure monomer and monomer-swollen polymer. Polymerization proceeds in both phases, but it is very much faster in the polymer-rich phase because the mobility of macro radicals and mutual termination reactions are. severely restricted (cf. Section 6.13.2). 

Nanoparticles, 10-1000 nm polymeric particles, are prepared from the same natural and synthetic biodegradable polymers as microspheres. ° Albumin nanoparticles are prepared by the cross-linking processes mentioned previously. For the preparation of particles from synthetic polymers, heterogeneous bulk polymerization techniques of suspension, emulsion, and micelle polymerization are often used. 

Many thermoplastics are heterogeneous (or heterophase) because they contain liquid or rubber dispersions that improve their physical properties with respect to those of the continuous brittle phase. Examples of this are the softening of PVC by the presence of phthalate droplets and the improved toughness of HIPS or the polymer of acrylonitrile-butadiene-styrene (ABS) by addition of PBD-based rubber particles. This chapter will focus on the (heterogeneous, bulk and free-radical) polymerizations leading to the production of HIPS and PVC. 

The relationships between the molecular mass and the composition of styrene-methyl acrylate copolymers prepared by radical polymerization in bulk were examined [47]. Experimental results agreed with polymerization kinetics for the low-conversion samples, where the chemical heterogeneity obtained by SEC was negligible. However, the methyl acrylate content for the... 

The first process used to polymerize vinyl chloride was a heterogeneous bulk polymerization process where the monomer and initiator were reacted in a rotating cylindrical reactor with steel balls used to remove heat away from the product (the tumbling also served to ground up the resin product). 

A theoretical treatment of soapless emulsion polymerization of methyl methacrylate in water has shown that the number of particles is determined during the initial stages, and has clarified the relationships between this method, normal emulsion polymerization, and bulk polymerization. Differences between the heterogeneous polymerization of acrylonitrile and vinyl chloride have been discussed, following the development of an elaborate model for the former case in which propagation proceeds in the liquid and, eventually, also in the solid phase. ... 

This Chapter deals with the non-destructive determination of additives in the solid polymeric matrix (bulk) by spectroscopic methods, however without any concern for surface distributions or micro-analytical aspects, for which the reader is referred to Chapters 4 and 5. As the additives might be heterogeneously distributed in the polymer, measurements at various positions are recommended. Table 1.2 indicates the main electronic and vibrational spectroscopic techniques currently in use for direct poly-mer/additive analysis. 

Most bulk polymerizations are homogeneous. However, if the polymer is insoluble in its monomer and precipitates as the reaction proceeds, the process is sometimes known as heterogeneous bulk or precipitation polymerization. Two examples of such polymers are polyacrylonitrile and polyvinyl chloride (PVC). The latter is produced commerdaJly by a heterogeneous bulk process, which allows control of particle size and porosity for optimum plasticizer absorption. Such heterogeneous polymerizations do not follow the kinetic scheme developed in Chapter X for homogeneous reactions. 

Alkali Metal Catalysts. The polymerization of isoprene with sodium metal was reported in 1911 (49,50). In hydrocarbon solvent or bulk, the polymerization of isoprene with alkaU metals occurs heterogeneously, whereas in highly polar solvents the polymerization is homogeneous (51—53). Of the alkah metals, only lithium in bulk or hydrocarbon solvent gives over 90% cis-1,4 microstmcture. Sodium or potassium metals in / -heptane give no cis-1,4 microstmcture, and 48—58 mol % /ram-1,4, 35—42% 3,4, and 7—10% 1,2 microstmcture (46). Alkali metals in benzene or tetrahydrofuran with crown ethers form solutions that readily polymerize isoprene however, the 1,4 content of the polyisoprene is low (54). For example, the polyisoprene formed with sodium metal and dicyclohexyl-18-crown-6 (crown ether) in benzene at 10°C contains 32% 1,4-, 44% 3,4-, and 24% 1,2-isoprene units (54). 

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... 

When we design commercial polymerization plants we must consider the characteristics of both the monomer and the final product. This allows us to define the optimum configuration to produce a specific polymer. Polymerization reactions can take place in homogeneous solutions or heterogeneous suspensions. For homogeneous processes, the diluted or pure monomer(s) are added directly to one another and the reaction occurs in the media created when mixing the reactants. When the reactants are added directly to one another, the process is referred to as a bulk process. With heterogeneous processes, a phase boundary exists which acts as an interface where the reaction occurs. 

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... 

The bulk polymerization of acrylonitrile has been studied by numerous workers (for a literature survey on the problem see ref. j O and JL1J. The kinetic features of this reaction at room temperature are summarized in Table I. It is one of the typical examples of polymerization under heterogeneous conditions in which the anomalies are generally assumed to arise as a result of non-stationary conditions caused by the "occlusion" of growing chains in the precipitated polymer (10). The presence of occluded radicals was indeed demonstrated by 5R measurements (12) and by... 

The features of the electro-oxidative polymerization can he explained as follows. The molecular weight of the obtained polymer stayed constant during the polymerization, because the polymerization proceeds heterogeneously in the diffusion layer of electrode. The C-0 coupling reaction is predominant, probably because the phenol is adsorbed and oriented on the electrode surface. The polymerization started from the dimer is much suppressed, because the dimer diffuses from the bulk phase into the diffusion layer very slowly. 

The solubility of polyoxymethylene is very poor so that the ring-opening polymerization of 1,3,5-trioxane proceeds heterogeneously both in bulk (melt) and in solution. 1,3,5-Trioxane can also be readily polymerized in the solid state this polymerization can be initiated both by high-energy radiation and by cationic initiators (see Example 3-24). 

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