Molecular weight distribution, effect

Several prelreatmcnt techniques have been practiced in conjunction with the use of organic polymeric membranes. The choice of a particular technique to apply depends to a great extent on the chemical nature of the feed, membrane resistance toward the feed stream and the product requirements. The characteristics of the feed such as the panicle size or molecular weight distribution, effective fluid viscosity and pH (and therefore the... 

Polyol Molecular Weight Distribution Effect on Mechanical and Dynamic Properties of Polyurethanes... 

Molecular Weight and Molecular Weight Distribution Effects of Electron Donors. The production of broad molecular weight distributed polypropylene is a fimction of the multiplicity of active centers, which differ in stereo- and regiospecificity, and the propagation rate. Lewis bases in general, and external alkoxy silane donors in particular can influence the molecular weight... 

In this chapter, we turn our attention to binary mixtures of different polymers. These are perhaps better termed pseudo-binary because here we do not consider molecular weight distribution effects of polymer chains of different molecular weights as independent species. Our hrst concern is with miscibility, as it was with polymer-solvent systems in Chapter 3 and with polymer-additive systems in Chapter 4. We consider which polymer structures are likely to lead to miscibility. This leads to a consideration of partially miscible systems and to mixtures involving copolymers. Finally, we consider immiscible polymer blends. Here we emphasize the role of interfacial tension between phases and the factors influencing phase morphology. 

We saw in Chap. 1 that the ratio M /M is widely used in polymer chemistry as a measure of the width of a molecular weight distribution. If the effect of chain ends is disregarded, this ratio is the same as the corresponding ratio of n values ... 

The molecular weight distribution for a polymer like that described above is remarkably narrow compared to free-radical polymerization or even to ionic polymerization in which transfer or termination occurs. The sharpness arises from the nearly simultaneous initiation of all chains and the fact that all active centers grow as long as monomer is present. The following steps outline a quantitative treatment of this effect ... 

AlkyUithium compounds are primarily used as initiators for polymerizations of styrenes and dienes (52). These initiators are too reactive for alkyl methacrylates and vinylpyridines. / -ButyUithium [109-72-8] is used commercially to initiate anionic homopolymerization and copolymerization of butadiene, isoprene, and styrene with linear and branched stmctures. Because of the high degree of association (hexameric), -butyIUthium-initiated polymerizations are often effected at elevated temperatures (>50° C) to increase the rate of initiation relative to propagation and thus to obtain polymers with narrower molecular weight distributions (53). Hydrocarbon solutions of this initiator are quite stable at room temperature for extended periods of time the rate of decomposition per month is 0.06% at 20°C (39). 

The methodology for preparation of hydrocarbon-soluble, dilithium initiators is generally based on the reaction of an aromatic divinyl precursor with two moles of butyUithium. Unfortunately, because of the tendency of organ olithium chain ends in hydrocarbon solution to associate and form electron-deficient dimeric, tetrameric, or hexameric aggregates (see Table 2) (33,38,44,67), attempts to prepare dilithium initiators in hydrocarbon media have generally resulted in the formation of insoluble, three-dimensionally associated species (34,66,68—72). These precipitates are not effective initiators because of their heterogeneous initiation reactions with monomers which tend to result in broader molecular weight distributions > 1.1)... 

Transamidation is an important process in the melt phase for polyamides because it is usually the process by which an equiUbrium molecular weight distribution is reestabUshed and, in the case of the melt blending of two or more polyamides to form a copolymer, it is the process by which randomi2ation of the individual monomers along the chain is effected. In the soHd phase, chain mobiUty is restricted and equiUbrium in either case often is not achieved. 

Cocatalysts, such as diethylzinc and triethylboron, can be used to alter the molecular-weight distribution of the polymer (89). The same effect can also be had by varying the transition metal in the catalyst chromium-based catalyst systems produce polyethylenes with intermediate or broad molecular-weight distributions, but titanium catalysts tend to give rather narrow molecular-weight distributions. 

In addition, subsequent chain transfer reactions may occur on side chains and the larger the resulting polymer, the more likely will it be to be attacked. These features tend to cause a wide molecular weight distribution for these materials and it is sometimes difficult to check whether an effect is due inherently to a wide molecular weight distribution or simply due to long chain branching. 

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