Asymmetric polymers

Aldehyde Polymers Asymmetric anionic polymerization can lead trichloroacetalde-hyde (chloral) to a one-handed helical, isotactic polymer having a 4/1-helical conformation with... 

MeniDrane Types A detailed taxonomy of membranes is beyond the scope of this handbook. Membranes may be made from physical solids (metal, ceramic, etc.), homogeneous films (polymer, metal, etc.), heterogeneous solids (polymer mixes, mixed glasses, etc.), solutions (usually polymer), asymmetric structures, and liquids. 

Keywords Transition metal complexes Living polymerization Rigid rod helical structure Optically active polymer Asymmetric polymerization... 

There has been very little progress in the last five years in improving the performance of single polymer asymmetric membranes. Meanwhile, the composite membranes have been improved and they exhibit a higher flux and better re-... 

In the systems of flexible chain polymers, asymmetric single elements are identified with the uniaxial statistical chain segments. Considering a cylindrical cluster of uniaxial elements oriented at 0 = (0, ), the condition of compliant orientation reduces fraction of the chain segments involved in the association process to w(6))A where... 

Heterocyclic polymer Asymmetric / membrane / 4. Toray-Polyamidic acid, Du Pont-DP-1, Monsanto 6. Cellanese-Polybenzimidazole... 

We have been studying the helix-sense-selective polymerization of bulky methacrylates such as triphenylmethyl methacrylate (TrMA), diphenyl-2-pyridylmethyl methacrylate (D2PyMA)phenyl-2-pyridyl-o- and m-tolylmethyl methacrylates (PPyoTMA and PPymTMA), and (S)-(-)-diphenyl(1-methylpyrrolidin-2-yl)methyl methacrylate (DMPMA) with chiral anionic initiators. In these polymerizations, optically active polymers with one-handed helical structure have been obtained and some of the polymers exhibited characteristic conformational transition in solution. In the present paper, we describe helix-sense-selective polymerization of 1 -phenyidibenzosuberyl methacrylate (PDBSMA), diphenyl-3-pyridylmethyl methacrylate (D3PyMA) and phenyl[bis(2-pyridyl)]methyl methacrylate (PB2PyMA) by means of chiral anionic initiators and conformational transition of the obtained polymers. Asymmetric radical polymerization of PDBSMA is also reported because this monomer can also afford a helical, highly isotactic polymer by radical mechanism. 

In polymers made of dis-symmetric monomers, such as, for example, poly(propylene), the stmcture may be irregular and constitutional isomerism can occur as shown in figure C2.1.1(a ). The succession of the relative configurations of the asymmetric centres can also vary between stretches of the chain. Configuration isomerism is characterized by the succession of dyads which are named either meso, if the two asymmetric centres have the same relative configurations, or racemo if the configurations differ (figure C2.1.1(b )). A polymer is called isotactic if it contains only one type of dyad and syndiotactic if the dyad sequence strictly alternates between the meso and racemo fonns. 

Structures [VIII] and [IX] are not equivalent they would not superimpose if the extended chains were overlaid. The difference has to do with the stereochemical configuration at the asymmetric carbon atom. Note that the asymmetry is more accurately described as pseudoasymmetry, since two sections of chain are bonded to these centers. Except near chain ends, which we ignore for high polymers, these chains provide local symmetry in the neighborhood of the carbon under consideration. The designations D and L or R and S are used to distinguish these structures, even though true asymmetry is absent. 

Complications arising from other types of isomerism. Positional and geometrical isomerism, also described in Sec. 1.6, will be excluded for simplicity. In actual polymers these are not always so easily ignored. Polymerization of 1,2-disubstituted ethylenes. Since these introduce two different asymmetric carbons into the polymer backbone (second substituent Y), they have the potential to display ditacticity. Our attention to these is limited to the illustration of some terminology which is derived from carbohydrate nomenclature (structures [IX]-[XII]) ... 

Fibers spun by this method may be isotropic or asymmetric, with dense or porous walls, depending on the dope composition. An isotropic porous membrane results from spinning solutions at the point of incipient gelation. The dope mixture comprises a polymer, a solvent, and a nonsolvent, which are spun into an evaporative column. Because of the rapid evaporation of the solvent component, the spinning dope solidifies almost immediately upon emergence from the spinneret in contact with the gas phase. The amount of time between the solution s exit from the spinneret and its entrance into the coagulation bath has been found to be a critical variable. Asymmetric fibers result from an inherently more compatible solvent/nonsolvent composition, ie, a composition containing lower nonsolvent concentrations. The nature of the exterior skin (dense or porous) of the fiber is also controlled by the dope composition. 

Any of the four monomer residues can be arranged in a polymer chain in either head-to-head, head-to-tail, or tail-to-tail configurations. Each of the two head-to-tail vinyl forms can exist as syndiotactic or isotactic stmctures because of the presence of an asymmetric carbon atom (marked with an asterisk) in the monomer unit. Of course, the random mix of syndiotactic and isotactic, ie, atactic stmctures also exists. Of these possible stmctures, only... 

Phase Inversion (Solution Precipitation). Phase inversion, also known as solution precipitation or polymer precipitation, is the most important asymmetric membrane preparation method. In this process, a clear polymer solution is precipitated into two phases a soHd polymer-rich phase that forms the matrix of the membrane, and a Hquid polymer-poor phase that forms the membrane pores. If precipitation is rapid, the pore-forming Hquid droplets tend to be small and the membranes formed are markedly asymmetric. If precipitation is slow, the pore-forming Hquid droplets tend to agglomerate while the casting solution is stiU fluid, so that the final pores are relatively large and the membrane stmcture is more symmetrical. Polymer precipitation from a solution can be achieved in several ways, such as cooling, solvent evaporation, precipitation by immersion in water, or imbibition of... 

Cellulose acetate Loeb-Sourirajan reverse osmosis membranes were introduced commercially in the 1960s. Since then, many other polymers have been made into asymmetric membranes in attempts to improve membrane properties. In the reverse osmosis area, these attempts have had limited success, the only significant example being Du Font s polyamide membrane. For gas separation and ultrafUtration, a number of membranes with useful properties have been made. However, the early work on asymmetric membranes has spawned numerous other techniques in which a microporous membrane is used as a support to carry another thin, dense separating layer. 

HoUow-fiber fabrication methods can be divided into two classes (61). The most common is solution spinning, in which a 20—30% polymer solution is extmded and precipitated into a bath of a nonsolvent, generally water. Solution spinning allows fibers with the asymmetric Loeb-Soufirajan stmcture to be made. An alternative technique is melt spinning, in which a hot polymer melt is extmded from an appropriate die and is then cooled and sohdified in air or a quench tank. Melt-spun fibers are usually relatively dense and have lower fluxes than solution-spun fibers, but because the fiber can be stretched after it leaves the die, very fine fibers can be made. Melt spinning can also be used with polymers such as poly(trimethylpentene), which are not soluble in convenient solvents and are difficult to form by wet spinning. 

These solvents include tetrahydrofuran (THF), 1,4-dioxane, chloroform, dichioromethane, and chloroben2ene. The relatively broad solubiHty characteristics of PSF have been key in the development of solution-based hoUow-fiber spinning processes in the manufacture of polysulfone asymmetric membranes (see Hollow-fibermembranes). The solvent Hst for PES and PPSF is short because of the propensity of these polymers to undergo solvent-induced crysta11i2ation in many solvents. When the PES stmcture contains a small proportion of a second bisphenol comonomer, as in the case of RADEL A (Amoco Corp.) polyethersulfone, solution stabiHtyis much improved over that of PES homopolymer. 

Most commercially available RO membranes fall into one of two categories asymmetric membranes containing one polymer, or thin-fHm composite membranes consisting of two or more polymer layers. Asymmetric RO membranes have a thin ( 100 nm) permselective skin layer supported on a more porous sublayer of the same polymer. The dense skin layer determines the fluxes and selectivities of these membranes whereas the porous sublayer serves only as a mechanical support for the skin layer and has Httle effect on the membrane separation properties. Asymmetric membranes are most commonly formed by a phase inversion (polymer precipitation) process (16). In this process, a polymer solution is precipitated into a polymer-rich soHd phase that forms the membrane and a polymer-poor Hquid phase that forms the membrane pores or void spaces. 

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