Polymer precipitation

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. 

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... 

A schematic diagram of the polymer precipitation process is shown in Figure 8. The hot polymer solution is cast onto a water-cooled chill roU, which cools the solution, causing the polymer to precipitate. The precipitated film is passed through an extraction tank containing methanol, ethanol or 2-propanol to remove the solvent. Finally, the membrane is dried, sent to a laser inspection station, trimmed, and roUed up. The process shown in Figure 8... 

Fig. 8. Equipment to prepare microporous membranes by the polymer precipitation by cooling technique (23).

Excessive hydrolysis of polyacrylamide in situ can promote undesirable polymer precipitation in the reservoir. The rate of this hydrolysis decreases with increasing level of anionic comonomers such as AMPS (130). 

Tempera.ture Effect. Near the boiling point of water, the solubiUty—temperature relationship undergoes an abmpt inversion. Over a narrow temperature range, solutions become cloudy and the polymer precipitates the polymer caimot dissolve in water above this precipitation temperature. In Figure 4, this limit or cloud point is shown as a function of polymer concentration for poly(ethylene oxide) of 2 x 10 molecular weight. 

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. 

Polymerization Kinetics of Mass and Suspension PVC. The polymerization kinetics of mass and suspension PVC are considered together because a droplet of monomer in suspension polymerization can be considered to be a mass polymerization in a very tiny reactor. During polymerization, the polymer precipitates from the monomer when the chain size reaches 10—20 monomer units. The precipitated polymer remains swollen with monomer, but has a reduced radical termination rate. This leads to a higher concentration of radicals in the polymer gel and an increased polymerization rate at higher polymerization conversion. 

Polymers that form from the liqmd phase may remain dissolved in the remaining monomer or solvent, or they may precipitate. Sometimes beads are formed and remain in suspension sometimes emulsions form. In some processes solid polymers precipitate from a fluidized gas phase. 

The solution of poly(vinyl butyral) is diluted with methanol and the polymer precipitated by the addition of water during vigorous agitation. The polymer is then stabilised, washed and dried. 

The reflux of aqueous Pu(IV) solutions containing <6 M HNO3 produces polymer precipitates that are resistant to subsequent dissociation and dissolution in nitric acid. Eapid aging of the Pu(IV) polymer to form a PuC -like structure is responsible for the unusually stable polymer. Comparative studies under nonreflux conditions show that polymer does not form at concentrations of HNO3 >3 M. 

Figure 4. Infrared spectra of KBr pellets containing Pu(IV) polymer precipitates, (A) prepared in -purged glove hag free of CO2 (B) prepared in laboratory atmosphere. (Reprinted with permission from Ref. 6.)...

In good solvents, a polymer becomes well solvated by solvent molecules and the conformation of its molecules expands. By contrast, in poor solvents a polymer is not well solvated, and hence adopts a relatively contracted conformation. Eventually of course, if the polymer is sufficiently poor the conformation becomes completely contracted, there are no polymer-solvent interactions, and the polymer precipitates out of solution. In other words, the ultimate poor solvent is a non-solvent. 

The successive fractions may be obtained by lowering the temperature in suitable increments rather than by varying the solvent composition isothermally. If a poor solvent is found from which the polymer precipitates in a convenient temperature range, it may be used alone without addition of another component. 

A temperature of 30-40 C and a moderate pressure are enough to cause a violent polymerisation, which can increase the pressure in the reactor to 1000 -1200 bar. In storage, a low polymerisation can also be dangerous for a different reason. In this case, polymer precipitates in the form of flakes causing the volume to rise, which can eventually cause the storage tanks to detonate. Butadiene can only be stored if it contains a poiymerisation inhibitor, which also plays the role of an oxidation inhibitor. Tert-butylcatechol concentrated at 0.2% is perfect for this use, but rust and water can damage the inhibitor. 

The polymer/additive system in combination with the proposed extraction technique determines the preferred solvent. In ASE the solvent must swell but not dissolve the polymer, whereas MAE requires a high dielectric solvent or solvent component. This makes solvent selection for MAE more problematical than for ASE . Therefore, MAE may be the preferred method for a plant laboratory analysing large numbers of similar samples (e.g. nonpolar or polar additives in polyolefins [210]). At variance to ASE , in MAE dissolution of the polymer will not block any transfer lines. Complete dissolution of the sample leads to rapid extractions, the polymer precipitating when the solvent cools. However, partial dissolution and softening of the polymer will result in agglomeration of particles and a reduction in extraction rate. 

HPLC methods of determining the amounts of different additives in polymeric materials are preceded by an extraction process or dissolution of the polymer matrix. Although extraction-HPLC is often observed to be superior to the traditional spectroscopic techniques (UV and IR) in analysing additives, it is frequently difficult to obtain reproducible results in view of the variability of the extraction yield. On the other hand, it is equally difficult to obtain quantitative data in the dissolution/reprecipitation-HPLC method because of entrapment of analytes in the polymer precipitate and the potential for high absorption of the additives on the polymer surface. 

The polymer molecular weight may be greatly diminished if polymerization takes place under conditions where polymer precipitates from solution and/or is not well solvated. The reacting functional groups become inaccessible to each other and polymerization stops before the desired DP is reached. 

Following solubilization of the PHA from the defatted plant material, recovery of PHA from the solvent can be accomplished in various ways (Fig. 5) [74-78]. Addition of a PHA non-solvent to the solution would lead to PHA precipitation. If a solvent was used which dissolves PHA only under high temperature and pressure, cooling the solvent may be used to recover the polymer. Alternatively, evaporation of the solvent could also lead to polymer precipitation. Each of these methods have their disadvantages. Precipitation of PHA... 

Linear absorption spectra for the three solutions considered herein are given in Fig. 1. The concentration range available in the yellow solution is 0-120 x 10 r.u./cm. For the other solutions an upper limit is imposed on the concentration range due to polymer precipitation 4 x 10 r.u./cm for the red soution and -9 x 10 r.u./cm for the blue solution. 

Simple removal of the catalyst using ion-exchange resins, extractions with water or polymer precipitation [148,149,150,151]... 

Nonsolvent bath, polymer precipitation by immersion in, 15 808-811 Nonspecific elution, in affinity chromatography, 6 398, 399 Nonstationary Poisson process, in reliability modeling, 26 989 Non-steady-state conduction, 9 105 Nonsteroidal antiinflamatory agents/drugs (NSAIDs) 21 231 for Alzheimer s disease, 2 820 for cancer prevention, 2 826 Nonsulfide collectors, 16 649 Nonsulfide flotation, 16 649-650 Nonsulfide mineral flotation collectors used in, 16 648-649t modifiers used in, 16 650, 651t Nonsulfide ores, 16 598, 624... 

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