Dilute solution gels

In 4.3 we have already seen that polymers, in the rubber or fluid condition, crystallize much more rapidly when their chains are oriented. Therefore a stretched rubber, if stereospecific in its molecular structure, is able to crystallize at a temperature considerably above its equilibrium thermodynamic melting point. Also a thermoplast such as polyethylene, when in the molten state or in solution, can crystallize spontaneously when the chains are being orientated in elongational flow. The latter case is utilized when polyethylene is spun from a diluted solution (gel spinning process), resulting in fibres of super-high strength and stiffness ( Dyneema fibres). 

Study of the structure and physicochemical properties of comb-shaped polymers in dilute solutions, gels, and the solid phase genoalized in [8] permitted describing the structural features of this special class of branched polym systems in detail within the framework of the so-called rotational-crystalline state, a variety of the LC state. 

Polymers in Solution. Polyacrylamide is soluble in water at all concentrations, temperatures, and pH values. An extrapolated theta temperature in water is approximately —40° C (17). Insoluble gel fractions are sometimes obtained owing to cross-link formation between chains or to the formation of imide groups along the polymer chains (18). In very dilute solution, polyacrylamide exists as unassociated coils which can have an eUipsoidal or beanlike stmcture (19). Large aggregates of polymer chains have been observed in hydrolyzed polyacrylamides (20) and in copolymers containing a small amount of hydrophobic groups (21). 

As the quinone stabilizer is consumed, the peroxy radicals initiate the addition chain propagation reactions through the formation of styryl radicals. In dilute solutions, the reaction between styrene and fumarate ester foUows an alternating sequence. However, in concentrated resin solutions, the alternating addition reaction is impeded at the onset of the physical gel. The Hquid resin forms an intractable gel when only 2% of the fumarate unsaturation is cross-linked with styrene. The gel is initiated through small micelles (12) that form the nuclei for the expansion of the cross-linked network. 

Among the techniques employed to estimate the average molecular weight distribution of polymers are end-group analysis, dilute solution viscosity, reduction in vapor pressure, ebuUiometry, cryoscopy, vapor pressure osmometry, fractionation, hplc, phase distribution chromatography, field flow fractionation, and gel-permeation chromatography (gpc). For routine analysis of SBR polymers, gpc is widely accepted. Table 1 lists a number of physical properties of SBR (random) compared to natural mbber, solution polybutadiene, and SB block copolymer. 

Molecular weights of PVDC can be determined directly by dilute solution measurements in good solvents (62). Viscosity studies indicate that polymers having degrees of polymerization from 100 to more than 10,000 are easily obtained. Dimers and polymers having DP < 100 can be prepared by special procedures (40). Copolymers can be more easily studied because of thek solubiUty in common solvents. Gel-permeation chromatography studies indicate that molecular weight distributions are typical of vinyl copolymers. 

With Acyl Halides, Hydrogen Halides, and Metallic Halides. Ethylene oxide reacts with acetyl chloride at slightly elevated temperatures in the presence of hydrogen chloride to give the acetate of ethylene chlorohydrin (70). Hydrogen haUdes react to form the corresponding halohydrins (71). Aqueous solutions of ethylene oxide and a metallic haUde can result in the precipitation of the metal hydroxide (72,73). The haUdes of aluminum, chromium, iron, thorium, and zinc in dilute solution react with ethylene oxide to form sols or gels of the metal oxide hydrates and ethylene halohydrin (74). 

In the present work, the technique of XO and MTB immobilization onto silica gel in the form of its complexes with Fe(III) and Bi(III) respectively were found. The acid - base and chemical-analytical characteristics of solid-phase reagents were examined. The optimal conditions of quantitative recovery of Pb(II) and Zn(II) from diluted solutions, such as acidity of aqueous phase, the mass of the sorbents, the volume of solutions and the time of equilibrium reaching, were found. The methods of and F" detenuination were based on a competitive reactions of Zr(IV) with immobilized MTB and or F". Optimal conditions of 0,0 and F" determination in solution using SG, modified ion associates QAS-MTB (pH = 1,5, = 5-10 mol/1). 

Sodium alginate [9005-38-3]. Freed from heavy metal impurities by treatment with ion-exchange resins (Na -form), or with a dilute solution of the sodium salt of EDTA. Also dissolved in 0. IM NaCl, centrifuged and fractionally ppted by gradual addition of EtOH or 4M NaCl. The resulting gels were centrifuged off, washed with aq EtOH or acetone, and dried under vacuum. [Buchner, Cooper and Wassermann J Chem Soc 3974 7967.]... 

It remains to evaluate the quantity c — Cs. Since an explicit general solution is not to be had, we resort to the consideration of special cases. First, suppose that the external electrolyte concentration Cs is very small compared with the concentration ic /z- of the ge-gen ions belonging to the polymer and occurring in the gel. Then the second term in the left-hand member of Eq. (45) may be neglected in comparison with the first. Furthermore, the very large ionic osmotic pressures developed in such cases will cause V2m to be very small, thus justifying adoption of the dilute solution approximations (see, for example, Eq. 40) for the right-hand member. The equilibrium relation reduces in this case to... 

While the condition of stoichiometric neutrality invariably must hold for a macroscopic system such as a space-network polyelectrolyte gel, its application to the poly electrolyte molecule in an infinitely dilute solution may justifiably be questioned. In a polyelectrolyte gel of macroscopic size the minute excess charge is considered to occur in the surface layer (the gel being conductive), which is consistent with the assumption that the potential changes abruptly at the surface. This change is never truly abrupt, for it must take place throughout a layer extending to a depth which is of the order of magnitude of the... 

Although poly(organo)phosphazenes have been characterized using dilute solution techniques (4-10), attempts to characterize polydichlorophosphazene directly have been limited (11,12,13). The presence of gel and the fact that polydichlorophosphazene is moisture sensitive generally have precluded an accurate analysis of its molecular weight and molecular weight distribution... 

Chain Length Properties of the Modified Polymers. A number of partially hydrogenated and hydroxymethyl ated polybutadienes were analyzed using vapour pressure osmometry, dilute solution viscometry and gel permeation chromatography. The parent polybutadiene had Mn in the range of 9,000 to 50,000. In the case of vapour pressure osmometry, the data were reproducible for polymers with Mn less than 20,000. All the polymers obtained (hydrogenated and... 

The extreme hazards involved in handling this highly reactive material are stressed. Freshly distilled material rapidly polymerises at ambient temperature to produce a gel and then a hard resin. These products can neither be distilled nor manipulated without explosions ranging from rapid decomposition to violent detonation. The hydrocarbon should be stored in the mixture with catalyst used to prepare it, and distilled out as required [1], The dangerously explosive gel is a peroxidic species not formed in absence of air, when some l,2-di(3-buten-l-ynyl)cyclobutane is produced by polymerisation [2], The dienyne reacts readily with atmospheric oxygen, forming an explosively unstable polymeric peroxide. Equipment used with it should be rinsed with a dilute solution of a polymerisation inhibitor to prevent formation of unstable residual films. Adequate shielding of operations is essential [3],... 

Recently, gel permeation chromatography (GPC) and other dilute solution techniques have been directly applied to the characterization of II (17-20). In our laboratory we have examined II prepared by the uncatalyzed bulk and solution polymerization processes. Polymers obtained from the former process have high molecular weights (MWs) and broad molecular weight distributions (MWDs, Mw/Mn=5). The dilute solution... 

Beta/montmorillonite composite was prepared under dynamic hydrothermal conditions. Firstly, montmorillonite calcined at 800 °C were added to a diluted solution of sodium hydroxide, potassium chloride and TEAOH in distilled water and the resulting mixture was vigorously stirred for 1 h secondly, silica sol was added into the above uniform mixture to allow at least 3 h stirring finally, the gel was moved into stainless steel autoclaves (1L) and heated at 413 K for 48 h. The samples were characterized by XRD, N2 adsorption-desorption, FT-IR and SEM-EDS. The catalytic assessment experiments were carried out in a flowing-type apparatus designed for continuous operation. 

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