Polystyrene solubility parameter

Domains in position 2 on Figure 7.17 are filled after free volume voids were already filled. This increases free volume and for this reason the mechanical strength of material decreases. The effect is more dramatic because mineral oil is incompatible with polystyrene (solubility parameters of mineral oil and polystyrene are 7.6 and 9.1 (cal cm ), respectively) therefore mineral oil-mineral oil attractive forces are stronger than mineral oil-polystyrene forces. Thus, the excess of mineral oil (above the amormt required to fill free volume voids in position 1) accumulates in the mineral oil domains (position 2), which increase in size with amormt of mineral oil increasing. It was determined that the domain sizes are kept low ( 0.2 nm) below 6 vol% mineral oil in a low molecular polystyrene but they are about 9 nm at 8 vol%. At 9 nm, domains are above the critical size which causes phase separation and thus more catastrophic decrease in mechanical strength. 

Tables 5.4 and 5.5 predict that unvulcanised natural rubber (8 = 16.5) will be dissolved in toluene (8 = 18.2) and in carbon tetrachloride (8 = 17.5) but not in ethanol (8 = 26.0), all values being in units ofMPa. This is found to be true. Similarly it is found that there is a wide range of solvents for polystyrene in the solubility parameter range 17.2-19.7 MPa. ...

Being a hydrocarbon with a solubility parameter of 18.6MPa - it is dissolved by a number of hydrocarbons with similar solubility parameters, such as benzene and toluene. The presence of a benzene ring results in polystyrene having greater reactivity than polyethylene. Characteristic reactions of a phenyl group such as chlorination, hydrogenation, nitration and sulphonation can all be performed with... 

In effect this means that, to achieve reasonable toughness, semicompatible rubbers should be used. Semicompatibility may be achieved (a) by selecting mixtures of slightly different solubility parameter from the polystyrene, (b) by... 

The major advantage of the capillary hydrodynamic chromatography is that the mobile phase does not need to have similar solubility parameter as the sample and packing material. (In SEC, nonsize exclusion effects may be observed if the solubility parameter of the sample, packing material, or mobile phase is considerably different.) Therefore, the hydrodynamic size of polymers can be studied in a 0 solvent and even in a solvent that is not compatible with any currently available SEC packing material (9). Figure 22.4 is an example of polystyrene separation in both THF and diethyl malonate. Diethyl malonate is the 0 solvent of polystyrene at 31-36 C. 

Figure 14 The variation of average size of the polystyrene particles by the average solubility parameter of the homogeneous alcohol-water dispersion medium. (From Ref. 89. Reproduced with the permission of John Wiley Sons, Inc.)...

Of the instances of so-called solvent cracking of amorphous polymers known to the author, the liquid involved is not usually a true solvent of the polymer but instead has a solubility parameter on the borderline of the solubility range. Examples are polystyrene and white spirit, polycarbonate and methanol and ethyl acetate with polysulphone. The propensity to solvent stress cracking is however far from predictable and intending users of a polymer would have to check on this before use. 

As shown in Figures 5 and 7 the nature of the solvent does not appear to have any effect on T0 within experimental error. However, the solvent can have a profound influence on the morphology of cast block copolymer specimens. Thus, instead of the continuous polybutadiene phase normally observed, a continuous polystyrene phase appears to exist in Kraton 101 films cast from solution in MEK/THF mixtures (2). Methyl ethyl ketone has a solubility parameter of 9.3, only slightly higher than that of the solvents used in our work. It is clear from the data presented here that our films must have had continuous polybutadiene phases. 

Many computational studies of the permeation of small gas molecules through polymers have appeared, which were designed to analyze, on an atomic scale, diffusion mechanisms or to calculate the diffusion coefficient and the solubility parameters. Most of these studies have dealt with flexible polymer chains of relatively simple structure such as polyethylene, polypropylene, and poly-(isobutylene) [49,50,51,52,53], There are, however, a few reports on polymers consisting of stiff chains. For example, Mooney and MacElroy [54] studied the diffusion of small molecules in semicrystalline aromatic polymers and Cuthbert et al. [55] have calculated the Henry s law constant for a number of small molecules in polystyrene and studied the effect of box size on the calculated Henry s law constants. Most of these reports are limited to the calculation of solubility coefficients at a single temperature and in the zero-pressure limit. However, there are few reports on the calculation of solubilities at higher pressures, for example the reports by de Pablo et al. [56] on the calculation of solubilities of alkanes in polyethylene, by Abu-Shargh [53] on the calculation of solubility of propene in polypropylene, and by Lim et al. [47] on the sorption of methane and carbon dioxide in amorphous polyetherimide. In the former two cases, the authors have used Gibbs ensemble Monte Carlo method [41,57] to do the calculations, and in the latter case, the authors have used an equation-of-state method to describe the gas phase. 

The system with which we have begun our investigations is the styrene-dimethylsiloxane system. The dimethylsiloxane blocks should be considerably less compatible with polystyrene blocks than either polybutadiene or polyisoprene since the solubility parameter of dimethylsiloxane is much farther from that of polystyrene than are the solubility parameters of polybutadienes or of polyisoprenes (17), no matter what their microstructure. Furthermore, even hexamers of polystyrene and of polydimethylsiloxane are immiscible at room temperature and have an upper critical-solution temperature above 35°C (18). In addition, the microphases in this system can be observed without staining and with no ambiguity about the identity of the phases in the transmission electron microscope (TEM) silicon has a much higher atomic number than carbon or oxygen, making the polydimethylsiloxane microphases the dark phases in TEM (19,20). 

At a given temperature, a solvent for the polymer should have a (5-value approximately between the limits, indicated by the two straight lines in the figure. An even better correlation of Flory-temperatures with solubility parameters can be given in a <5h-<5v-diagram. This is shown in Fig. 7.9 for polystyrene. The circle drawn in Fig. 7.9 corresponds again with Eq. (7.18). 

Prior to this discovery, in 1954 Silberberg and Kuhn (62) were first to study the polymer-in-polymer emulsion containing ethylcellulose and polystyrene in a nonaqueous solvent, benzene. The mechanisms of polymer emulsification, demixing, and phase reversal were studied. Wetzel and Hocks discovery would then equate the pressure-sensitive adhesive to a polymer-polymer emulsion instead of a polymer-polymer suspension. Since the interface is liquid-liquid, the adhesion then becomes one type of R-R adhesion (35, 36). According to our previous discussion, diffusion is not operative unless both resin and rubber have an identical solubility parameter. The major interfacial interaction is physical adsorption, which, in turn, determines adhesion. Our previous work on the wettability of elastomers (37, 38) can help predict adhesion results. Detailed studies on the function of tackifiers have been made by Wetzel and Alexander (69), and by Hock (20, 21), and therefore the subject requires no further elaboration. 

Compatibility of polymers implies a semi-quantitative measure can be used to predict whether two or more polymers are compatible. The use of one of the semi-quantitative approaches, solubility parameter, was demonstrated by Hughes and Britt (22). It was concluded (8) that one parameter was insufficient to predict the compatibility. In this paper, we now introduce critical surface tension which is determined from the surface properties of a polymer. Though both of these parameters have been related by Gardon (15), we are inclined to use the latter because we can further describe the wettability between two polymers. For instance, by the use of yc, we can predict equally well that compatibility between polystyrene and polybutadiene can be improved if butadiene is... 

Kambour et al. performed extensive studies on the mechanisms of plasticization [18-25]. The correlation observed between the critical strain to craze and the extent of the glass-transition temperature (Tg) depression speaks strongly in favor of a mechanism of easier chain motion and hence easier void formation. In various studies on polycarbonate [19,24], polyphenylene oxide [20], polysulfone [21], polystyrene [22], and polyetherimide [25], Kambour and coauthors showed that the absorption of solvent and accompanying reduction in the polymer s glass-transition temperature could be correlated with a propensity for stress cracking. The experiments, performed over a wide range of polymer-solvent systems, allowed Kambour to observe that the critical strain to craze or crack was least in those systems where the polymer and the solvent had similar solubility values. The Hildebrand solubility parameter S [26] is defined as... 

Calculate the value of % for solutions of polystyrene in these solvents (use a fudge factor of 0.34). Indicate which solutions are likely to be single phase and which are likely to be phase-separated. Use Table 11-1 to calculate the solubility parameter of polystyrene from group contributions. 

Since the initial work of Smidsrod and Guillet numerous investigators have used I.G.C. to determine physicochemical parameters characterising the interaction of small amounts of volatile solutes with polymers Baranyi has shown that infinite dilution weight fraction activity coefficients, interaction parameters and excess partial molar heats of mixing can be readily determined with this technique. Partial molar heats and free energies of mixing, and solubility parameters of a wide variety of hydrocarbons in polystyrene and poly(methyl methacrylete) have been determined The temperature dependence of the interaction parameter between two polymers has also been studied... 

Benzene is termed a good solvent for polystyrene since Its solubility parameter (6=9.2H) Is within a previously established range of 1.8 for polystyrene (6=9.2H). When hexane (6=7.3H) was used at the same concentration, very little polymerization retardation was observed. The intrinsic viscosity and GPC elution times of the polymer resulting from the hexane modified emulsion Indicated it was substantially lower in molecular weight than the control. 

As shown In Figure 4, the rate of polymerization of styrene was retarded by good nonvlscous solvents such as benzene, cyclohexane, and octane whose solubility parameters (6) were within 1.5H of that of polystyrene at styrene to additive ratios of 3 to 1. The absolute rates were slightly Increased In poorer nonvlscous solvents such as heptane and hexane and were fastest In viscous nonsolvents such as dllsoctyl phthalate and Nujol. Rate studies Indicated a Rp dependency on [E] substantially greater than unity for the styrene emulsion systems modified with viscous poor solvents. 

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