Solubility parameter effect

The swelhng method may not determine solubility parameters effectively if the rigid crosslinked samples tend to chip or split on swelling. The method can be used for polymers with a physical network that contains knots formed by polymer crystalhtes. Samples of unplasticized PVC do not swell in ester plasticizers, but if the same polymer is hot-compounded with dioctyl phthalate and cooled, it can swell to equilibrium as does the amorphous crosslinked elastomer. Note that such swelling of PVC depends on the thermal treatment history of samples. 

Poly(methyl methacrylate) prepared by free radical polymerization is amorphous and is therefore soluble in solvents of similar solubility parameter. Effective solvents include aromatic hydrocarbons such as benzene and toluene chlorinated hydrocarbons such as chloroform and ethylene dichloride and esters such as ethyl acetate and amyl acetate. Some organic materials, although not solvents for the polymer, cause crazing and cracking, e.g., aliphatic alcohols and amines. Poly(methyl methacrylate) has very good resistance to attack by water, alkalis, aqueous inorganic salts and most dilute acids. Some dilute acids such as hydrocyanic and hydrofluoric acids, however, do attack the polymer, as do concentrated oxidizing acids. Poly(methyl methacrylate) has much better resistance to hydrolysis than poly(methyl acrylate), probably by virtue of the... 

There are thus no solvents at room temperature for polyethylene, polypropylene, poly-4 methylpent-l-ene, polyacetals and polytetrafluoroethylene. However, as the temperature is raised and approaches F , the FAS term becomes greater than AH and appropriate solvents become effective. Swelling will, however, occur in the amorphous zones of the polymer in the presence of solvents of similar solubility parameter, even at temperatures well below T. ... 

From Table 5.7 it will be seen that plasticisers for PVC such as the octyl phthalates, tritolyl phosphate and dioctyl sebacate have solubility parameters within 1 cgs unit of that of the polymer. Dimethyl phthalate and the paraffinic oils which are not PVC plasticisers fall outside the range. It will be noted that tritolyl phosphate which gels the most rapidly with PVC has the closest solubility parameter to the polymer. The sebacates which gel more slowly but give products which are flexible at lower temperatures than corresponding formulations from tritolyl phosphate have a lower solubility parameter. It is, however, likely that any difference in the effects of phthalate, phosphate and sebacate plasticisers in... 

All PVC plasticisers have a solubility parameter similar to that of PVC. It appears that differences between liquids in their plasticising behaviour is due to differences in the degree of interaction between polymer and plasticiser. Thus such phosphates as tritolyl phosphate, which have a high degree of interaction, gel rapidly with polymer, are more difficult to extract with solvents and give compounds with the highest brittle point. Liquids such as dioctyl adipate, with the lowest interaction with polymer, have the converse effect whilst the phthalates, which are intermediate in their degree of interaction, are the best allround materials. 

Table 12.3 Effect of solubility parameter of mbber on its effect on the impact strength of a PVC-rubber blend (5 parts rubber per 100 parts PVC) ...

The anomalous effect of the last two rubbers in the table with their low solubility parameters is possibly explained by specific interaction of PVC with carbonyl and carboxyl groups present respectively in the ketone- and fumarate-containing rubbers to give a more than expected measure of compatibility. It is important to note that variation of the monomer ratios in the copolymers and terpolymers by causing changes in the solubility parameter and eompatibility will result in variation in their effect on impact strength. 

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 solubility parameter is calculated at 20 MPa and therefore the polymer is swollen by liquids of similar cohesive forces. Since crystallisation is thermodynamically favoured even in the presence of liquids of similar solubility parameter and since there is little scope of specific interaction between polymer and liquid there are no effective solvents at room temperature for the homopolymer. 

Acetal homopolymer resins show outstanding resistance to organic solvents, no effective solvent having yet been found for temperatures below 70°C. Above this temperature some phenolic materials such as the chlorophenols are effective. Stress cracking has not been encountered in organic solvents. Swelling occurs with solvents of similar solubility parameter to that of the polymer (8 = 22.4 MPa ). 

The solubility parameter of poly(ethylene terephthalate) is about 21.8 MPa but because it is a highly crystalline material only proton donors that are capable of interaction with the ester groups are effective. A mixture of phenol and tetrachloroethane is often used when measuring molecular weights, which are about 20 000 in the case of commercial polymers. 

Hansen [137-139], and later van Krevelen [114] proposed the generalization of the solubility parameter concept to attempt to include the effects of strong dipole interactions and hydrogen bonding interactions. It was proposed that the cohesive energy density be written as the sum of three terms, viz. 

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. 

In this approach, connectivity indices were used as the principle descriptor of the topology of the repeat unit of a polymer. The connectivity indices of various polymers were first correlated directly with the experimental data for six different physical properties. The six properties were Van der Waals volume (Vw), molar volume (V), heat capacity (Cp), solubility parameter (5), glass transition temperature Tfj, and cohesive energies ( coh) for the 45 different polymers. Available data were used to establish the dependence of these properties on the topological indices. All the experimental data for these properties were trained simultaneously in the proposed neural network model in order to develop an overall cause-effect relationship for all six properties. 

Paine et al. [85] extensively studied the effect of solvent in the dispersion polymerization of styrene in the polar media. In their study, the dispersion polymerization of styrene was carried out by changing the dispersion medium. They used hydroxypropyl cellulose (HPC) as the stabilizer and its concentration was fixed to 1.5% within a series of -alcohols tried as the dispersion media. The particle size increased from only 2.0 /itm in methanol to about 8.3 /itm in pentanol, and then decreased back to 1 ixm in octadecanol. The particle size values plotted against the Hansen solubility parameters... 

Table 9. Effect of organic substituents on the solubility parameter and the glass transition temperature of an organosiloxane polymer...

The rate constants in organic reaction in a solvent generally reflect the solvent effect. Various empirical measures of the solvent effect have been proposed and correlated with the reaction rate constant [5]. Of these, some measures have a linear relation to the solubility parameter of the solvent. The logarithms of kj and k2/ki were plotted against the solubility parameter of toluene, NMP and DMSO[6] in Fig. 2. As shown in Fig.2, the plots satisfied the linear relationship. The solvent polarity is increased by the increase of solubility parameter of the solvent. It may be assumed that increase of unstability and solvation of Ci due to the increase of solvent polarity make the dissociation reaction of Ci and the reaction between Ci and COisuch as SNi by solvation[7] easier, respectively, and then, k2/ki and ks increases as increasing the solubility parameter as shown in Fig. 2. 

The overall reaction between CO2 and GMA was assumed to consist of two elementary reactions such as a reversible reaction of GMA and catalyst to form an intermediate and an irreversible reaction of this intermediate and carbon dioxide to form five-membered cyclic carbonate. Absorption data for CO2 in the solution at 101.3 N/m were interpreted to obtain pseudo-first-order reaction rate constant, which was used to obtain the elementary reaction rate constants. The effects of the solubility parameter of solvent on lc2/k and IC3 were explained using the solvent polarity. 

In reality, finding a suitable solvent is not as easy as simply matching the polymer s solubility parameter (8 value). It is also important to take into account the effects of polymer crystallinity (as in the case of aPP and iPP, LDPE and HDPE). Because of their various chemical structures, it may be necessary to experiment with solvent, temperature, and time conditions to optimise the extraction strategy. 

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