80. Relation of Structure to Chemical Properties Intermolecular forces are generally less than 10 kcal/mole. In polymers, in the absence of hydrogen bonding, the intermolecular force is primarily due to dispersion effects 5.3 POLYMER SOLUBILITY ‘A chemical will be a solvent for another material if the molecules of the two ‘materials are compatible, ie. they can co-exist on the molecular scale and there is no tendency to separate. This statement does not indicate the speed at which solution may take place since this will depend on additional considerations such as the molecular size of the potential solvent and the temperature, Molecules of ‘wo different species will be able to co-exist if the force of attraction between different molecules is not less than the forces of attraction between two like molecules of either species. Ifthe average force of attraction between dissimilar ‘molecules A and B is Fag and that between similar molecules of type B Figa and between similar molecules of type A Faq then for compatibility Fay 2 Fag and Fg 2 Fan. This is shown schematically in Figure 5.5 (3) © © Figure 5S. Schematic representation of compatible and incompatible systems. (a) Fay 2 Fax Fay 2 Fn: Mint compasibe (0) Fag 0 Fyy > Fas. Molecules sepurte If either Fa, or Fyp is greater than Fay the molecules with the highest intermolecular attraction will tend to congregate or cohere and they will expel the dissimilar molecule with the result that two phases will be formed. These conditions are shown in Figure 5.5 (b. It now becomes necessary to find some suitable measure of the forces of attraction holding molecules together. If we first consider like molecules we ‘might expect the latent heat of vaporisation L to provide a useful basis, but this ‘would exceed the value of interest to us by an amount corresponding to the ‘mechanical work done on evaporation, an amount approximating to RT where R is the gas constant and T the absolute temperature. The value of L—RT, the eneray of vaporisation, will also clearly depend on the molecular size, a parameter which would not be expected to have large effect on the forces of attraction between two dissimilar molecules. More relevant will be the terms (L-RTIM (a measure of the energy of vaporisation per unit weight) and L-RT ‘MIDPolymer Solubility 81 the energy of vaporisation per molar volume (where M is the molecular weight). ‘This latter term is known as the cohesive energy density and has often been expressed in units of cal/em*. However, these units are contrary to the SI system. ‘where the units will be expressed asMPa. More commonly encountered in ‘qualitative studies is the square root of the cohesive energy density, which is known as the solubility parameter and given the symbol 8, Le. 7 (1) Amorphous non-polar polymers and amorphous non-polar solvents. (2) Crystalline non-polar polymers and amorphous solvents G) Amorphous non-polar polymers and crystalline solvents. (4) Amorphous polar polymers and solvents. (5) Caystalline polar polymers and solvents (6) Vuleanised rubber and thermosetting plastics. Amorphous non-polar polymers and amorphous non-polar solvents It is assumed in these circumstances, by analogy with gravitational and electrostatic attraction, that Fag will be equal to the geometric mean of Fy, and Fay. If by arbitrary definition we take Fx, > Fan then Fan > Faw > Fos Since we have already seen that solution will only occur when Fag 2 Fan and Fay 2 Fog then compatibility between amorphous non-polar polymers and solvents can only occur when Fan = Faw = Fon that is, when polymer and solvent have similar solubility parameters (in practice within about 2 MP2?) Tables 5.4 and 5.5 predict that unvulcanised natural rubber (8 dissolved in toluene (8 = 18.2) and in carbon tetrachloride (6 = 17.5) but not in ethanol (8 = 26.0), all values being in units of MPa”. This is found to be true. Simi ts found that there isa wide range of solvents for polystyrene in the solubility parameter range 17.2-19.7 MPa" 6.5) will be82 Relation of Structure to Chemical Properties Table $4 Solubility parumcters of polymers Potymer pat? (caller) Polyttafluroehylene 126 62 PoiyehlortriNaoroetiyne 147 2 Polymethysitoxane 49 3 iylene-propyene rubber Ie 1B Poiisobuylene 16 19 Polyethylene 163 80 Polypropyene 163 80 Polysoprene (aura rubber) 165 81 Polybutadiene m a4 Styrene-buadiene rubber m4 a4 Poly(-buty methacrylate) 169 83 Polyi-hexyt methacrylate) 16 86 Poly-tuy! methacrylate) ns 87 Polybuty atzlate) 130 85 Polyetyl methacrylate) 133 90 Plymetylpheay soxane 183 90 Polyetylacrylate) 187 92 Polyulphide rubber 83-192 90-94 Polystyrene 187 92 Polyehoropene rubber 187-192 92-94 Polymetymetiacylte) 187 92 Polyvinyl acct) 2 oa Polyvingl chris) wa 95 Bisshhenol A polycarbonate wa 95 Polyvinglidene chloride) 200-250 94-122 Ethyleallose 173-210 85-103 Cellulose ita) 216 oss Polyethylene terepthalste) 218 wr ‘Acca eine 26 mt Callulose dace 232 35 Nylon 66 28 136 Polyanethy a-eyanoueryate) 287 ta Polya tonite 287 fl ces fabs ie nee aid ra en oe mg (sion he nee qa np a ge |Polymer Solubility 83 ‘Table 85 Solubility parameters and partial poares(P) of some common solvents Polymer 8 ° pe" (eaten)? Neo-pentane 28 63 ° Isobutlene By 87 ° snltexane 149 3 0 Diet ether 1st 74 03 Octane 135 16 ° Methyleyelonexane 159 18 ° Ethyl sobayete I 73 2 Dssopropyl ketone 163 x0 03 Methyl amlaceate 163 80 = “Turpentine 165 aI ° Cycloerane 167 82 ° E2-Dichioropropane 67 2 = seerAmyl acetate 169 3 = Dipentene 13 85 © Amy acetate mn 83 on Meth mba ketone 06 a6 035 Pine ei 6 86 = Gabon tetrachloride 16 86 ° Methyl mpeopy ketone ns 82 on Bipendine na 87 a Xylene 180 88 ° Dimethyl eter 180 Bs = “Toluene Iz 8S ° By cllooive 182 89 ° Dichloropropane 183 30 = Mesity oxide 183 50 = Tsophorone 6 Mt = tig sutte 88 at on Benzene 187 92 ° Diacstnealeohot 187 92 2 Chloroform 130 93 om ‘rihloroetlene 190 93 ° ‘etrachloroethytene 192 94 oor ‘Telia 4 93 = arto! 196 96 = Meth chloride 198 97 = Methylene debonde 198 97 = Ethylene dehlode 200 os ° CCyelotexanone| 202 99 = Ctsaive m2 99 = Dioxane 202 99 oot (Carbo disuipide 204 tno ° Accone 204 too 009 Osta 210 103 00 Buyronle 218 103 on Henao! 218 10 8.0684 Relation of Structure to Chemical Properties ‘Table 85 Continued Polymer 3 A (ealen?)"? sec-Butana 108 u Pyridine 109 on Niothane mt o71 -Butanol 232 ua 010 ycloherano 233 nt 08 Isepropanl 24 us ss Propuna 242 19 ois Dimethonmamide 3a Bi 07 ‘yarogen cyanide 2a 1B af ‘Acetic aid 283 126 030 260 27 02 mm 53 eS 2s BS = 28 43 039 Phenol 296 006 Giycerat Se 047 Water 3 OR ‘These tables are of greatest use with non-polar materials with values of 8 less than 19.4MPa!? and where the polymers are amorphous. It will now be necessary to discuss other systems. Crystalline non-polar polymers and amorphous solvents Most polymers of regular structure will crystallise if cooled below a certain temperature, the melting point T,.. This isin accord with the thermodynamic law (ee Section 5.3.4) thata process will only occur if there isa decrease in free energy F in going from one state to another. This free energy change AF is related to the heat of melting AH, the temperature T and the entropy change AS by the equation AF =AH-TAS Since on crystallising the AH is negative, the free energy change AF is also negative. The process will reverse, ie. melting will occur, only when TAS becomes equal to AH. Immersing the crystalline polymer in a liquid of similar solubility parameter at temperatures well below Ty, will do little to change the balance although the entropy term AS would increase slightly owing to an increase in molecular disorder on dissolution. Tere are thus no solvents at room temperature for polyethylene, polypropyl- ene, poly-4 methylpent-I-ene, polyacetals and polytetrafluoroethylene. However, as the temperature is raised and approaches Ty the TAS 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 Ty,Polymer Solubility 85 ‘Amorphous non-polar polymers and crystallising solvents ‘This situation is identical to the previous one and occurs for example when paraffin wax is mixed into rubber above the melting point of the wax. On cooling, the wax starts to crystallise, some of it forming a bloom on the rubber surface. Such a bloom assists in protecting a diene rubber from ozone attack, Amorphous polar polymers and solvents As already mentioned molecules cohere because of the presence of one or more ‘of four types of forces, namely dispersion, dipole, induction and hydrogen bonding forces. In the case of aliphatic hydrocarbons the dispersion forces predominate. Many polymers and solvents, however, ae said to be polar because they contain dipoles and these can enhance the total intermolecular attraction. It is generally considered that for solubility in such cases both the solubility parameter and the degree of polarity should match. This latter quality is usually expressed in terms of partial polarity which expresses the fraction of total forces due to the dipole bonds, Some figures for partial polarities of solvents are given in Table 5.5 but there is a serious lack of quantitative data on polymer partial polarities. At the present time a comparison of polarities has to be made on a ‘commonsense rather than a quantitative approach, ‘An alternative approach, due to Hansen, isto partition the solubility parameter into three components, 8,, 8, and 8), due t0 contributions from dispersion forces, dipole-dipole forces and hydrogen bonding forces respectively. The three components may be represented by co-ordinates in three-dimensional space. Partitioning can, at least in theory, be carried out for the solubility parameters of both solvents and polymers. It may be argued that for each polymer there is a characteristic radius originating from its point in space which encloses the points forall liquids that are solvents for the polymer. AS a very rough guide this radius is about 2 SI units. Whilst data for many solvents have been presented there is ‘only limited information on polymers. Values for some solvents and polymers are given in Table 5.6. Table 56 Parone values ofthe solubity paramcter (after Hansen!) 5. &, 8 eavem®)"? | eave)? | Geaem®y!® Hexane bs o ° Bas Benzene fet tos 05 Lo ois Terahydrofuran | az 28 39 932 ‘Acetone 138 st a 977 Dionane 930 oo as 0.00 Dimethjformamide = | 82 67 55 ius Methanol 7a 60. 109 i438 Ethylene glycol { a se | oat | i630 water | soo an 2350 Polythene a o | a | at Polystyrene 89s os te} on Polymetiyl methacrylate) @ 40 py || ey crn86 Relation of Structure to Chemical Properties Crystalline polar polymers and solvents It has already been pointed out that crystalline non-polar polymers do not rormally have solvents well below their crystalline melting point and the same ‘comment can apply to a large number of polar crystalline polymers. It has, however, been possible to find solvents for some polar crystalline polymers such as the nylons, poly(vinyl chloride) and the polycarbonates. This is because of specific interactions between polymer and solvent that may often ‘occur, for instance by hydrogen bonding. For example, nylon 66 will dissolve in formic acid, glacial acetic acid, phenol and cresol, four solvents which not only have similar solubility parameters but also ate capable of acting as proton donors whilst the carbonyl groups on the nylon act as proton acceptors (Figure 5.6). 3 : j ono) Y A more interesting example is given with PVC and the polycarbonate of bis- phenol A, both slightly crystalline polymers. It is noticed here that whilst methylene dichloride is a good solvent and tetrahydrofuran a poor solvent for the polycarbonate the reverse is true for PVC yet all four materials have similar solubility parameters. It would seem that the explanation is that a form of hydrogen bonding occurs between the polycarbonate and methylene dichloride and between PVC and tetrahydrofuran (Figure 5.7). In other words there is a specific interaction between each solvent pair. i oh i cco a-F-a cH, ‘cH, —CH, a i Figure 57 Many studies have been made to try to assess the propensity to hydrogen bonding of chemical structures, As a result the following broad generalisations may be made! (1) Proton donors include highly halogenated compounds such as choloroform and pentachlorethane. Less halogenated materials are weaker donors. (2) Polar acceptors include, in roughly descending order of strength, amines, ethers, ketones, aldehydes and esters (with aromatic materials usually being ‘more powerful than aliphatics).Polymer Solubility 87 (3) Some materials such as water, alcohols, carboxylic acids and primary and secondary amines may be able to act simultancously as proton donors and acceptors. Cellulose and poly(vinyl alcohol) are two polymers which also function in this way. (4) A number of solvents such as the hydrocarbons, carbon disulphide and carbon tetrachloride are quite incapable of forming hydrogen bonds, Vulcanised rubber and thermosetting plasties ‘The conventionally covalently cross-linked rubbers and plastics cannot dissolve ‘without chemical change. They will, however, swell in solvents of similar solubility parameter, the degree of swelling decreasing with increase in cross-link density, The solution properties of the thermoelastomers which are two-phase ‘materials are much more complex, depending on whether or not the rubber phase ‘and the resin domains are dissolved by the solvent. 53.1 Plasticisers thas been found that the addition of certain liquids (and in rare instances solids) to a polymer will give a non-tacky product with a lower processing temperature and which is softer and more flexible than the polymer alone, As an example the addition of 70 parts of di-iso-octyl phthalate to 100 parts of PVC will convert the polymer from a hard rigid solid at room temperature to a rubber-like material Such liquids, which are referred 10 as plasticisers, are simply high boiling solvents for the polymer. Because itis important that such plasticisers should be ‘non-volatile they have a molecular weight of at least 300. Hence because of their size they dissolve into the polymer only at a very slow rate at room temperature. For this reason they are blended (fuxed, gelled) with the polymer at elevated temperatures or in the presence of volatile solvents (the latter being removed at some subsequent stage of the operation). For a material to act as a plasticiser it must conform to the following requirements: (1) It should have a molecular weight of at least 300, (2) It should have a similar solubility parameter to that of the polymer, (3) Ifthe polymer has any tendency to crystallise, it should be capable of some specific interaction with the polymer. (4) It should not be a crystalline solid at the ambient temperature unless it is capable of specific interaction with the polymer, ‘The solubility parameters of a number of commercial plasticisers ate given in Table 5.7 From Table 5.7 it will be seen that plasticisers for PVC such as the octyl phthalates, titolyl phosphate and dioctyl sebacate have solubility parameters within I egs 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 tothe polymer. The sebacates which gel more slowly but give products, which are flexible at lower temperatures than corresponding formulations from tritoly! phosphate have a lower solubility parameter. It is, however, likely that any difference in the effects of phthalate, phosphate and sebacate plasticisers in