MOLECULAR WEIGHT AND POLYMER SOLUTIONS 2.1 Number Average and Weight ‘Average Molecular Weight Molecular weight is an extremely important variable because it relates directly to a poly- mer’s physical properties. In general. the higher the molecular weight. the tougher the poly- mer; however (as will be shown in the next chapter). too high a molecular weight can lead to processing difficulties. What defines an optimum molecular weight depends in large mea- sure on the chemical structure of the polymer and the application for which it is irmended. In this chapter we will be concerned with molecular weight definitions. methods of deter- mining molecular weight, and methods of determining the distribution of molecular weights in a polymer sample. We will reserve our discussion of molecular structure for the follow- ing chapter. We will also be concerned with solution properties of polymers, because solu- bility is prerequisite to most methods for determining molecular weight. ‘Given that polymers are high-molecular-wei ght compounds. we must begin with the ques- tion, what do we mean by high molecular weight? Where does low molecular weight end and high begin? There is no simple answer. because what constitutes a “low” molecular weight for a sample of polyethylene, for example. might be ideal for a sample of polyamide. Furthermore, some polymers are deliberately prepared with low molecular weight (even as oligomers) to facilitate initial processing. and the molecular weight is increased in a subse- quent processing step. In general, however. we think of polymers as having molecular weights that run from the low thousands up to the millions, with optimum molecular weight depend- ing on chemical structure and application. Vinyl polymers of any commercial import normatly have molecular weights in the range of 10° to 10°. Polymers having very polar functional groups, such as polyamides, may have molecular weights as low as 15.000 to 20,000. ‘To determine molecular weights of simple (nonpolymeric) compounds, we employ the familiar techniques of mass spectrometry, freezing-point depression (cryoscopy), boiling- point elevation (ebulliometry), and, where suitable functional groups are present, titration (for example, neutralization or saponification equivalents), Determining molecular weights 35 Scanned with CamScanner“ Polymer Structure and Properties of polymer. however, is considerably more complex for two basic reasons, First, in any poly. merization process, itis virtually impossible forall prewing polymer chains to terminate at the same size; hence one must necessarily deal with average molecular weights, (Certain natura} polymers having discrete molecular weights provide exceptions to this nile.) Second, the tech- niques of cryoscony. ebulliometry, and titration are effective only with relatively low-molecu. lar-weight polymers: more sophisticated methods must be used for polymers with molecular weights higher than about 40,000, Conventional mass spectrometry has not been used exten- sively in the polymer field beyond the characterization of polymer degradation products because Of the requirements for volatilizable samples. Recent years, however, have seen some exciting new developments that have extended mass spectrometry into the macromolecular range. Techniques more commonly used for determining molecular weights of polymers in- clude osmometry. light scattering, and ukracentrifugation, although titration (end-group analysis), cryoscopy, and cbulliometry are also used in some applications.'2 The most con- venient method for routinely determining molecular weights involves measuring solution vis- ccosities, but this is not an absolute method and can be used only in conjunction with one of the techniques of measuring absolute molecular weights. Molecular weight values obtained depend in large measure on the method of measure- ment, Methods that depend on end-group analysis or colligative propenties (freezing-point depression. boiling-point elevation, osmotic pressure) give rise to the number average mo- lecular weight, My, because the number of molecules of cach weight in the sample are ‘counted. This is defined as: = SNM: Mn Sy where N, is the number of molecules—or the number of moles of those molecules—having molecular weight M,. Suppose. for example, we have a polymer sample consisting of 9 moles having molecular weight 30,000 and 5 moles having molecular weight 50,000: (9 mol X 30,000 g/mol) + (5 mol x 50,000 g/mol) 9 mol + 5 mol = 37,000 gimol ‘Suppose, instead, our sample consists of 9 grams having molecular weight 30,000 and 5 grams having molecular weight 50,000. Given that NiM; is equal to the weight, wi, then: Wi =>———__22 58 __ 36.000 gimol =“ 4730,000 gimal) + (5 g/50,000 gimoh ~ °52°0 emo Light scattering and ultracentrfugation, on the other hand, are methods of determining mo- lecular weight based on mass or polarizability of the species present, The greater the mass, the greater is the contribution to the measurement, In contrast to number average molecular weight (which is the summation of the mole fraction of each species times its molecular weight), these methods sum the weight fraction of each species times its molecular weight. The value thus ob- tained is called the weight average molecular weight, My, and is expressed mathematically as yy, <2 _ INMP “s “ay SNM; Scanned with CamScannerMolecular Weight and Polymer Solutions a Consider the same two samples described previously. Nine moles having 30.000 mo- lecular weight and 5 moles having 50,000 molecular weight: < __ 9-mol(30,000 g/mol)? + 5 mol(50,000 g/mol)? ce EES OO YEO AO Mr = 9 rm0( 30,000 gmol) + 5 mol(50,000 g/mol) me geet Substituting grams for moles: Fi, = 28020000 glmoly + 5 150.000 g/m “ 9g+Sg = 37,000 g/mol In cach instance, we see that M, is greater than fy. In measurements of colligative properties, each molecule contributes equally regardless of weight, whereas with light scattering, the larger molecules contribute more because they scatter fight more effectively. It is for this reason that weight average molecular weights are always greater than sumber average molecular weights except of course. when all molecules ae of the en M,, = M,,. The narrower the molecular weight range. the closer are the values Jecular weight range in a polymer sample. This rato is called the potydispersiry index, and my system having a range of molecular weight is said o be potiisperse. tal polymer molecules present have the same molecular weight (a protein, for example). tbe sysem is monodisperse. ‘There is a general equation for molecular weight averages: oN For M, and M,.. a is equal to 0 and 1, respectively. A higher-order molecular weight aver- age, the z average (M.), results when a > Wy> M,,. Processing characteristics of molten polymer are more dependent oa W, than on My, | or My | In our discussions of molecular weight measurement (Section 2). detailed descriptions of apparatus and derivations of working equations are not given. Students who wish to ex- | plore these areas in more detail are encouraged to consult the references provided. First, how ever, we will look briefly at solution properties of polymers because the various methods of determining molecular weight or molecular weight distribution depend in most instances on solubility and polymer-solvent interactions 2.2. Polymer Solutions Dissolving a polymer is unlike dissolving low-molecular-weight compounds because of the vasily diferent dimensions of solvent and polymer molecules. Solution occurs in two stages. Initially the solvent motecules diffuse through the polymer matrix to form a swollen, solvated mass calle {in the second stage, the gel breaks up and the molecules are dispersed into 4 trae solution. Dissolution ix often 2 slow process. While some polymers dissolve readily in certain solvents, others may’ require prolonged periods of heating at temperatures near the melting point of the polymer. Network polymers do not dissolve, but usually swell in the Scanned with CamScanners Potymer Siructure and Properties Presence of solvent. (Any student who has stoppered a flask containing an organic solvent with a rubber stopper has undoubtedly observed this phenomenon.) Even some linear poly. mers defy all attempts to dissolve them: hence lack of solubility does not necessarily mean that the polymer is of the network type, How does one choose a solvent? The simplest way is to consult a polymer handbook, where extensive lists of solvents and nonsolvents for numerous polymers are compiled.4# Detailed studies of polymer solubilities using thermodynamic principles have led to semi- empirical relationships for predicting solubility. Any solution process is governed by the free- ‘energy relationship. AG = 4H - TAS ‘When a polymer dissolves spontaneously, the free energy of solution, AG, is negative. The entropy of solution. AS. invariably has a positive value arising from increased conforma- tional mobility of the polymer chains. Therefore, the magnitude of the enthalapy of solution, AM. determines the sign of AG. It has been proposed that the heat of mixing, AHmix, for a binary system is related to concentration and energy parameters by the expression ia = Vaal (7)? ~ (FE) tate 1 V2 where Voi, is the total volume of the mixture, V; and V; are molar volumes (molecular \weight/density) of the two components, ¢ and ¢2 are their volume fractions, and AE, and AE are the energies of vaporization. The terms AF/V, and AF2/V2 are called the cohesive energy densities. If (AEN')'" is replaced by the symbol 6, the equation is written more simply: AHmix = Vix(51 — 62)? ide ‘The symbol 5 is called the solubility parameter. Clearly, for the polymer to dissolve (nega~ tive AG), AMmx must be small; therefore, (5; — 52)? must also be small. In other words, 61 and 6; should be of about equal magnitude. Where 6, = 8, solubility is governed sotely by eauropy effects. Predictions of solubility are therefore based on finding solvents and poly- mers with similar solubility parameters, which requires a means of determining cohesive en- exgy densities. Cohesive energy density is the energy needed to remove a molecule from its nearest neighbors, thus is analogous to heat of vaporization per volume for a volatile compound. For the solvent, 5, can be calculated directly from the latent heat of vaporization (AHvap) using the relationship AE = AHyay — RT where R is the gas constant, and Tis the temperature in kelvins. Thus (tszaty" 4 Vv Since polymers have negligible vapor pressure, the most convenient method of deter- mining 5) is to use group molar attraction constants. These are constants derived from stud ies of low-molecular-weight compounds that lead to numerical values for various motecular groupings on the basis of considerations of intermolecular forces. Two sets of values (des- Scanned with CamScannerMolecular Weight and Polymer Solutions » TABLE 2.1. Representative group molar attraction constants? G [(cat crf? mot” Group Small Hey CHs— 214 1473 —cH,— 133 BIS SS cH 28 8599 Ne IK -93 3203 =cH, 190 1265 =CH— 19 8451 —CcHs (phenyl) 3S = —CH— (aromatic) — 17 Dc=0 tetone) ms 2627 —Coz— (ester) 310 3266 "Values taken from Refs. 5 and 6, ignated G) have been suggested, one by Small.) derived from heats of vaporization. and the other by Hoy,® based on vapor pressure measurements. Typical G values are given in Table 2.1. Clearly there are significant differences between the Small and Hoy values. Which set one uses is normally determined by the method used to determine 6; for the solvent. G values are additive for a given structure, and are related to & by oo where d is density and M is molecular weight For polystyrene. for example, which has a density (obtained from a handbook") of 1.05, a repeating unit mass of 104, and structure Ey 6 is calculated, using Small’s G values, as 5 = 1.05133 + 28 + 735) 10s 28 or using Hoy’s data, 1,05[131.5 + 85.99 + 6(UI7.D1 _ cr 93 Solvent & may be calculated similarly. A major problem with solubility parameters as discussed above is that they do not take into account strong dipolar forces such as hydrogen Scanned with CamScanner“a Polymer Sucture and Properties ponding, Proposals have been made.” however, to separate solubility parameters into com- ponents reflecting dispersion forces, dipole-dipole attractions, and hydrogen bonding, ‘Compilations of 6 for solvents and polymers are available in the literaturc.*“* Once a polymer-solvent system has been selected, another consideration is how the poly- mer molecules behave in that solvent, Particularly important from the standpoint of molec- ular weight determinations is the resultant size. or hydrodynamic volume, of the polymer molecules in solution. Assuming polymer molecules of a given molecular weight are fully separated from one another by solvent. the hydrodynamic volume will depend on a variety of factors, including interactions between solvent and polymer molecuies, chain branching, conformational effects arising from the polarity and steric bulk of the substituent groups, and restricted rotation caused by resonance, for example, of the type common to polyamides, 9 I. CNH — —C=nH— Because of Brownian motion, molecules are changing shape continuously. Hence any method of trying to predict molecular size must necessarily be based on statistical considerations and average dimensions. If a molecule were fully extended, its size could casily be computed from a knawledge of bond lengths and bond angles. Such is not the case. however, with most common polymers: therefore, size is generally expressed in terms of the mean-square aver- age distance between chain ends, F?, for a linear polymer, or the square average radius of gyration about the center of gravity, 32, for a branched polymer. Figure 2.1 illustrates the meaning of r and s from the perspective of a coiled structure of an individual polymer mol- cule having its center of gravity at the origin. The average shape of the coiled molecule is spherical. The greater the affinity of solvent for polymer, the larger will be the sphere, that is. the hydrodynamic volume. As the solvent-polymer interaction decreases, intramolecular interactions become more important, leading to a contraction of the hydrodynamic volume. tis convenient to express r and s in terms of two factors: an unperuerbed dimension (ry r 59) and an expansion factor (a). Thus, rea? = sya? FIGURE 2.1. Schematic representation of a molecular coil, 1 end-to-end distance; s = radius of gyration. Scanned with CamScannerMolecular Weight and Polymer Solutions a ‘The unperturbed dimension refers to the size of the macromolecule exclusive of solvent effects. It arises from a combination of free rotation and intramolecular steric and polar in- teractions. The expansion factor, on the other hand, arises from interactions between solvent and polymer. For a linear polymer, 7? = 632. Since it follows that a will be greater than unity in a “good” solvent. and the actual (j dimensions will exceed the unperturbed dimensions. The greater the value of a. the “better” the solvent. For the special case where @ = 1, the polymer assumes its unperturbed dimen- sions and behaves as an “ideal” statistical coil. Because solubility properties vary with temperature in a given solvent. a is temperature dependent, For a given polymer in a given solvent, the lowest temperature at which a = 1 is called the theta (@) temperature (or Flory temperature). and the solvent is then called a theta solvent. Additionally, the polymer is said to be in a theta state. {tis convenient to think of the theta state as that in which the polymer is on the brink of becoming insoluble: in other words, the solvent is having a minimal solvation effect on the dissolved molecules. Any fur- ther diminution of this effect causes the attractive forces among polymer molecules to pre- dominate, and the polymer precipitates. Extensive compilations of theta solvents and tem- peratures are avaifable in the literature,” From the standpoint of molecular weight determinations. the significance of these para- meters is that they can be related to dilute solution viscosity according to the Flory-Fox equa- tion, oye Waa where [7] is the intrinsic viscosity (to be defined later), M is the average molecular weight, and ¢ is a proportionality constant (called the Flory constant) equal to approximately 3 X 1024 mol~!. Substituting 7o2a? for F2, we obtain y= which can be rearranged to (nl = 6762“? 18? then Since 9 and M are constants, we can set K = (Fg! (n] = KM Pas At the theta temperature, a = 1 and [n] = KM? For conditions other than the theta temperature, the equation has the form (n] = Kite Scanned with CamScannera Polymer Structure and Properties where a is a constant that varies with polymer, solvent, and temperature. Known as the Mark-Houwink-Sakurada equation, this is an important relationship that, as we shall see in Section 2.5, is used to relate dilute solution viscosity to molecular weight. ‘Apart from molecular weight determinations, important practical considerations arise from solubility effects. As one moves in the direction of “good” solvent to “poor,” and in- tramolecular forces become more important, the polymer molecules shrink in volume. This increasing compactness leads to reduced “drag” and hence a lower viscosity. Paint chemists are particularly concemed with solvent effects because viscosity is of fundamental impor- tance in spray or brush applications of solvent-based paints or lacquers. Fiber manufactur- ers can also reduce energy costs involved in spinning fibers from solution (see Chapter 4) by reducing solution viscosity. 2.3 Measurement of Number Average Molecular Weight 231 End-group Analysis ‘The number average molecular weight of any linear polymer having end groups that can be measured by chemical or physical means can theoretically be determined if the method of measurement is sensitive enough. It must be remembered, however, that end groups are present in very low concentrations. Presently available techniques! allow a practical up- per limit of molecular weight measurement of about 50,000. Some of the current methods of end-group determination include (1) titration, using either indicators or potentiometric techniques; (2) elemental analysis of element-specific end groups; (3) measurement of ac- tivity of a radioactive-tagged end group: and (4) ultraviolet spectroscopic determination of an end group with a characterizable chromophore. Infrared and nuclear magnetic resonance (NMR) spectroscopic techniques are of more limited use. Points to be kept in mind in applying end-group analysis are the following: 1. The method cannot be applied to branched polymers unless the number of branches is known with certainty; thus it is practically limited to linear polymers. 2. Ina linear polymer there are twice as many end groups as polymer molecules. 3. If the polymer contains different groups at each end of the chain and only one char- acterizable end group is being measured, the number of this type is equal to the num- ber of polymer molecules. 4, Measurement of molecular weight by end-group analysis is only meaningful when the mechanisms of initiation and termination arc well understood. ‘Asatypical example, let us consider the unsaturated polyesters (Chapter 12). These are linear polymers of relatively low molecular weight prepared from anhydrides or dicarboxylic ‘acids and diols, and they are normally crosslinked in a subsequent fabrication step. (Saturated polyesters of the type used in film and fiber applications are usually of too high molecular weight for end-group analysis.) Scanned with CamScannerMolecular Weight and Polymer Solutions o To determine the number average molecular weight of the linear polyester before crosslinking, one can titrate the carboxyl and hydroxyl end groups by standard methods, In the case of carboxyl, a weighed sample of polymer is dissolved in an appropriate solvent such as acetone and titrated with standard base to a phenolphthalein end point. For hydroxyl, a sample is acetylated with excess acetic anhydride, and liberated acetic acid, together with carboxyl end groups, is similarly titrated. From the two titrations, one obtains the number of milliequivalents of carboxyl and hydroxy! in the sample. The number average molecular weight (i.¢., the number of grams per mole) is then given by: yi, 2.x 1000 x sample wt meq COOH + meq OH ‘The 2 in the numerator takes into account that two end groups are being counted per molecule. In polyester processing. the acid number. defined as the number of milligrams of base required to neutralize 1 g of polyester. is frequently used to monitor reaction progress. (Other titratable end groups include amino groups in polyamides. acetyl groups in acetyl-terminated polyamides, isocyanate in polyurethanes, and epoxide in cpoxy poly- mers. A number of factors can complicate end-group analysis: lack of solubility, high so- lution viscosity. severe steric hindrance. But where these difficulties can be surmounted, end-group analysis is preferred for polymers in the 5,000 to 10,000 molecular weight range. 2.3.2. Membrane Osmometry Of the various methods of number average molecular weight determination based on col- ligative properties, membrane osmometry is most useful. When pure solvent is separated from a solution by a semipermeable membrane that allows passage of solvent but not solute molecules, solvent will flow through the membrane into the solution. As the liquid level rises in the solution compartment, the hydrostatic pressure increases until it prevents further pas- sage of solvent or, more exactly. until solvent flow is equal in both directions. The pressure at equilibrium is the osmotic pressure. A schematic representation of an osmometer is given in Figure 2.2. Osmotic pressure may be determined by allowing the system to reach equilibrium and measuring the hydrostatic head that develops. This is referred to as the static equilibrium method. Alternatively, one can apply a counterpressure to the measuring tube connected to the solution compartment, which prevents flow of solvent and maintains equal liquid levels in the two measuring tubes. This is called the dynamic equilibrium method. Because the for- mer method usually requires long periods of time to attain equilibrium, the dynamic method is preferred, A variety of dynamic membrane osmometers are manufactured, which usually encom- pass a horizontal membrane separating solution and solvent cells. The type shown schemat- ically in Figure 2.3 measures osmotic pressure directly via a strain gauge transducer attached toa flexible diaphragm in the solvent cell. Semipermeable membranes are usually constructed from polymeric materials such as cellulose acetate, cellulose nitrate, rubber, and poly(vinyl alcohol). Scanned with CamScannerPolymer Structure and Properties Measuring tubes ‘Semipermeable membrane FIGURE 2.2. Schematic representation of a membrane osmometer. SOLUTION NLET i lags A old FIGURE 2.3. Automatic membrane osmomeier [Courtesy of Wescan Instruments, Inc.) Scanned with CamScannerMolecular Weight and Polymer Solutions 45 He Bia / Slope = A c FIGURE 2.4. Plot of reduced osmotic pressure (7/C) versus concentration (C). Osmotic pressure is related to molecular weight by the van't Hoff equation extrapolated to zero concentration: (Cleo where 7, the osmotic pressure, is given by w= pg Ah where R is the gas constant, 0.082 L atm mol~! K~! (CGS) or 8314 J mol! K-! (SD; T is the temperature in kelvins; C is the concentration in grams per liter: p is the solvent den- sity in grams per cubic centimeter. ¢ is the acceleration due to gravity. 9.81 m/s*: Mh is the difference in heights of solvent and solution in centimeters: and Az is the second virial co- efficient (a measure of the interaction between solvent and polymer). A plot of reduced osmotic pressure. mC. versus concentration (Figure 2.4) is linear with the intercept equal to RT/M, and slope equal to Az. Usits for 7/C are dyn L g~! cm=! (CGS) or J kg~! (SD. Because Az is a measure of solvent-polymer interaction, the slope is zero at the theta temperature. Thus osmotic pressure measurements may be used to determine theta conditions. The major source of error in membrane osmometry arises from low-molecular-weight species diffusing through the membrane. It explains why molecular weight values obtained are generally higher than those obtained by other colligative property measurements where all species present are counted, Membrane osmometry is generally useful over a molecu- lar weight range of about 50.000 to 2 million, the limiting factors being the permeability of the membrane at the lower end and the smallest measurable osmotic pressure at the up- per. Because most polymers of commercial significance fall in this range, membrane os- mometry is the most widely used method of determining absolute number average mole- cular weights. Scanned with CamScanner