MOLAR MASS of POLYMERS

• Recognize the influence of molar mass (molecular
weight) on polymer properties.
• Understand the relationship between molecular
weight and degree of polymerization.
• Understand the significance of number-average (Mn)
and weight-average (Mw) molecular weights.
• Understand the nature of polydispersity.
• Recognize that the molecular weight of a polymer
influences its physical properties.

X: Degree of Polymerization

• The molecular weight (M) of a homopolymer is the
sum of the masses of the repeat units (M0) in the
polymer chain:
M = XM0
where X is the degree of polymerization, the number
of repeat units in the chain.
• The molecular weight of a copolymer is based on a
weighted average of the masses of all repeat units
(Mi0, Mj0 Mk0, etc.) in the polymer chain:
M0copoly = χiMi0 + χjMj0 + χkMk0 + …
where χi, χj, χk, etc. are the mole fractions of the
repeat units.

Mol Wgt 2-1

. Mass Distribution in Low-MW Polystyrene n = 110 n = 120 H H C C H Signal n Intensity n = 100 n = 130 n = 140 9000 11000 13000 15000 M Adapted from K.. 355-359 Mol Wgt 2-2 . the weight-average molecular weight – Mz. Polymer Size and Shape • Most polymers are polydisperse — they contain more than one chain length. the number-average molecular weight – Mw. Rollins et al. • The average distribution of chain masses can be described in more than one way: – Mn. 1990 Rapid Commun. the viscosity-average molecular weight • Mz ≥ Mw ≥ Mv > Mn • Each value is determined by an aspect of polymer structure. the z-average molecular weight – Mv. 4. Mass Spectrom.

osmometry. Mol Wgt 2-3 . Mn: Number-Average Mol. Mw is Σ NiMi2 Mw = Σw M Mw = ———— ΣN M i i i i • Mw accounts for the distribution of molar mass in the polymer. ebullioscopy (bp elevation). and cryoscopy (fp depression). In terms of wi or numbers of molecules. • Mn may be determined directly by end-group analysis. Wgt. Mw: Weight-Average Mol. • Mw may be determined directly by light scattering. Wgt. • The weight-average molecular weight (molar mass) is the sum of the products of the molar mass of each fraction multiplied by its weight fraction (wi). • The number-average molecular weight (molar mass) of a polymer containing Ni molecules of mass Mi is the arithmetic mean of the molar mass distribution: Σ NiMi Mn = ———— ΣN i • Mn determines the polymer’s colligative properties and tensile strength (= C1 – C2/Mn).

is the ratio of the weight-average molecular weight to the number-average molecular weight: Mw PDI = —— Mn • The polydispersity index of a monodisperse polymer is 1.000 4 50.000 5 400. Da* N 1.00. Mw. and the polydispersity index? Mol Wgt 2-4 . g/mol What are Mn.000 10 100.000. • The polydispersity index increases as the polymer distribution broadens.000 2 700. or polydispersity index. Molecular Weight Distribution • The molecular weight distribution. Example You have a polymer sample that contains the following molecules: M.000 2 Total: 23 *Da = dalton.

01 500 Totals: 23 10. Da2 1.500 Da Mw = ———————— PDI = ——————— 1.000 10 4.000 100.000 2 2.500 Da PDI = 1.000 Da Mw = 609.000 2.000.040×1012 50.000 50.000 0.000 700.095×1012 Mol Wgt 2-5 .00 609.000 0.000 0.000 Da Mw = 609.500.500.000 5 3.40 160.000.000 4 400.000. Da N N·M. Da w w·M. Da N N·M.500 ΣN M i i 2 Mw PDI = —— Mw = ———— Mn ΣN M i i 6.000 2 100.000 2.000 400.005×1012 Totals: 23 10.600×1012 100.35 245.000 10 4.000.04 4.000.000 Da Mn = ————————— 23 ΣN M i i Mn = 435.500 Da M.000 0.000 2 2.095×1012 Da2 609.000 1.20 200.000 0.000 0.000.000.000×1012 700.000 4 400.000 5 3. Da 1.000 0.40 M.000.000 6.000 1.000×107 Da 435. Da N·M2.450×1012 400. Σ NiMi Mw = Σw M i i Mn = ———— ΣN i NiMi wi = ———— 10.000.000 2 100.

5 ≤ a ≤ 2. Mw > Mv > Mn. • Mv may be determined indirectly by dilute solution viscometry. and temperature. Wgt. • The z-average molecular weight (molar mass) is Σ NiMi3 Mz = ———— ΣN M i i 2 • Mz is especially sensitive to the presence of high-MW chains. Mz: Z-Average Mol. solvent. Mv: Viscosity-Average Mol. • For typical polymers.0) is determined by the polymer. • Mz may be determined directly by sedimentation equilibrium (ultracentrifugation) and light scattering. Wgt. • The viscosity-average molecular weight (molar mass) is : ΣNiMi(1+a) 1/a Mv = —————— ΣN M i i where the exponent a (0. • Mw = Mv when a = 1. Mol Wgt 2-6 .

000.z < 1.000 Membrane osmometry A n > 5. Adapted from H.5 6.000 Mass spectrometry A n.000 Sedimentation equilibrium A w. Elias.-G.13 Mz = 259.299 Mn = 181.091 PDI = 1.0 6.w.392 5. 2nd Ed.43 RI Mz = 417.w.715 PDI = 1.000 Vapor phase osmometry A n < 50.500. cryoscopy A n < 20. 1997. E = mass calculation requires information about polymer structure.z < 1.z > 1.000 Dynamic light scattering R z < 10.0 5.000 Ebullioscopy.000 End group analysis (titration) E n < 40. p 31 Mol Wgt 2-7 . “An Introduction to Polymer Science”.5 log M Experimental Methods Method Type* Mi Range.986 Mw = 260.322 Mw = 220. g/mol Static light scattering A w > 100 Dilute solution viscometry R v > 200 Small angle X-ray scattering A w > 500 Size-exclusion chromatography R n. Mn = 195.000 *A = mass calculation requires no assumptions about polymer structure.000. R = mass calculation requires information about polymer structure and polymer-solvent interactions.

940 PDI = 1.01 Polystyrene Oligomer H H C C H Signal n Intensity 9000 11000 13000 15000 M Adapted from K. 4. 519-528 Mol Wgt 2-8 . 355-359 Mass Distribution in a Chain-Growth Polymer O O O O ( CH2)4 O−C ( CH2)4 C−O ( CH2)4 O−C ( CH2)8 C−O m n Copolyester Mn = 3.980 (115n) Mz = 12. 12.780 3000 4000 5000 6000 7000 8000 M Adapted from M. Montaudo et al. Rollins et al.980 (114n) PDI = 1..060 (116n) Mn = 11. 1998 Rapid Commun.320 Intensity Mz = 4. 1990 Rapid Commun. Mass Spectrom. Mass Distribution in a Step-Growth Polymer Mw = 11...S.10 Signal Mw = 4. Mass Spectrom.

melt viscosity • Mv: Solution viscosity. Impact of MW on Physical Properties • Mn: Brittleness (resin versus elastomer). stiffness. stress- strain properties • Mw: Tensile strength. extrudablility. molding properties Mol Wgt 2-9 . hardness • Mz: Flex life.