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Techniques of polymer characterisation

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1. 2. 2.1 2.2 2.3 2.4 2.5 Polymer Properties and Characterization Methods The Single Macromolecule, Polymer Chain Configuration Conformation - models of polymer chains, end-to-end-distance, radius of gyration, concentration range, entanglement, rubber elasticity Constitution - Linear, Branched and Cross-linked Polymers The Statistical Character of Polymer Properties - molecular weight, chemical heterogeneity, tacticity The Polymer Solution - solubility of polymers, dilute polymer solution, the FLORY-HUGGINSeq., solubility parameter, - phase separation, theta-temperature

3 3.0 3.1

Determination of Molar Masses Overview Colligative Properties - thermodynamic relations 3.2 Vapor Pressure Osmosis 3.3 Membrane Osmosis (3.4 End group analysis) 4 4.1 4.2 4.3 Scattering Methods RAYLEIGH-Scattering - determination of weight-average molecular weight DEBYE-Scattering - determination of shape and size of macromolecules, the scattering function Dynamic Light Scattering - diffusion coefficient, hydrodynamic radius Ultracentrifuge

5.

6. Viscometry of Dilute Polymer Solution - KUHN-MARK-HOUWINK-eq., FLORY-FOX-eq.

7. 7.1

Molecular Weight Distribution General Characterization of Distribution Curves - mathematical formalism, types of m.w.d. 7.2 Separation effects and methods for polymer fractionation 7.3 Polymer-Chromatography - Fundamental, HPLC, SEC, equipment, application, detectors (7.4 Field-Flow-Fractionation) 8. Nonlinear Polymers 8.1 Branched Polymers - short chain branching - long chain branching 8.2 Cross-linked Polymers - mechanical properties - swelling

Copyright © 2008 by Karl-Fr. Arndt Physical Chemistry of Polymers TU Dresden, D-01062 Dresden, Germany No part of this booklet (esp. figures!) may be reproduced or copied in any form or by any means without permission! Only for personal use!

**1. Polymer Properties and Characterization Methods
**

Polymer solution: Polymer chains in dilute solutions are isolated and interact with each other only during brief times of encounter determination of structural parameters of single chains by measurements of the properties of a polymer solution:

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osmometry (membrane, vapour) light scattering (static, dynamic) viscometry of dilute polymer solution ultracentrifugtion molecular weight distribution fractionation gel chromatography chemical heterogeneity special techniques of chromatography and fractionation (combined methods) chain length light scattering viscometry (hydrodynamic properties) diffusion coefficient dynamic light scattering shape of polymer chain scattering methods branching determination of typical dimensions of macromolecules – LCB spectroscopy (number of end-groups) – SCB swelling change of macroscopic dimension of a cross-linked polymer – determination of cross-linking density

further aims of investigations of polymer solutions: solubility of polymers (thermodynamic of polymer solution, interaction polymer – solvent) concentration range (dilute regime – semi-dilute regime) polymer solution at high concentration

54 Δ) πCCC (η): 109.or trans-isomers). f = nCC lCC 1 − cos ϑ 2 = 2 nCC lCC ~ M 1.2. ls = f (chain stiffness) .1 Configuration Position and arrangement of atoms in a polymeric chain can be divided into two categories: . The Single Macromolecule.252 nm 2 〈 h² 〉 o.Structural differences originating from rotations around single bonds (various forms of polymer chains in solution).0 1 + cos ϑ Restricted Rotation 2 〈 h² 〉 o.5° 0. hindrance parameter 〈cos φ 〉 = ∫0 exp(−U (φ ) / kT ) cos φ dφ π ∫0 exp(−U (φ ) / kT ) dφ ns = 7 π Freely Jointed Chain KUNH segment chain ns = number of segments ls ls = length of one segment.154 nm (1.r = nb lb 1 − cos ϑ 1 + 〈cos φ 〉 1 + cos ϑ 1 − 〈cos φ 〉 = 〈 h² 〉 o.Position fixed by chemical bonds (cis.2 Conformation Freely Rotating Chain C C η C lCC: 0. This kind of order which can be changed only by disrupting chemical bondsand is known as configuration. f σ ² σ : steric factor. . Polymer Chain 2. conformation 2.

.0 0 ∫ *) unperturbed (undisturbed) dimension (sum of all interactions = 0 ! see theta-condition) Contour length: maximum chain length hmax = ns ls Æ h²max = n²sl²s ~ M² . for vinyl-polymer: *) ∞ 0 hmax = nCC lcc(eff) = 2 (M/Mo) lcc(eff) = ns ls Æ ns = 2 (M/Mo) (lcc(eff)/ls) ∫x 2 n − ax ² e dx = 1 ⋅ 3.. y.h: end-to-end distance ⎛ ⎞ 3 w(x.( 2 n − 1) π 2 n + 1 a n + 1/ 2 .z) dxdydz = ⎜ ⎟ ⎝ 2 π 〈 h² 〉 o ⎠ Cartesian coordinates 3/ 2 ⎧ ⎪ ⎪ ⎛ 3( x ² + y ² + z ² )⎞ ⎫ ⎟ ⎬ dx dy dz ⎨exp⎜ − 2 〈 h² 〉 o ⎠⎪ ⎪ ⎭ ⎩ ⎝ w(h): density function of distribution of h: ⎛ ⎞ 3 w( h) dh = ⎜ ⎟ ⎝ 2 π 〈 h² 〉 o ⎠ 3/ 2 ⎧ ⎫ ⎛ 3 h² ⎞ ⎪ ⎪ ⎟ ⎬ 4π h² dh ⎨ exp⎜ − ⎝ 2 〈 h² 〉 o ⎠ ⎪ ⎪ ⎩ ⎭ ∞ spherically symmetrical Mean-Square Value: 〈 h² 〉 o = dh w( h)h² = ns ls ~ M 1.

lim C n = C∞ .Radius of Gyration 〈s²〉 o = 1 2n² ∑∑ i j 2 rij = 1 n +1 ∑si2 i Characteristic Ratio C∞: 2 〈 h² 〉 o = ns ls2 = nCC lCC C n .

polyethylene: PE-HD (high-density): 1. radius R *) disc.g. 10..10 SCB/1000 C-atoms PE-LD (low density): SCB + LCB PE-LLD (linear-low-density): copolymerisation with 1-olefins. radius R ellipsoid *) Example: r= R Characteristic dimension Characteristic dimension – radius of gyration – molecular weight <h²>o = 6 <r²>o <h²> = (2 +ε)(3 + ε) <r²> <L²> = 12 <r²> <R²> = (5/3) <r²> <R²> = 2 <r²> (a² + b² + c²) = 5 <r²> <h²>o ~ M <h²> ~ M 1 + ε L~M R~ M1/3 R ~ M1/2 < r² > = r = 0 ∫ r² 4πr² dr r =0 r= R ∫ 4πr² dr 3 = R² 5 2..d..40 SCB/1000 C-atoms . length L hard sphere. good solvent thin rod. density) e.Radius of gyration and characteristic chain dimension of different types of macromolecules: Shape of macromolecule unperturbed coil random coil.6 C-atoms influences properties in solid state (crystallinity..w. influences melt and solution properties short chain branching (SCB): 2.3 Constitution Branching long chain branching (LCB): < 10 C-atoms broader m..

PC . PP.step-growth (step polymerization. other vinyl-polymers) . monomer + oligomer.) step growth reaction: 1 monomer + monomer.g.d. epoxy-resin) interpenetrated networks 2. macromolecules + macromolecules (polycondensation : PA. PVC. step polyaddition) polymerization .w. EP) chain-growth reaction: 2 monomer + macromolecule (polymerization: PE.chain-growth (or addition) polymerization Distinction between these processes can be made on mechanistic grounds (dissimilar reaction kinetics): Æ different distributions of species as a function of the extent of reaction Æ different molecular weight distribution (m.other branched structures: hyperbranched polymers dendritic polymers Crosslinking elastomers (rubber) high-crosslinked polymers (e. polyaddition : PUR. monomer/oligomer + macromolecules.4 The Statistical Character of Polymer Properties Polydispersity and Mechanism of Polymerization Formation of polymers from monomers is divided into two reaction classes: .

P n 2 T2 > T1 2 t 1 1 M reaction time n = Zahl der Moleküle t1 < t2 < t3 < t4 Distributions and Statistical Weights g = fraction distribution of a property Q moment of a distribution (general definition): frequencyg discontinuous ⎛ ⎜ Qg = ⎜ ⎜ ⎝ ∑ gi Qia ⎞ ⎟1 i ⎟a ∑ gi ⎟ ⎠ i cumulative-distribution g Q Q g continuous .

Mw wi ∑ wi M i Mw = i ∑ wi i ∑ ni M i2 Mw = i ∑ ni M i i z-averaged. Mn = ∫ M h( M ) dM 0 ∫ h( M ) dM =1 or: gw = (σw/Mw)² = Mz/Mw = 1 as a measure of polydispersity .Average Molecular Weights Average Number. U = non-uniformity index (SCHULZsche Uneinheitlichkeit). −∞ +∞ 0 +∞ +∞ μ= −∞ ∫ x f ( x ) dx +∞ σ2 n= +∞ 0 ∫ ( M − M n )² h( M ) dM . Mz zi ∑ zi M i Mz = i ∑ zi i ∑ wi M i2 Mw = i ∑ wi M i i Viscosity-average. U = (σn/Mn)² σ ² = ∫ ( x − μ )² f ( x ) dx . wi M0 ⎛ ⎜ Mη = ⎜ ⎜ ⎝ ∑ i ∑ wi i wi M ia ⎞ ⎟ ⎟ ⎟ ⎠ 1 a Polydispersity and Mechanism of Polymerization The width of a molecular mass distribution curve is characterized by the ratios of averages of molecular mass (polydispersity index. combined with one absolute value of an average mass (Mw). Q = Mw/Mn). Mn Statistical Weight ni Definition ∑ ni M i Mn = i ∑ ni i Alternative Form ∑ wi i Mn = w ∑ i / Mi i Weight. Also (Q – 1) = U is used.

3…polymer Entropy of mixing: The Flory-Huggins theory (1) Deviation of polymer solutions from ideal behavior is mainly due to low mixing entropy. Æ Flory (1942) and Huggins (1942) Calculation of ∆Gm = ∆G (A..05 ~2 2 – 10 2 – 30 2 – 50 ∞ at the gel-point Branched polymers Radical addition Network polymers Step-reaction of tri-. (metal-organic complexes) Mw/Mn = 1. 2. „Living Polymers“ Condensation polymers Addition polymers Anionic Group-transfer Step reaction of bifunctional monomers Radical addition Kationic addition Coordination-polym. This is the consequence of the range of difference in molecular dimensions between polymer and solvent.0…1.B) .The numerical value of Q is determined by the reaction mechanism of the polymerization and by the condtions (p. perfectly ordered state to a state of disorder .) under which it was carried out. B = solute (polymer) in case of copolymers or multi-component systems: 1 = solvent.{∆G (A) + ∆G (B)} ∆H = 0 Æ ∆Gm = -T ΔSm • lattice model • transfer of the polymer chains from a pure. T. tetrafunctional monomers 2.5 Thermodynamics of Polymer Solutions Notation: A = solvent.

VA/VB) ΦB) ∆µB = RT ln aB = RT (ln ΦB + (1 – VB/VA) ΦA) Æ ∆µA = f (M) ! VA/VB = [ρBMA/ρAMO] 1/P Æ VA/VB ~ 1/P ~1/MB Enthalpy change of mixing = RT nA ΦB χ χ = Huggins interaction parameter Æ ∆H Gibbs enthalpy based on Flory-Huggins theory: ∆Gm = RT (nA ln ΦA + nB ln ΦB + nA ΦB χ) . NB) . chemical potential ∆µA = RT ln aA = RT (ln ΦA + (1 .• mixing process of the flexible chains with solvent molecules ∆Sm = S (NA.{S(NA) + S(NB)} Æ ∆Sm = -R (nA ln ΦA + nB ln ΦB) ΦA = volume fraction solvent = NA/K = nAVA/( nAVA + nBVB) ΦB = volume fraction polymer = NB/K = nBVB/( nAVA + nBVB) Flory-Huggins theory (3).

c = 1 1+ VB / VA . χc = 1 + 2 VA V + A VB 2 VB .Theta-temperature and Phase separation (1) critical point: Φ B.

Hildebrand showed a relationship between solubility and the internal pressure of the solvent. Since intermolecular interactions of solvent and solute must be overcome when a solute dissolves. Scatchard incorporated the CED concept into Hildebrand´s eq.δB)² = nAVAΦB (δA .δB)² “Like dissolves like” is not a quantitative expression! Problems: polymers with high crystallinity.Solubility Parameter The strength of the intermolecular forces between the polymer molecules is equal to the cohesive energy density (CED). • 1926. ΔH = heat of vaporization) heat of mixing: ∆Hm = VΦAΦB(δA . Æ δ = 2 ΔH V (nonpolar solvent. polar polymers – hydrogen-bonded solvents or polymers Æ additional terms . which is the molar energy of vaporization per unit volume. CED values may be used to predict solubility. • 1931.

It is widely used for correlating polymer solvent interactions.The square root of cohesive energy density is called “solubility parameter”.δS)² has to be small! . For the solubility of polymer P in solvent S (δP .

) ***) parameter of Kuhn-Mark-Houwink equation were determined only in a small range of molar mass. equipment.3.0 Overview Method absolute Osmometry Isothermal distillation Ebullioscopy Cryoscopy Vapor pressure osmometry*) Scattering methods Ultracentrifugation relative Viscosity Size exclusion chromatography equivalent End group determination Molar mass average Mn Mn Mn Mn Mn Mw Mw.. M w . Determination of Molar Masses 3. M z Range (g/mol) **) 104 < M < 106 M < 104 M < 104 M < 104 M < 104 M > 5 102 M > 102 M > 103 M < 106 Mn M < 5 104 *) relative method due to experimental condition **) depends on experimental condition (solvent. . KMH is not valid in low molar mass range. Mz Mη M n. polymer.

solution ∆T/c solvent Ke = calibration constant.5 x 10-4 evaluation (°C) *) 1% solution of polystyrene in benzene. Mn > 103 g/mol: A2.v = A2.0 − Tm = 2 RTm . c = g/g. ⎛ 1 ⎞ ΔT = + ρ K A c ⎜ e 2. v A ⎟ Æ c ⎝ Mn ⎠ solv.5 x 10-5 Æ only vapor pressure osmometry is used in polymer (oligomer) characterization 3.2 Vapor Pressure Osmometry Measurement ΔT = ΔH b RTo2 Data evaluation ln a A with FH − equ. 25°C Mn = 106 g/mol 0.5 x 10-3 2.3.3 8 x 10-5 5 x 10-5 2.0 x B ΔH m → xB ΔTb = Tb − Tb. xB ≈ c MA MB Relative Comparison of the Sensitivity of Various Colligative Properties*) Property Mn = 104 g/mol Mn = 105 g/mol Osmotic pressure (cm 30 3 solvent) Vapor pressure 8 x 10-3 8 x 10-4 lowering (cm Hg) Freezing point 5 x 10-3 5 x 10-4 depression (°C) Boiling point 2.0 x B ΔH b → xB .1 Colligative properties: cryoscopy: ebulliometry: ΔTm = Tm.0 = RTb2.0 c .

3. Schematic representation of the osmotic pressure between solvent (´) and solution (´´) Osmotic equation: Data evaluation: π cB = ⎛ 1 ⎞ RT + B c B = RT ⎜ + A2 c B ⎟ Mn ⎝ Mn ⎠ .3 Osmotic Pressure The measurement of osmotic pressure is the most important method for the determination of the number average molar mass Mn.

r distance sample-detector.1 Rayleigh-Scattering Lord RAYLEIGH (1842-1919): Intensity of scattered light ~ (wave length)-4 We measure the reduced scattered intensity (RAYLEIGH I(θ ) r 2 Rθ = ≡ R θ ( solution) .: F(θ ) = sin θ Light-scattering equation monodisperse: K cB 1 = + 2 A 2 c B + . Rθ M . π = R T⎜ B + A 2 c B ⎟ ⎜ ⎝M ⎠ Rθ R T ⎝ ∂ cB ⎠ T ⎛ ∂π ⎞ ⎛1 ⎞ ⎟ = R T ⎜ + 2A 2 c B ⎟ ⎜ ⎠ ⎝ M ⎝ ∂ cB ⎠ T 2 ⎛ ∂n ⎞2 4π 2 n o ⎜ ⎜∂c ⎟ ⎟ F(θ ) N L λ4 B⎠ o ⎝ with K = optical constant: K= F(θ): polarization of the primary light and dependence of the effective scattering volume on the scattering angle (1/sinθ): −1 F(θ ) = (sin θ ) vertical pol.: 1 + cos 2 θ non-polarized: F(θ ) = 2 sin θ cos 2 θ horizontal pol. Io intensity of the Concentration fluctuations determine the intensity of the scattered light: K cB 1 ⎛ ∂π ⎞ ⎛c 2⎞ = ⎟ .... Scattering Methods 4.R θ ( solvent) ratio) Rθ : I o primary radiation (incident beam) θ angle of observation..4..

Rθ M w 4. or: large particles. intramolecular interference K cB 1 ⎛ 16 π 2 2 ⎜ 1+ r = 2 R (θ . P(θ ) -1 =1+ q 2 r 2 3 3 Light-scattering equation. small angles) follows: 1 1 P(θ ) =1.q 2 r 2 . c = 0 R(θ)c=0 ⎞ sin θ / 2⎟ + 2 A 2 c B Z ⎠ 2 R (cB)θ =0 z-average of radius of gyration: s2 Z ≡ r2 Z ∑ wi Mi = Mw r2 i .. c B ) M w ⎝ 3λ R θ = 0...2 DEBYE-Scattering (M > 105 g/mol) interference between the light scattered from various positions on the particle (intramolecular interference): K cB 1 = + 2 A 2 c B + . all angles.polydisperse: K cB 1 = + 2 A 2 c B + .. Rθ P (θ ) M w particle scattering function P(θ): P(θ) = R(θ)/R(θ = 0) sin(qrij ) 1 P(θ ) = 2 ∑ ∑ qrij N i j P(θ ) = 1 Mw Rθ ⎞ ⎛ ⎜K ⎟ c ⎝ B ⎠ C→ 0 q scattering vector: q =( 4 π / λ )sin θ / 2 ... λ = λ o / n For q rij << 1 (that means: small particles.....

Zimm-Plot 4. a shift of the frequency of the scattered light occurs in analogy to the well-known Doppler effect of acoustic waves νLight ~ 1015 Hz.. ∆ν: 105. Hydrodynamic radius: kB T Rh = 6π ηA D .. the diffusion coefficient D of the particles may be obtained from an analysis of the line width of the spectral density profile of the scattered light intensity.107 Hz).. In principle.3 Dynamic Light Scattering – Fundamental Due to the Brownian motion of the scattering particles.

dx / dt and s = ω²x s = sedimentation c. Sedimentation velocity large angular velocities. Svedberg equation friction force = centrifugal force – buoyancy force K f = Ks f df M B = ω ² x (1− ρ A v B ) dt N L with f = kBT/D f = friction c.1 ⎟ ⎠ ⎝ [(1− ρ A 2 v B )ω ² x 2 2 − x1 ( )] . and virial coefficients. s ~ Ma Æ MB = RT s D 1− ρ A v B Svedberg-equ. concentration at two x-values ..absolute method . diffusion coefficients. D = diffusion c.besides the molar mass and molar mass distribution the AUC makes it possible to determine sedimenation coefficients.5. . Ultracentrifugation .2 ⎞ ⎟ MB = ⎜ R Tln ⎜ c B. Sedimentation equilibrium cross-section q net-mass transport: dm/dt = dms/dt + dmD/dt Diffusion dmD/dt Sedimentation dms/dt equilibrium: dm/dt = 0 ! ⎛ ∂c ⎞ dm = q ⎜ s cB ω ² x − D B ⎟ = 0 ∂x ⎠ dt ⎝ ⎡M ⎤ 2 c B (x) = c B (x = x b ) exp ⎢ B (1 − ρ A v B ) ω ² ( x ² − x b )⎥ ∂ cB Æ s cB ω ² x = D ∂ x Æ ⎣ RT ⎦ xb = bottom Æ ⎛ c B.large scale of molar masses between 10³ and 109 g/mol .

2 days..Experiments Powerful tool. and energy is dissipated (internal friction). left: velocity profile. polymers with microgels. multicell-rotors different detectors 6... Viscometry of Dilute Polymer Solution Viscometry is the most widely utilized method for the characterization of polymer molecular mass since it provides the easiest and most rapid means of obtaining molecular mass–related data and requires a minimum amount of instrumentation.freely-draining.. A most obvious characteristic of polymer solutions is their high viscosity.. Æ increase of viscosity . and copolymers (sedimentation in a density gradient). equilibrium hours. especially for complicated systems such as polyelectrolytes. . heterogeneous polymers.60. the higher is the stress to maintain the velocity gradient. partially-draining As a result of the velocity distribution the macromolecule rotates.000 rpm. flow through a tube right: velocity gradient in a macromolecule relatively to the center of mass: . The higher the internal friction in the fluid.. even when amount of added polymer is small...

correction for contribution to kinetic energy: B η = A − .Measurement of viscosity: HAGEN-POISEUILLE`s law: π r 4g h ρ t η= = A ρ t ⇒ η~ t 8l V Hagenbach-correction.6..5 aη = 0 aη = 0.0. cB B η0 c B → 0. 1/t² The limiting viscosity number (intrinsic viscosity): [η] = lim c ηsp 1 η − η0 = lim . intrinsic viscosity): [η] ηo = viscosity of solvent Determination of the limiting viscosity: SCHULZ-BLASCHKE: HUGGINS: KRAEMER: ηred = kSB [η]ηsp + [η] ηred = kH [η]² cB + [η] ηinh = kK [η]² cB + [η] Limiting viscosity number and molecular weight Æ KUHN-MARK-HOUWINK: [ η] = K η M rodlike molecule: random coil freely-draining limit : non-draining limit (theta conditions): sphere: disk: aη aη = 2 aη = 0.. laminar Nomenclature of solution viscosity (IUPAC): Viscosity ratio (relative viscosity): Specific viscosity: Viscosity number (reduced viscosity): Logarithmic viscosity number (inherent viscosity): η rel = η η0 = t / t0 ηsp = η rel − 1= t − t0 t0 η η red = sp cB ηinh = ln η rel cB Limiting viscosity number (STAUDINGER index. G → 0. for t > 100 s no correction . ρt t² experimental determination of B: η/ρt vs.9 aη = 1 aη = 0.5 ..

(α²r = <r²>/<r²>o) [η] = 6 3 2 ⎛α ⎞ Φ 0 .∞ ⎜ h ⎟ ⎝ αr ⎠ 3 r² M 3 2 .Experimental: Common solution viscometers: a) OSTWALD-viscometer b) UBBELOHDE-viscometer PHILIPOFF´s rule (empirical): Æ ⎛ Mη = ⎜ ⎜ ⎝ [η] = ∑ ∑ wi w i [ η]i ∑ ∑ wi Mi η ⎞ ⎟ wi ⎟ ⎠ a 1/ a η FLORY-FOX eq.

polydispersity 2 U=σ 2 n Pn = Pw Pn −1. Pz = = Pn k k ∫ H(P)dP ∫ P H(P) dP dH( P ) P(max): = 0 for P = Pn dP U = Pw/Pn – 1 = 1/k ∞ 0 ∫x n − ax e dx = Γ (n + 1) a n +1 . P ⎝ n ⎠ k ∫ H(P)dP = 1 0 Evaluation of mean values: PH(P)dP k + 1 P 2 H(P) dP k + 2 ∫ ∫ Pw = = Pn .Pn) ∞ ( ) H(P) = k Pn k +1 k! ⎛ k P⎞ P exp⎜ − ⎟ . H(M)= 0 dI(M) dM molecular inhomogeneity. Molecular Weight Distribution 7.1 General Characterization of Distribution Curves h(M) density function of number frequency distribution H(M) density function of mass frequency distribution H(M) = M h(M) I(M) distribution function. frequently termed “integral mmd” (M = P M0. Γ (n + 1) = nΓ (n) ( = n! if n > 0. 2 g w =σ 2 w Pw = Pz Pw −1 Distribution Functions: SCHULZ-ZIMM (FLORY): ⎛ P⎞ 1 h(P) = exp⎜ − ⎟ .7. whole number) . Pn ⎝ Pn ⎠ SCHULZ-ZIMM (FLORY): ∞ 0 1-parameter (Pn) ∫ h(P)dP = 1 2-parameter (k. P = polymerization degree M I(M) = ∫ H(M) dM .

5 : chain transfer to solvent molecules. β = (dI(P)/dP)P=Po β π P² ⎢ ⎣ ⎦ Pn = Poexp(-β²/4).saturated chain end k = 2 : combination (formation of a σ-bond.5. monomers. Pw = Poexp(β²/4).POISSON-Distribution h(P) = P Pn exp(− Pn ) P!Pn Pw = 1+ Pn. formation of one chain k = 1. when free radical sites collide. polymerization regulators (no branches) or other polymer chain backbone Æ branching . 1 SCHULZ-ZIMM (FLORY): k = coupling constant. numerical value depends on termination reaction (radical polymerization) k = 1 : disproportionation ( hydrogen abstraction from one growing chain by the radical end of another) Æ two chains . U = 1/Pn „living polymerization“ WESSLAU-Distribution ⎡ ⎛ ln P / P ⎞ 2 ⎤ 1 o h(P)= exp ⎢− ⎜ ⎟ ⎥ ⎝ β ⎠ ⎥ I(lnPo) = 0.unsaturated terminal unit .

Fractional Precipitation Addition of nonsolvent (or precipitant) (continuously – column fractionation. volume of system is constant.7.2 Separation Effects and Methods for Polymer Fractionation Separation effects Thermodynamic properties precipitation fractionation solubility fractionated extraction solubility fractionation with or without supporting materials with solvents/precipitation agents and/or temperature gradients in separation columns thin-layer chromatography (separating copolymers acc. to chemical heterogeneity) ultrazentrifugation field-flow-fractionation migration in an electrical electrophoresis field Separation methods adsorbability Kinetic effects diffusion and sedimentation Particle size effects size exclusion chromatography field-flow-fractionation Combination of different separation effects! Experimental . discontinuously – fractionation flask) Elimination of solvent by evaporation (not common) Lowering the temperature of the system (ucst.Fractional Solution Fractionation by direct extraction (successive extraction of polymer with a series of solvents) Fractionation by film extraction . control of fraction size can be adjusted more precisely) . or vice versa) (experiment is carried out in one solvent.

a nonsolvent is slowly added to a dilute polymer solution.Fractionation by column elution (polymer on a support.) . 5-10 µm film of the polymer is deposited onto an aluminum foil by dipping the foil into the polymer solution) Fractionation by coacervate extraction (coacervate = polymer-rich liquid phase.g.(FUCHS.Turbidimetric Titration fractional precipitation.. addition of a nonsolvent until essentially all of the polymer is in the coacervate. glass beads. then extraction of the coacervate. the concentration of precipitated polymer is measured by optical methods (turbidity of the liquid phase) Applying the method to copolymers (block and graft copolymers): information is desired concerning the extent of copolymer formation and the amount of homopolymer present cloud point titration: cloud point depends on the chemical constitution . e. the polymer is precipitated selectively. polymer-poor phase is removed and polymer in it is isolated. additional temperature gradient) .. gradient elution – increasing content of solvent in the nonsolvent.

radius of gyration. separation process RI and light-scattering . ternary. Reversed phase columns: the packings are less polar than the mobile phase Binary.. and copolymers retention time ~ A + B lg M SEC: entropic effects.3 Separation effects in high performance liquid chromatography (HPLC) and size exclusion chromatography (SEC): • HPLC: energetic effects (enthalpic).. association. gradient elution: ratio vary with time) Æ HPLC is used to analyze small molecules (end-group).B lg M Detector combinations and their application (SEC): concentration concentration and size RI. microgels. UV. interaction between the stationary phase and the molecules. HPLC utilizes columns that are intended to encourage adsorption and partition mechanism. long-chainbranching. FTIR RI and viscosity copolymers molecular weigth distribution.7. conformation of the macromolecules • retention time ~ A .miscible mixtures of organic solvents and water are employed (isocratic elution: constant ratio. constants of KMH molecular mass (absolute!).

x K η . exp.x and a0. equivalent to [η]PS.i is measured . PS indicate data of calibration standard With Kuhn-Mark-Houwink follows: Universal Calibration: lg M x = K η . Mx can be derived from measurements performed with an SEC equipped with an online viscosity detector.PS 1 lg + lg M PS 1+ a η .i Æ Mx.Calibration of SEC Calibration with narrow standards: Ve = f (lg Mstandard) Æ Ve = A – B lg M Problem: A. Rempp: at constant Ve [η]x Mx = [η]PS MPS x indicate data of unknown polymer. Æ [η]x.x are not available. but complicate. hydrodynamic volume: Vh = [η] M/2.x 1 + a η . condition) In the general case the lgM – Ve dependence is not linear and can be V = approximated by polynomials of the form: e ∑ a (lgM) i i= 0 n i (Calibration by using broad (polydisperse) standards with known molecularweight distribution is possible.i or: direct monitoring of MW by light-scattering detector! Molecular Weight Distribution: w(M) = F(Ve) [dVe/dM] . Grubisic.5 Vh = molar volume of impenetrable spheres which would have the same frictional properties or enhance the viscosity to the same degree as the actual polymer in solution 1966 – Benoit.i vs Ve. solvent.PS 1 + a η .i vs Ve. ) MWD of standards logarithmic normal distribution: maxima in their chromatograms can be related to M = (Mw Mn)1/2.x and a0.i Mx.i MPS.x Æ MW of unknown sample can be calculated if K0. B = f (polymer.x are known! If K0.

• electrical fields for protein separation and purification. f = friction coefficient . D = kT/f Æ l = kT/F F = force. open channel through which samples are transported by a laminar flow of liquid (1966 Giddings). • thermal gradient – thermal FFF. • hydraulic gradient – flow FFF.7. formulation of rigorous theories for both retention and column dispersion! Retention Mechanism: x x=w flow (v(x)) field Side view of the FFF channel field perpendicular to separation axis (z) z x=0 parabolic velocity profile v(x): v(x) = 6 v ⎜ ⎝ ⎛ x x² ⎞ − ⎟ w w² ⎠ Sample is exposed to the field Æ minimization of potential energy Æ steady state velocity U (proportional to the strength of interaction with the field). D = diffusion coefficient (back diffusion) Æ concentration distribution: c(x) = c(x=0) exp(-x/l).4 Field-Flow-Fractionation The separation takes place in a thin. The action of a field. • centrifugal fields for the characterization of colloidal materials. causes a partitioning of the various components into regions of different flow velocitiesÆ differential migration and separation. applied perpendicular to the channel flow. The migration is hindered by the channel wall Æ formation of a layer with thickness l = D/U. if lA ≠ lB) with: U = F/f. In contrast to SEC: analysis in an open channel with defined dimension. l = thickness of the distribution of particles (fractionation.

average molecular weight and distribution of backbone chain Influence of chain branching on polymer properties: SCB Crystallinity Density Melting point Dielectric constant Creep and fracture LCB Limiting viscosity Elution volume in SEC Sedimentation Virial coefficient Angular distribution of scattered light intensity Radius of gyration short chain branching (SCB) long chain branching (LCB) . comb . non-branched chain segments.average number of branching-points per molecule. e. branching density or branching frequency . .g.number of branching end points .average length of side branch and no-branched chain .functionality of branching points . star.type of branching.1 Branched Polymers: comb-model star-model tree-model Structural parameters for describing branching structures: .distribution of branch lengths.8. Nonlinear Polymers 8.

br g′ o = ⎜ ⎟ R h . were derived . Experimental background: Viscosity lg[η] Light scattering <r²> lg M (--.by ZIMM and STOCKMAYER for randomly branched monodisperse and polydisperse polymers.Method (LDPE: absorption at 1378 cm-1) 1 -H nmr (LDPE: CH3 at 9.g. . branch length and their concentration (e. experiments: g′ = g . ____ linear polymer) lg M .br ⎞ R 3/ 2 = go = h 3 . IR .br ⎞ ⎟ radius of gyration g o = ⎜ ⎝ < r² > o . scission of branches at branch points (PVAc: saponification of ester branch units and calculation of initial and final molecular weight) Radiolysis gas chromatography: analysis of the decomposition gases 13 • Determination of LCB: Branched molecules have a smaller coil dimension than a linear molecule of the same molecular weight.5 ≤ b ≤ 15 Theoretical equations relating the shrinking factor (branching degree) and the number of branch points.72 ppm) 13 -C nmr (side chains up to C6) • Specific methods for determination of SCB: -C nmr spectrum. Æ shrinking factor g ⎛ < r² > o .Determination of total number of branches: determination of the concentration of end-groups compared with C-atoms in the backbone (CH3/ 1000 CH2). CH2 at 8.branched polymer. h = h .lin ⎠ M = M br lin viscosity ⎛ < η > o . n-pentyl: 12 %. n-ethyl: 8.lin ⎠ M br = M lin b .11 ppm.lin ⎝ < η > o . 0.LDPE: n-butyl: 67 %.by OROFINO and BERRY for star-branched polymers. n-hexyl and longer: 5 %) Degradation.

ν = cross-linking density Mc = Molecular weight of the cross-linked chain ν = ρB/Mc .2 Cross-linked Polymers chemically cross-linked polymer interpenetrating network physically cross-linked f = functionality.8.

each one running between two cross-links (junction points). It is necessary two assume correlation between the macroscopic dimension of the sample and the chain dimension (deformation model). xo = non-deformed dimension) η = memory-term (depends on polymer concentration at cross-linking. ν .increase of entropy as a result of the introduction of solvent molecules . their displacement is linear in the macroscopic strain (other limit: free-fluctuating phantom network) σ = AηνRT λ −λ −2 ( ) σ = stress (force/area non-deformed sample) λ = deformation ratio (λx = xdef/xo. only change of entropy (∆U = 0).: Two competing processes take place: . statistical theory. no hindrance at deformation Æ phantom-network Gaussian distribution of chain length.Rubber-Elasticity-Theory (RET): A rubber represents an ensemble of polymer chains. A = 1 affine deformation. calculation of change of freeenergy or chemical potential of solvent due to swelling Æ measurement of Q Æ Mc. (dry state: η = 1) A = microstructure factor.decrease of entropy of the network chain as a result of the dilation Swelling degree: Q = Vswollen/Vnon-swollen = 1/(volume fraction polymer) or: Qm = (mpolymer + msolvent)/mpolymer (independent of T !) FR: 1943. λxλyλz = 1) affine deformation: the cross-link points are fixed within the sample. the FLORY-REHNER-eq. no volume change at deformation (Vdef = Vnondef. A = (1 – 2/f) freefluctuating Experimental Background: a) compression of swollen sample b) stress-strain Swelling.

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