Vorlesung MCII

Struktur-Wirkungsbeziehungen in der Makromolekularen

Chemie
Klaus Huber

Gehalten im SS 2013

Im Masterstudiengang Chemie

1
A Structure of Polymer Chains

A.1 Introductory Remarks on Real Linear Polymer Chains

Simple case linear monodisperse C-C backbone chain

Example chain model for polymethylene

z number of point-like methylene-monomers

b distance between neighboring monomers (C-C -bond length)

n number of bonds

n=z1

angle between two neighbouring bonds (bond angle)

109

2
 sequence of n-2 rotational angles

conformation

Fig.A1-1 Figure III.4 Morawetz, 1st Ed.

conformation at time t1

rotation around
C-C backbone bond

conformation at time t2

Fig.A1-2 Figure 1.5 Teraoka

3
abolition of free rotation around backbone bonds

simplest case ethane

rotation around C-C sigma bond

rotational angle (for definition see Fig.A2-1)

potential energy depends on rotational angle

V()

V() is largest -> Hs are eclipsed

V() is lowest -> Hs are staggered
maximum for potential energy Vo

conformation is repeated after 120

V() = (Vo/2)[1-cos(3)]

V() = 0 fr = 0, 120, 240 .

4
V() for n-butane

Fig.A2-1 Figure III.6 und III.7 Morawetz, 1st Ed.

paraffin chain

- two of the H-atoms are replaced by carbon

backbone chains

- =0 carbon backbone chain in all-trans

conformation

- V() = V(-)

all-trans conformation is energetically the most favored

5
A.2 Model Chains

2.1 Model of Rotational Isomeric States (RIS)

real system : varies continuously

model system : three distinct states with

= 0 trans
= 120 gauche +
= 240 = -120 gauche -

statistical thermodynamics
weighting factor exp{-V()/kT}

Fig.A2-2 Figure 74 Flory

6
2.2 Freely Jointed Chain Model

z number of points (monomers)

b distance between neighboring monomers

n number of bonds

n=z1

bond angle no restriction

rotational angle no restriction

sequence of n-1 values for

n-2 values for

shape of one Freely Jointed Chain

7
 n

Calculation of R li li nl
2 2

8
we get

n
R li li nl 2
2
(A-1)
i

corresponds to Gauss-Model Eq(A-4) !

Analogy
Random Flight <-> Freely Jointed Chain

Random Flight of particle Freely Jointed Chain-Model

Mean free step length Bond length

l
Number of steps Number of bonds
n z1=n
Total path Contour length
n nl
Averaged squared displacement Averaged squared end-to-end
covered distance distance of chain
2 = n nl2

9
 step length is constant

analogy turns into identity

Solutions :
Random flight with constant step length (=FJC) and
Random flight with uniform or variable averaged step length
Chandrasekhar, S. Rev. Mod. Phys. (1943) 15, 1
Wang, M. C. ; Uhlenbeck, C. E. Rev. Mod. Phys. (1945) 17, 323

10
2.3 Gaussian-Chain Model

n number of bonds

n = 1 one bond

l2 squared averaged distance between neighbouring monomers

(bond length) obeys Gaussian distribution
3/ 2
3
= 2 exp{(3 / 2l 2 ) R ( x, y, z ) 2 } dx dy dz
2l
R ( x, y , z ) 2 x 2 y 2 z 2

n=z1
bond angle no restriction
rotational angle no restriction
probability for the end-to-end distance of chain R
x<<nl, y<<nl, z<<nl
three dimensions are independent
(no preferential orientation)
product from three one-dimensional distributions
11
W(R) dR = W(x) W(y) W(z) dx dy dz

3

W(R) dR = 1 / 2 exp{ ( x y z )} dx dy dz
2 2 2 2
(A-2a)

3

= 1 / 2 exp{ R( x, y, z ) } dx dy dz
2 2
(A-2b)

= probability to find end of vector of R in

volume increment dx dy dz
chain starts at the origin of coordinate system

1/ 2
3
with = 2
2nl

Fig.A2-3 Figure 76 Flory

12
Important results

- most probable value is at R = 0

- distribution only depends on the magnitude of R

- distribution decreases monotonously with |R| = R

- distribution gets unphysical for R approaching the contour length L = nl fully extended chain

All vectors R which end on the surface of a sphere have equal probability

Cartesian coordinates x, y, z

Spherical coordinates r/R

with r end-to-end distance of a contour segment

R end-to-end distance of total contour

13
cubic volume increment incremental spherical shell
dV = dx dy dz dV = 4R2 dR
local probability density radial probability density
W(R)= W(x) W(y) W(z) = W(R)
W(x,y,z)

3

W(R) dR = 1 / 2 exp{ R } 4R2 dR
2 2
(A-3a)

Important Results

- most probable value is at R = 1/

3

- Factor 1 / 2 exp{ R }
2 2
is the number density of chains ending in

cubic volume increment
3

- Faktor 1 / 2 exp{ R }
2 2
decreases with R

- Factor 4R2 dR is proportional to the number of chains having

values for R between R and R+dR
- Factor 4R2 dR increases with R2
14
Fig.A2-4 Figure 77 and 78 Flory

Description of sub-chains (segments)

needed : Probability for the distance r between any two

point-like monomers selected within a chain

phantom nature : Any sub-chain behaves as if dangling

chain extensions on either side are non-existent

3


W(r) dr = 1 / 2 exp{ 2 2
r } 4r2 dr (A-3b)

Gauss-Modell - W(R) (A-3a) and (A-3b) are valid for all segments
including i bonds with 1 < i < n

15
The Model of a Gaussian-Chain:

W(R) (A-3) is valid for all n > 1

W(R) is valid also for n = 1
Due to cancellation effects from various model deficiencies the Gaussian-Chain model remains a valuable approximation down to very short chains.

Parameters determined by chain conformations require

probability distribution of distances from any monomer combinations within a chain

Averaging via integration

F ( R)W ( R)dR
F ( R) 0

W ( R)dR
0

nominator is 1

16
average value for R

R R 3 4 ( / ) 3 exp{ 2 R 2 }dR
0

with

R 2 /( )

averaged square of the end-to-end distance

R 2 3 /(2 2 ) l 2 n R 2 (A-4a)

2
value for R is identical to Eq(A-1)

Gaussian-Chain model represents limit of FJC-

Model at large n

Fig.A2-5 Figure II.3 Yamakawa

17
Interpretation of Entropy Elasticity

Etropy of a chain S(z, R )

18
2.4 Characteristic Size Parameter for Chains

material parameters

number of bonds n

degree of polymerization z = n +1

molar mass of macromolecule M

z~M

geometric parameters Gaussian Chain / Freely Jointed Chain

end-to-end distance R

R2 l n R

advantage illustrative

disadvantage not accessible directly from experiment

meaningless for non-linear polymers (rings, stars etc.)

19
 radius of gyrations

1 n 2
S si
2
(A-5)
z i 0

averaged squared distance of all mass points

from the center of gravity

the z monomers (mass points) are indicated with 0, 1, 2.n

definition of the center of gravity

n

s4
s
i 0
i =0

s1

Fig. A2-6 Figure radius of gyration center of gravity

distance between center
20
si of gravity and monomer i
advantage universally applicable
directly accessible with scattering techniques

disadvantage not illustrative

definition <S2> Rg

comparison

end-to-end distance <-> radius of gyration

sphere with corresponding radius is indicated in the representation of the chain.

Fig. A2-7 and Fig. A2-8 Figure Teraoka 1.20 and 1.21

21
Derivation of an alternative expression for Rg

22
in the limit of large n Eq(A-7) turns into

<S2> = nl2/6 = R
2
/6

with the abbreviation <S2> = Rg

Rg = ln/6 = R /6 = R /2.45 (A-8)

End-to-end distance is 2.45 times larger than the radius of gyration

degree of polymerisation ~ molar mass

n~M

Rg = K M1/2 (A-9)

23
First experimental verification for scaling law

viscosity measurements in dilute polymer solutions

sol viscosity of pure solvent

pol viscosity of polymer solution

spspecific viscosity

pol sol
sp
sol

specific viscosity versus polymer concentration c

pol sol
sp [ ]c k ' c 2 ...
sol

sp
[ ] k ' c ...
c

24
intrinsic viscosity [] also denoted as Staudinger index

lim sp lim sp
[ ] [ ] KM a scaling law
c0 c c0 c

M averaged molar mass of polymer chains

Theoretical Predictions

spheres Einstein law

sp = 2.5

Vh
sp 2.5cN A Vh : hydrodynamically effective volume of sphere
M

Rh : hydrodynamically effective radius of sphere

4Rh3
Vh
3

25
 4Rh3
sp 2.5cN A
3M

Rh R ~ M1/3

sp ( M 1 / 3 )3
[ ] M0
c M

Gaussian chains Einstein law

sp = 2.5

Vh
sp 2.5cN A Vh : hydrodynamically effective volume of chain
M

4R 3
estimation with end-to-end distance Vh
3

26
 4R 3
sp 2.5cN A
3M

R ~ M1/2

sp ( M 1 / 2 )3
[ ] M 1/ 2
c M

rod / long cylinder extension of Einstein law to anisometric structures ( Kuhn )

(L / d ) 2
sp 2.5
30

L : cylinder length

d : cylinder radius

27
 limit of very large L

( L / d )2
sp
30

d 2L
cylinder volume Vh 4

d 2L ( L / d )2
sp cN A
4M 30

L ~ M1

sp ( M 1 )3
[ ] M2
c M

28
29
Light scattering measurements in dilute polymer solutions

Ni M i
c M i i V M i N M 2

Mw i i
i i i
weight averaged molecular weight Mw i i
c N M
i Vi i N M
i i i

i : degree of polymerisation
Mi : molar weight of chains with degree of polymerisation i
Ni : moles of chains with degree of polymerisation i
ci : concentration of chains with degree of polymerisation i in g/L

Mw > 1 kD

2
Rg
i i i
N M 2
S 2
i
NM
2
z-averaged squared radius of gyration <S >z = 2
i i i

Rg > 10 nm

30
if - solvent is a -solvent
- M > 103-104 g/mol

Rg ~ M1/2

Fig. A2-9 Rg versus Mw

from Myiaki et al. Macromolecules 11 1180

31
Fig. A2-10 Scaling Law

(, ) Cotton et al. Macromolecules (1974) 7, 863-871

32
Fig. A2-11 Discussion of the trend of Rg2/L versus L

Focus on shorter chains

lower molecular weights
values decay
0.4
() PS in cyclohexane (-solvent)
() PE in biphenyl-d-10 (-solvent)
Boothroyd et al. Macromolecules (1989) 22,
3130-3137 0.3

Rg /L / nm
0.2

2
0.1

-200 0 200 400 600 800 1000 1200 1400

L / nm

33
Unresolved issues:

1. How can we map the Gaussian-Chain model onto the results from real polymer chains, despite the fact
that the model is based on assumptions, which entirely contradict the feature of a chain with fixed
valence angles and excluded volume effects? (2.4)
2. Why does the decay of Rg versus M gets steeper while low molar mass values are approached ?
3. Why are the exponents in many solvents larger than the value of 0.5 predicted by Eq(A-9).

Calculation of the Dimensions of real Polymer Chains

From Eq(A-4) and Eq(A-8) we receive

Rg = K M1/2 (A-9)

Both quantities are accessible by static light scattering.

In deed the trend according to Eq(A-9) could successfully be verified, although only in so called -solvents.

Freely Jointed Chain as model chain

FJC-monomer does not correspond to chemical monomer
34
First step Establish a chemical monomer with its corresponding monomer length b

length of monomer in a C-C backbone chain Ci-Ci+2 = b = 0.25nm

FJC as a model for a real polymer chain

Macromolecule in FJC-model chain

chemical language
Monomer b l
Number of bonds n N
Contour length L nb Nl

Prerequisites

1) Identity of the contour lengths

L = Nl = nb (A-10)

Identity of the end-to-end distance

R l N (A-11)

crucial model parameter : l

35
l: Length of a statistical segment length
or
Kuhn segment length

a statistical segment length comprises as many chemical monomers as are necessary to assure that restriction in
bond angles disappear between neighbouring statistical segments

prerequisite for applicability:

macromolecule has to be large enough

to include several Kuhn segment lengths.

Fig.A2-12 Abbildung Stuart X.6.a

36
 bridge between FJC and macromolecule

Second step Establishing a Kuhn segment length from experiment

known : molar mass M

molar mass of monomer Mo
radius of gyration Rg

1. Estimation of contour length

L = M/Mo b

2. calculation of Kuhn segment length from Eq(A-8) Rg2 = l2N/6 = l L / 6

l = 6 Rg2/L

Notice !

l>b and N < n = M/Mo

Issue 1 is solved

37
2.5 Worm-like chain model

Kratky and Porod

Receuil des Travaux de Chimie de Pays Bas (1949) 68, 1106

Model valid for all chain lengths

descriptions
model of a continuously bended wire (kontinuierlich gekrmmter Faden)
in english worm-like chain

1) starting point for deduction chain with discrete elements

Valence chains fixed valence angle

free rotation -> unrestricted

persistence of direction (chain with discrete monomers)

direction of the n-th bond influences
the direction of the (n+1)-th bond

= 180 -

38
first bond lies on z-axis
starts at origin

requested
averaged displacement of the other end in z-direction Lz
n

Lz = l (cos )
i 1
(A-12)
i 1

limit of an infinitely long chain

lim
Lz = a* = l/(1-cos) (A-13)
n

2) transition to continuously bended wire

substitution of variable k=cos

persistence of direction (continuously bended chain)

l
(A-12) turns into Lz = - [1 e ( L / l ) ln k ]
ln k

39
 lim
L z = a* = -l/lnk
L

k=cos loses its original meaning

a* displacement of an infinitely long thread in z-direction

persistence length

lim
Lz = a* = -l/lnk (A-14)
L/l

displacement in z-direction of a thread with finite length L

L / a*
Lz = a * [1 e ] (A-15)

40
Averaged end-to-end distance

R 2 = [2 Lz ( )]d
o

= 2a*[L+a*{e-L/a*-1}] (A-16)

limiting cases of Eq(A-16)

Case 1 L ->

R 2 = 2a*L
a comparison with Eq(A-11)

R 2 = 2a*L = l2N
l = 2a*

Kuhn segment length is twice the persistence length a*

41
Case 2 L -> 0

Taylor-series of Eq(A-16) at L=0

R 2 = 2a*[L+ a* {1 (1/a*)e-0/a*L + (1/2a*2) e-0/a*L2 -. . . -1}]

= 2a*[0.L + (L2/2a*)] = L2

correct result for rod-limit

Animation worm-like chain model

Calculation of squared radius of gyration

Benoit und Doty (J.Phys.Chem. 1953, 57, 958)

lL l 2 l 3 l4
Rg =2 [1 exp{ L 2 / l}] (A-17)
6 4 4 L 8L2

42
 with L ~ M

bridge
between

model experiment
real chain

limiting bahavior for small L

series expansion of 1-exp{-2L/l} at L=0

2 4 8 16
1-{1- L 2 L2 3 L3 4 L4 ...}
l 2l 3!l 4!l

entered in Eq(A-17) leads to

lim L2
Rg 2

L0 12

43
limiting behavior for large L

lim lL l 2 lL
Rg
2

L 6 4 6

limiting behavior for small M Rg ~ L1 ~ M1

transition

limiting behavior for large M Rg ~ L0.5 ~ M0.5

Rg = K M0.5 (A-18)

transition regime -> characterizes chain stiffness (a*)

44
 determines pre-factor of Eq(A-18)

valence angle rotational hindrance

a*
excellent confirmation from experiment

45
 Rg versus L
at variable chain stiffness
Fig. A2-13a Rg versus L for 5
different l
l = 5.0 nm
= 3.5 nm
10
= 2.0 nm

Rg / nm
= 1.0 nm
1
= 0.5 nm
0.1

0.01

0.01 0.1 1 10 100 1000

46
L / nm
 Characteristic ratio

0.9
Fig. A2-13b Fitting of worm-like chain model 0.8
represented as Rg2 /L versus L
l = 5 nm
0.7
0.6
= 3.5 nm

Rg /L / nm
0.5
0.4
0.3
= 2 nm

2
0.2 = 1 nm
0.1 = 0.5 nm
0.0
0 200 400 600 800 1000 1200 1400

L / nm

polyethylene in biphenyl-d10 as -solvent

polystyrene in cyclohexane as -solvent
47
Fig.A2-14 Master Curve
Norisuye and Fujita Polymer J. (1982) 14, 143

Issue 2 solved

48
A.3 Impact of Branching and Ring Closure on Chain Structure

Star-like branching number of branches is uniform

branch (arm) length is uniform

number of arms: f

causes shrinking of polymer dimensions

shrinking is characterized by the

branching factor

49
 2
R g star
g 2
R g linear

Zimm-Stockmayer formula for unperturbed Gaussian coils

3f 2
g (A-19)
f2

Figure A3-1, Rg versus Mw for PI stars

(Bauer et al. Macromolecules (1989) 22, 2337-2347)
good solvent

-solvent
50
 0.8 PI in theta solvent
0.7 PI in good solvent
PS in theta solvent
0.6
PS in good solvent
Figure A3-2, shrinking ratios
0.5

g
PS and PI stars
0.4

0.3

0.2

0.1
2 4 6 8 10 12 14 16 18 20

f 2
R g star
shrinking ratio g 2
51 R g linear
number of arms f
Randomly branched chains A function reacts with A function

number of functionalities per molecule: f

formation with f-functional monomers Af system A3

A
AA
AA A
A
3( f 1) A A A
g (A-20) AA
f AA
AA A
A
Figure A3-3 randomly branched chain AA A
AA
A

A
52 monomer A
A
A reacts with A
 - extremely broad molecular weight distribution

- any monomer as starting site

- gelation at critical point of reaction

- Flory-Stockmayer theory (J.Am.Chem.Soc. (1941) 63, 3083, 3091, 3096; J.Chem.Phys. (1943) 11, 45 and (1944) 12, 125)
- Percolation theory (J.Chem.Soc. Farad. Trans. 2 (1976) 72, 1354)

Non-randomly branched chains building unit of ABC-type

A reacts with B or C
A does not react with A
B only reacts with A C only reacts with A

preparation with a one-pot process

Example for a non-randomly branched polymer: glycogen

53
Figure A3-4b glycogen as an example for non-randomly branched chain
(Burchard, W. Advances in Polym.Sci. (1983) 48, 1- 124,
C-III-3)

A reacts with B and C

25 % of A reacts C
A

C C
B A A
B

54
 3(1 2 )
g (A-21)
2(1 ) 2

special case: B unit = C unit

modern name: hyperbranched chains

system AB2
B
gelation not possible
BA
BA B
A B
1 B B
in (A-21) gets: BA
4(1 p ) BA
BA B
B
BA B
p = Areacted/Atotal BA
B

B
monomer A
B
Figure A3-4 hyperbranched chain
A reacts with B
55
gelation

the Af system

has 1 bond to preceding neighbour/generation

has potentially f-1 new/additional bonds to succeeding neighbours/generation

extent of reaction of functional groups is

p = Areacted/Atotal

each new generation adds p(f-1) new neigbours

particle size diverges if

p(f-1) > 1 (at least one chain emanates from group)

pc = 1/(f-1)

gelation for p > pc

56
The ABf-1 system

concentration of A units: [A]

concentration of B units: [B]

[B] = [A].(f-1) [A]reacted = [B]reacted

p(A) = [A]reacted/[A]total = [B]reacted/[A]total = [B]reacted/{[B]total/(f-1)}

p(B) = [B]reacted/[B]total

p(A) = [B]reacted/{[B]total/(f-1)} = p(B).(f-1)

p(B)c = c[B]reacted/[B]total = 1/(f-1) (identical to the Af system)

c[B]reacted = [B]total/(f-1) = [A]total = c[A]reacted

gelation only at 100% conversion of A units

57
dendrimers ABf-1 as building unit

Extent of reaction is 100%

on each generation

cumbersome preparation of each generation (100% extent of reaction)

see similarities and differences to

non-randomly branched ABf-1

58
regularly branched polymers monodisperse chains with n monomers
are connected by f-functional branching units

first branching unit is origin

number of generations: m

number of chains per branch: x = ((f-1)m 1)/(f-2)

= 2m 1 (f=3)
number of chains: fx

degree of polymerisation: z = nfx

most prominent example f = 3

g = (9n3/z3){x(1/3+10m-6) + 6x2(m-2) + 4m + [2(x+1)m-3x]/n} (A-22)

59
limiting cases:
n=1 dendrimer
m=1 3-arm star

Figure A3-5 Figure 9 Nerger et al. J.Polym.Sci. Pol.Phys.Ed. 157-171, (1982)

Shrinking ratio g for regularely branched particles (R) and star-branched polymers (S) as a function of the
number of branches (R, abscissa3x) or the number of arms (S, abscissaf).

60
Ring closure chain ends connected

flexible polymer ring

shrinking ratio

g = 1/2

can be prepared by anionic polymerisation

n ~ 105

61
A.4 Structur Information from Scattering Curves

dispersed particles scatter light electromagnetic wave

x-rays electromagnetic wave
neutrons particle wave

scattered intensity I

as a function of observation angle

of momentum transfer q
with

q = (4/) sin(/2)

as a function of rescaled q u = Rg q
sample
source
Figure A4-1 Introduction into scattering
q = (4n/).sin{/2}
detector

(q)
62
= scattering intensity
from particles
the intercept of scattering curves

lim
I (q) I 0
q0

formfactor as normalized scattering curve

I (q)
P(q)
I0

series expansion of P(q) in powers of q2 around q = 0 gives squared radius of gyration <S2>

lim 2 S
2
P(q ) 1 q ...
q0 3

initial part of P(q) determined by size of polymer

trend of P(q) determined by shape of polymer

63
 The significance of formfactors

a comparison of sphere
Gauss-model for coils
rod

self-similarity normalization of q: u = q Rg

formfactors of samples differing only in size fall on each other if plotted versus u

Figure A4-2 comparison of sphere-coil-rod

linear scale logarithmic scale

1
1.0

0.8 rod rod

0.1
0.6 coil coil
P(u)

P(u)
sphere sphere
0.4 0.01

0.2

0.0 1 10
0 2 4 6 8 10 64
u
u
 1.0

0.8 rod

linear chain impact of chain stiffness 0.6 worm Nk = 5

uP(u)
0.4 worm Nk = 10

limiting behavior at large q Gauss coil

0.2

Gauss-coil P(q) ~ q-2 q2P(q) = constant 0.0

rod P(q) ~ q-1 qP(q) = constant 0 2 4 6 8 10

u
Holtzer-Plot

10
rod
Figure A4-3 Holtzer and Kratky plots chains with 8
variable degree of stiffness worm Nk = 5
6 worm Nk = 10

u P(u)
4 Gauss coil

2
2
P(u) is not self similar for worm-like chains
Kratky-Plot 0

65 0 2 4 6 8 10

u
Holtzer-Plot Kratky-Plot

Cyclohexane 34C
Mw = 4kD
Nk = 4

d = 0.0 nm
d = 2.0 nm
d = 2.6 nm

Polymer (1987) Vol.28, 863-872

h-polystyrene in melt
Schelten etal. Europ. Polymer J. (1974) Vol.10, 861-864 Mw = 103 kD
Nk = 103
66
linear chain impact of branching

star-branched chain

randomly branched chain

non-randomly branched chains

dendrimer

regularely branched chains

Figure A4-4: Figures 2 and 3 of Nerger et al. J.Polym.Sci. Pol.Phys.Ed. 157-171, (1982)

Figure A4-5: Formfactors of star branched polymers

67
Burchard, Advances in Polym. Sci., (1983) Vol.48, 1ff Polymer (1987) Vol. 28, 1997-2003

theoretical curves for Gaussian chain model polystyrene star Mw = 467 kD

variable arm number in h-cyclohexane, T = 34C
(SANS-experiment )

normalised variable u = Rg q

68