Chapter 2 Chain conformation in polymers 2.

1 Flexibility mechanism
polymerization various long chains (molecules of polymers) Degree of rotation about σ bond
Monomer
Configuration conformation Flexibility
collection of these long chains States and properties of Polymers
1. Ethane (CH3-CH3)
In different conformations (plastics, rubbers or fibers)
There are many possible conformations for
eclipsed
polymer chains can be flexible or rigid (stiff, non flexible) and polymers ethane, However, Interaction between H produces the energy
maximum and minimum.
could be crystalline or amorphous.
Molecules take the conformation with lowest
energy.

staggered

Conformation: 3D spatial arrangement of atoms or groups that is The symmetry of the molecule gives 3 equivalent
changed under the effect of thermal motion, but doesn’t involve minima and maxima per revolution
breaking of chemical bonds.
1 The energy barrier (eclipsed) is equal to 11.8 kJ mol-1. 2

2. n-butane (CH3-CH2-CH2-CH3)
Has 3 different stable conformational states
Trans(T) and gauche (G) and gauche’(G’) 15 kJ mol-1

?
2.1±0.4

The energy difference between the trans and gauche states is

2.1±0.4 kJ mol-1. The energy barrier between the trans and the
gauche states is 15 kJ mol-1.

E(GT) ~ RT at 300K, therefore, T, G and G’ have similar

probability, 3 isomers exist in butane.
Only rotation about middle bond can change the direction of backbond, the 3 4
rotation about two end bond do not change conformation.

The contour length of the chain

3. Pentane (CH3-CH2-CH2-CH2-CH3)

Any section of the chain with consective trans states of

1 rotation bond 3 conformations T, G, G’ torsion angle is zig-zag conformation (rod-like)
2 rotation bonds 9 combinations and 6 distinguished

)θ

If whole chain in trans, the chain has the largest end-to-end distance

consider an Alkane with n C, n-1 σ bonds, two end bonds don not contribute q
to different conformation. Others are in one of 3 conformations (T, G, G’). the Rmax = nl cos
number of conformations is 3n- 3 . Due to symmetry and low possibility of high 2
energy states, the number of conformations less than 3 n-3

The conformations of polymers are changing at 1011-1012Hz

5 6

1
 Gauche states of torsion angles lead to flexibility 2.2 Conformation of an ideal chain
in the chain conformation
ideal chains (no long range interaction between repeat units)
In general, Polymer chains
rod-like
real chains
… TTTTTGTTTGGTTTTTTG…… .
rod-like
rod-like
polymer molecules prefer strongly one conformational state to other states, which solvent (surroundings)
Real chains interact with
are stiff
polymers have similar preferences for a number of different torsional states, themselves
which are flexible.

Polymer chains exhibit in several cases a random

attract
chain conformation, i.e. a random distribution of T repel
and G states. Macromolecular chains with random In solvent, at low T attract > repel
conformation (random coils or Gaussian chains) are
at Tθ, attract ~ repelideal chains
found in solutions of polymers in good solvents, in
polymer melts and in glassy amorphous polymers. High T attract < repel, polymer swell
Gaussian chain
7 8

Conformations of polymers in solutions How the interaction influence the conformation?

Consider a chain with n=1010 bonds, l ≈ 10-10m, contour length L=nl=1010×10 10 ≈
1m Magnify all lengths by 108, that is l ≈ 1cm

1. strong attraction between monomers, the conformation of the polymer is a dense

object called collapsed globule, V ≈ nl3 ≈ 104m3, R=3√V≈20 m, a classroom
2. No interaction between monomers, Random walk, R ≈n 1/2l ≈ 103 m, a campus
3. With excluded volume repulsions, R ≈ n3/5 l ≈10 km, a city
4. With long-range repulsions, R ≈ nl ≈ 105 km, the order of the distance to the
Moon.

The multitude of conformations available for polymers is very

9 10

important for their properties

R nn nn
Models for calculating the average end-to-end distance l = ri
2 = ∑∑ ri × rj =l 2
∑∑ cosqij If
i =1 j =1 i=1 j =1

Consider a flexible polymer of n+1 backbond atoms Ai (0≤i≤n) 1. Freely jointed chain
The freely jointed chain consists of a i≠j
The end-to-end vector is the sum of all n bond vectors in the chain
n continuous chain of bonds: the orientation of the cosqi , j = 0
= r different bonds is completely uncorrelated. No
R n ∑i direction is preferred. Thus,
cosqi , j = 1
i=j
i=1

The average end-to-end vector of an isotropic collection of 2 2

chains of n backbond atoms is zero. R = nl

Rn = 0 Flory’s characteristic ratio

The simplest non-zero average is the mean-square end-to-end distance Ideal chain, there is no interaction between repeat units separated by a
great distance along the chain contour- no correlation between
n n nn
directions of distant bond vectors
=
R 2 º R n2 = Rn × Rn = ∑ri × ∑rj ∑∑ ri × rj
i=1 j =1 i =1 j =1
If i - j >> 1 No interation -- ideal chain
11 12
2
 2. Freely rotating chain
Experimental and theoretical estimates of the
characteristic ratio (C) for polyethylene at Assumptions: all bond length (l) and bond angles (θ) are fixed
ignores the variations of potential U(φi)
140°C. all torsion angles are equally likely and independent of each other.
n
n

R 2 = Rn × Rn = ∑∑ ri × rj
i =1 j=1

The correlation between rj

bond vectors ri and rj lcos θ 2
must be determined,
which pass along rj-1
through the chain of ri
bonds connecting bond ri ri+1
and rj. lcos2θ
rj-2
lcos Ij-iIθ

lcos3θ

13 14

3. Hindered rotation model

T and E dependence of conformation

Potential of torsion angle

Simulated polyethylene chains

The probability of any value of torsion angle φi is taken to be ( E=2.5 kJ mol-1), n=50.
proportional to Boltzmann factor. Simulated polyethylene chains (T=400 K; n=50).
The energy difference between G and T ( E) is
φi close to T or G states, at normal T there are some Φi shown below each simulate molecule.
corresponding to high energy
15 16

Random walk in one dimension

N- b mb N+ b

17