Chapter 2 Chain conformation in polymers

Monomer
polymerization
Configuration

2.1 Flexibility mechanism

Degree of rotation about bond conformation Flexibility
1. Ethane (CH3-CH3)
There are many possible conformations for ethane, However, Interaction between H produces the energy maximum and minimum. Molecules take the conformation with lowest energy. eclipsed

various long chains (molecules of polymers) States and properties of Polymers (plastics, rubbers or fibers)

collection of these long chains

In different conformations

polymer chains can be flexible or rigid (stiff, non flexible) and polymers could be crystalline or amorphous.

staggered

Conformation: 3D spatial arrangement of atoms or groups that is changed under the effect of thermal motion, but doesnt involve breaking of chemical bonds.
1

The symmetry of the molecule gives 3 equivalent minima and maxima per revolution

The energy barrier (eclipsed) is equal to 11.8 kJ mol-1.

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

?
2.10.4

The energy difference between the trans and gauche states is 2.10.4 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 rotation about two end bond do not change conformation.
3 4

3. Pentane (CH3-CH2-CH2-CH2-CH3)
1 rotation bond 2 rotation bonds 3 conformations T, G, G 9 combinations and 6 distinguished

The contour length of the chain

Any section of the chain with consective trans states of torsion angle is zig-zag conformation (rod-like)

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

consider an Alkane with n C, n-1 bonds, two end bonds don not contribute to different conformation. Others are in one of 3 conformations (T, G, G). the number of conformations is 3n-3 . Due to symmetry and low possibility of high energy states, the number of conformations less than 3n-3 The conformations of polymers are changing at 1011-1012Hz
5

Rmax = nl cos

Gauche states of torsion angles lead to flexibility in the chain conformation

In general, rod-like TTTTTGTTTGGTTTTTTG. rod-like rod-like polymer molecules prefer strongly one conformational state to other states, which are stiff polymers have similar preferences for a number of different torsional states, which are flexible. Polymer chains exhibit in several cases a random chain conformation, i.e. a random distribution of T and G states. Macromolecular chains with random conformation (random coils or Gaussian chains) are found in solutions of polymers in good solvents, in polymer melts and in glassy amorphous polymers. Gaussian chain
7

2.2 Conformation of an ideal chain

ideal chains (no long range interaction between repeat units) Polymer chains real chains

Real chains interact with

solvent (surroundings) themselves

attract repel
In solvent, at low T at T, High T

attract > repel

attract ~ repel ideal chains attract < repel, polymer swell
8

Conformations of polymers in solutions

1. 2. 3. 4.

How the interaction influence the conformation?

Consider a chain with n=1010 bonds, l 10-10m, contour length L=nl=10101010 1m Magnify all lengths by 108, that is l 1cm strong attraction between monomers, the conformation of the polymer is a dense object called collapsed globule, V nl3 104m3, R=3V20 m, a classroom No interaction between monomers, Random walk, R n1/2l 103 m, a campus With excluded volume repulsions, R n3/5 l 10 km, a city 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 important for their properties

10

Models for calculating the average end-to-end distance

Consider a flexible polymer of n+1 backbond atoms Ai (0in)

R 2 = ri rj = l 2 cos ij
i =1 j =1 i =1 j =1

If

l = ri

1. Freely jointed chain

The end-to-end vector is the sum of all n bond vectors in the chain

R n = ri
i =1

The freely jointed chain consists of a continuous chain of bonds: the orientation of the different bonds is completely uncorrelated. No direction is preferred. Thus,

cos i , j = 0 cos i , j = 1

ij i=j

The average end-to-end vector of an isotropic collection of chains of n backbond atoms is zero.

= nl

Rn = 0
The simplest non-zero average is the mean-square end-to-end distance
n n n n R2 R2 n = Rn Rn = ri r j = r i rj i =1 j =1 i =1 j =1

Florys characteristic ratio

Ideal chain, there is no interaction between repeat units separated by a great distance along the chain contour- no correlation between directions of distant bond vectors

11

If

i j >> 1

No interation -- ideal chain

12

Experimental and theoretical estimates of the characteristic ratio (C) for polyethylene at 140 C.

2. Freely rotating chain

Assumptions: all bond length (l) and bond angles () are fixed ignores the variations of potential U(i) all torsion angles are equally likely and independent of each other.

R 2 = Rn Rn = ri rj
i =1 j =1

The correlation between bond vectors ri and rj must be determined, which pass along through the chain of bonds connecting bond ri and rj.

rj lcos rj-1 ri+1 lcos2 rj-2 lcos3 lcosIj-iI ri 2

13

14

3. Hindered rotation model Potential of torsion angle

T and E dependence of conformation

The probability of any value of torsion angle i is taken to be proportional to Boltzmann factor. i close to T or G states, at normal T there are some i

Simulated polyethylene chains (E=2.5 kJ mol-1), n=50.

Simulated polyethylene chains (T=400 K; n=50). The energy difference between G and T (E) is shown below each simulate molecule.
16

corresponding to high energy

15

Random walk in one dimension

N- b O

mb

N+ b

17