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Chapter 2

Size and shape of polymers


2.1
2.2
2.3
2.4

Single chain conformation


Statistical description of coil size
Conformation of an ideal chain
Characteristic ratio

2.5
2.6
2.7

Equivalent freely jointed chain


Freely rotating chain
Hindered rotation model

2.8
2.9

Radius of gyration
Radius of gyration of an ideal linear chain

2.10 Distribution of end-to-end vectors


2.11 Free energy of an ideal chain

2.1 Single chain conformation


ideal chain:
interactions between monomers are neglected
thermal fluctuations
around the bond length,
for -C-C- bond: 1.54 , only 0.05 negligible
around the bond angle,
e.g. for the tetrahedral angle of 68,
the variation is only 3-5 % negligible
rotations around bonds
are more easily possible
2

conformations
= all states
which can be generated
by rotations around bonds
polymers are loose coils
(Knuel)
continuous change
by statistical movements

parameters:
flexibility of the chain
interactions between monomers on the chain
interactions with surroundings
3

2.2 Statistical description of coil size


conformations
= all states
which can be generated
by rotations around bonds

polymers are loose coils


(Knuel)
2

1/2

continuous change
by statistical movements

parameters:
flexibility of the chain
interactions between monomers on the chain
interactions with surroundings

The most general picture

bond angle may be


considered as fixed
bond vector between
atoms Ci-1, Ci is the
axis of rotation for +1

torsion angle may vary


certain values may be favorable
5

Distribution of bond angles

energy in dependence
on the torsion angle
because of sterical hindrance

: probability for gauche state


determines the static conformation
: energy barrier between trans / gauche
dynamics of conformational rearrangements

2.3 Conformation of an ideal chain


+ 1 backbone atoms

A2
A0

A3

A1

Ai

Ai-1

. denotes the ensemble average


mean-square end-to-end distance:

Aj-1
An

A4

= 0

Aj

2 = 2 =
=1 =1

all bond vectors are assumed


to have the same length: =

A2
A0

A3

A1

Ai

Ai-1
cos
Aj-1

An

= 2 cos

A4

Aj

2 = 2 cos
=1 =1

freely jointed chain:


cos = 0 for all

2 = 2

However, usually, there are correlations


between bond vectors, expecially neighboring ones
cos 0 for
ideal chain:
for large separation distance along chain contour,
we still have: lim cos = 0

define:

=1

=1

cos 2 = 2

: characteristic ratio

=1

2.4 Characteristic ratio


infinite chain: = for all

real chain: cutoff at finite smaller


Cn

polymer

8
6
4

100

for long chains:

200

1,4-polybutadiene
polypropylene
poly(dimethylsiloxane)
polyethylene
atactic polystyrene

5.5
6.0
6.8
7.4
9.5

2 2

the more bulky the side groups, the higher

10

2.5 Equivalent freely jointed chain


It has the same 2 value and
the same (i.e. the maximum end-to-end distance,
or contour length) as the ideal chain,
but freely-jointed bonds of length (Kuhn length)
The contour length is = .
2 = 2 = = 2

number of Kuhn segments: =

and the Kuhn segment length: =

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Summary
polymer
1,4-polybutadiene
polypropylene
poly(dimethylsiloxane)
polyethylene
atactic polystyrene

()

5.5
6.0
6.8
7.4
9.5

9.9
11
13
14
18

: degree of polymerization
: monomer length

or : number of Kuhn segments


or : Kuhn segment length

root mean square end-to-end distance:


0 =

1/2

1
2

12

2.6 Freely rotating chain

assumptions:
1. all bond lengths and bond angles fixed
2. all torsion angles < are equally probable,
i.e. the potential = .
= 2 cos

13

=1

=1

=+1

2 = 2 = = + 2 +
=1 =1

=1

=1

= 2 + 2 (cos ) + (cos )
=1

=+1

= 2 + 2 (cos ) + (cos )
=1

=1

k = i-j.
j = 1 k = i-1.
j = i-1 k = 1.

=1

k = j-i.
j = i+1 k = 1.
j = n k = n-i.

14

=1

=1

=1

(cos ) + (cos )

2
2

2cos
1+
1 cos

1 + cos
1 cos

2 (cos ) = 2
=1 =1

cos
1 cos

freely rotating chain

The bond angle of -C-C- bonds is = 68 = 2.2

This value is lower than the measured values,


i.e. there are additional steric hindrances.

15

2.7 Hindered rotation model


assumptions:
1.

all bond lengths and


bond angles are fixed

2.

the potential ( )
is not constant

The probability of a certain torsion angle

is proportional to the Boltzmann factor

1 + cos 1 + cos
=

1 + cos 1 + cos

( )

where the average torsion angle is given by cos =

( )

0 cos exp

( )

0 exp

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2.8 Radius of gyration


characterize size of
polymer of any architecture
(linear, branched...)


Ri R j

square radius of gyration:


average square distance between
monomers at position
and polymers center of mass

Rj

cm


R i R cm

R cm

Ri

with

=1

=1

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=1

=1

=1

1
1
1
2
= 2 +

1
1
2
= 2 2 + = 2 2

=1 =1

=1 =1

1 1
1
2
2
2
=

2 2
2
=1 =1

2
2

=1 =1

1
=

2
2
=1 =1

1
= 2

=1 =

now, every monomer is counted twice


as an alternative, let the
second sum start from =

alternative definition of
radius of gyration (useful
for scattering experiments!)

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2.9 Radius of gyration of an ideal linear chain


use continuous coordinates:
=1

1
2
= 2

0 and
=

section of monomers = shorter ideal chain

= ( )2

2
2
( )2
2
= 2 ( ) =

2 2
3
0

for ideal linear chains:

2
6

2 3
=

2 2 3

2
=
6

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