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Problem Set 1

Introduction to Polymer Physics, SS 2011, 13.4.10

1. Using two polystyrene fractions with very uniform molecular weight distribution (P 1), a bimodal mixture with a mass average molecular weight of M w = 25000 g/mol and a polydispersity of P = 1.25 should be prepared. The mixture should contain equal numbers of the different chains. Calculate the molecular weight and the number average degree of polymerization of the two components.

2. Step-growth polymerization.

(a)

(b)

Using the equations given in the lecture, prove that the number and weight average

degrees of polymerization are given by N n = respectively (x is the extent of reaction).

Comment on the behavior of N n for x 1. In how far does this make sense physi- cally? What would rather happen in a real system? Why is it hardly possible to ever achieve x = 1, i.e, what are the factors that limit the molecular weight in step-growth reactions?

1x (Carothers equation) and N w = 1+x

1

1x ,

3. Explain why the intensity of light scattered by a polymer solution depends on the second virial coefﬁcient (A 2 ) of the solution. The central argument rests on a question of length scales: How does the wavelength of visible light compare to the average distance between coils (estimate this for a polystyrene solution with M n = 10 5 g/mol at 1 g/l, assuming e.g. a cubic arrangement)? Would the polymer fraction (as compared to the pure solvent) scatter any appreciable excess amount of light if the molecules were ﬁxed at their positions?