Mayo-Lewis equation

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The Mayo-Lewis equation or copolymer equation in polymer chemistry describes the distribution of monomers in a copolymer [1]:

Taking into consideration a monomer mix of two components M_1\, and M_2\, and the four different reactions that can take place at the reactive chain end terminating in either monomer (M^*\,) with their reaction rate constants k\,:

M_1^* + M_1 \xrightarrow{k_{11}} M_1M_1^* \,
M_1^* + M_2 \xrightarrow{k_{12}} M_1M_2^* \,
M_2^* + M_1 \xrightarrow{k_{21}} M_2M_1^* \,
M_2^* + M_2 \xrightarrow{k_{22}} M_2M_2^* \,

and with reactivity ratio's defined as:

r_1 = \frac{k_{11}}{k_{12}} \,
r_2 = \frac{k_{22}}{k_{21}} \,

the copolymer equation is given as:

\frac {d\left [M_1 \right]}{d\left [M_2\right]}=\frac{\left [M_1\right]\left (r_1\left[M_1\right]+\left [M_2\right]\right)}{\left [M_2\right]\left (\left [M_1\right]+r_2\left [M_2\right]\right)}

with the concentration of the components given in square brackets. The equation gives the copolymer composition at any instant during the polymerization.

Contents

[edit] Limiting cases

From this equation several limiting cases can be derived:

  • r_1 = r_2 >> 1 \, with both reactivity ratios very high the two monomers have no inclination to react to each other except with themselves leading to a mixture of two homopolymers.
  • r_1 = r_2 > 1 \, with both ratio's larger than 1, homopolymerization of component M_1 is favored but in the event of a crosspolymerization by M_2 the chain-end will continue as such giving rise to block copolymer
  • r_1 = r_2 \approx 1 \, with both ratio's around 1, monomer 1 will react as fast with another monomer 1 or monomer 2 and a random copolymer results.
  • r_1 = r_2 \approx 0 \, with both values approaching 0 the monomers are unable to react in homopolymerization and the result is an alternating polymer
  • r_1 >> 1 >> r_2 \, In the initial stage of the copolymerization monomer 1 is incorporated faster and the copolymer is rich in monomer 1. When this monomer gets depleted, more monomer 2 segments are added. This is called composition drift.

An example is maleic anhydride and stilbene, with reactivity ratio:

  • Maleic anhydride (r_1\, = 0.08) & cis-stilbene (r2, = 0.07)
  • Maleic anhydride ((r_1\, = 0.03) & trans-stilbene (r2, = 0.03)

Both of these compounds do not homopolymerize and instead, they react together to give exclusively alternating copolymer.

Another form of the equation is:

F_1=1-F_2=\frac{r_1 f_1^2+f_1 f_2}{r_1 f_1^2+2f_1 f_2+r_2f_2^2}\,

where F\, stands the mole fraction of each monomer in the copolymer:


F_1 = 1 - F_2 = \frac{d M_1}{d (M_1 + M_2)} \,

and f\, the mole fraction of each monomer in the feed:

f_1 = 1 - f_2 = \frac{M_1}{(M_1 + M_2)} \,

When the copolymer composition has the same composition as the feed, this composition is called the azeotrope.

[edit] Calculation of reactivity ratio's

The reactivity ratio's can be obtained by rewriting the copolymer equation to:

\frac{f(1-F)}{F} = r_2 - r_1\left(\frac{f^2}{F}\right) \,

with

f = \frac{[M_1]}{[M_2]} \, in the feed

and

F = \frac{d[M_1]}{d[M_2]} \, in the copolymer


A number of copolymerization experiments are conducted with varying monomer ratio's and the copolymer composition is analysed at low conversion. A plot of \frac{f(1-F)}{F}\, versus \frac{f^2}{F}\, gives a straight line with slope r_1\, and intercept r_2\,.

A semi-empirical method for the determination of reactivity ratio's is called the Q-e scheme.

[edit] Proof

Monomer 1 is consumed with reaction rate [2]:

\frac{-d[M_1]}{dt} = k_{11}[M_1]\sum[M_1^*] + k_{21}[M_1]\sum[M_2^*] \,

with \sum[M_x^*] the concentration of all the active centers terminating in monomer 1 or 2.

Likewise the rate of disappearance for monomer 2 is:

\frac{-d[M_2]}{dt} = k_{22}[M_2]\sum[M_2^*] + k_{21}[M_2]\sum[M_1^*] \,

Division of both equations yields:

\frac{d[M_1]}{d[M_2]} = \frac{[M_1]}{[M_2]} \left( \frac{k_{11}\frac{\sum[M_1^*]}{\sum[M_2^*]} + k_{21}} {k_{12}\frac{\sum[M_2^*]}{\sum[M_2^*]} + k_{22}} \right) \,

The ratio of active center concentrations can be found assuming steady state with:

\frac{d\sum[M_1^*]}{dt} = \frac{d\sum[M_2^*]}{dt} \approx 0\,

meaning that the concentration of active centres remains constant, the rate of formation for active center of monomer 1 is equal to the rate of their destruction or:

k_{21}[M_1]\sum[M_2^*] = k_{12}[M_2]\sum[M_1^*] \,

or

\frac{\sum[M_1^*]}{\sum[M_2^*]} = \frac{k_{21}[M_1]}{k_{12}[M_2]}\,



[edit] External links

  • copolymer equation applet @eng.utah.edu Link
  • copolymers @zeus.plmsc.psu.edu Link

[edit] References

  1. ^ Copolymerization. I. A Basis for Comparing the Behavior of Monomers in Copolymerization; The Copolymerization of Styrene and Methyl Methacrylate Frank R. Mayo and Frederick M. Lewis J. Am. Chem. Soc.; 1944; 66(9) pp 1594 - 1601; doi:10.1021/ja01237a052
  2. ^ Introduction to polymers R.J. Young ISBN 0412221705