Polymer Synthesis

Step growth polymerization: slow building up of chains in a step-wise fashion example: Polyester condensation reaction Addition or Chain polymerization: chains grow at one end by the sequential addition of monomers example: Free radical polymerization of Poly(ethyl acrylate)

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Step growth polymerization: Example Polyester condensation reaction

the repeat unit in the polymer has a different molecular formula than the monomers as the result of condensation of certain groups (often as water) monomers, dimers, trimers etc may all react togetherjust need the appropriate groups to meet in space

ester group
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Polymers from stepwise polymerization

GCH 6101- Polymer Synthesis

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Polymers from stepwise polymerization

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Addition polymerization: Example: Free radical polymerization of poly(ethyl acrylate)

3 major steps in the reaction: initiation, propagation and termination Initiation includes: Formation of free radical Addition of first monomer Note: the active center is at the opposite end of the chain to the initiator unit, R.
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Addition polymerization: Example: Free radical polymerization of poly(ethyl acrylate)

Propagation: many monomers are added sequentially and very rapidly

Note: the active center is always at the opposite end of the chain to the initiator unit, R.
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Addition polymerization: Example: Free radical polymerization of poly(ethyl acrylate)

Termination: Two growing chains react with each other either by combination or disproportionation. In combination the two chains join together to form a longer chain. In disproportionation a hydrogen is transferred from one chain to another.

Note: No active center exists, therefore the reaction stops.

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Polymers from addition polymerization

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Probability theory
We can use probability theory and knowledge about the reaction mechanism to find information about the molecular structure of a polymer Basic tools of probability theory: Probability that event A will occur, P(A)
P(A ) = NA number of A events occuring = N total number of events occuring

Probability that event A will occur if B has already occurred, P(A B) Probability that both A and B will occur, P(A,B)
P(A B) = P(A, B) P(B)

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Probability theory continued

Bayes theorem:
P(A B) = P(B A )P(A ) P(B)

If events A and B are statistically independent then:

P(A, B) = P(A ) P(B)

This means: P(A B) = P(A )

P(B A ) = P(B)

If there are N possible events then: P(i ) = 1

i =1

The probability that an event other than A occurs:

P A C = 1 P(A )

( )

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Example
Consider a system of N polymer chains If we can grab a chain only by its end, the probability that we grab a chain with molecular weight M is n(M) If we can grab a chain by any backbone bond, the probability that we grab a chain with molecular weight M is w(M). (Note we are working with discrete molecular weight distributions instead of continuous distributions) Explain this using probability theory.

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