Addition Polymerization

Choose one:
Part 3: Monomers: The Double Bond
Part 4: The Mechanism of Addition Polymerization
Part 5: A Simulation of Addition Polymerization

Part 3: Monomers: The Double Bond

You know from your studies that a double bond is two pairs of electrons being shared by two atoms. This arrangement is fairly strong, but when other molecules - molecules that like to react with electrons - are near, one of these pairs of electrons is vulnerable to attack. One such attacking species is the free radical.

Below is an example of how a free radical forms (this one starts with peroxide, HOOH):
The peroxide molecule has an easy-to-break O-O single bond. Heat or light energy can break this O-O single bond ().

The single dot represents one electron from the O-O peroxide bond. The HO· fragments are the free radicals, and they are very unstable and reactive.

Free radicals are very reactive. When a free radical gets close to a double bond, one of the bonds is disrupted. One of the electrons in the double bond is attracted to the free radical. The double bond breaks, and a new single bond is formed ( ).

Notice that in forming this bond, one electron from the double bond is left alone. Thus, another (larger) free radical has been formed.

In Summary:
The double bond is a great place for a reaction to occur. The electrons are available here to make new bonds. Reactive species disrupt the double bond. We have seen a free radical attack a double bond, but cations (+ ions) and anions (– ions) also can attack double bonds.

By the way, we say that the free radical adds to the double bond. Get it? Addition polimarization.

Let's look at the steps involved in a typical addition polymerization.

Part 4: The Mechanism of Addition Polymerization

The formation of a polymer by addition polymerization is an example of a chain reaction. Once a chain reaction gets started, it is able to keep itself going. The three steps of this reaction to focus on are
how the reaction gets started (INITIATION)
how the reaction keeps going (PROPAGATION)
how the reaction stops (TERMINATION)

A Note About This Example:
There are various methods used to carry out addition polymerization chain reactions. The details vary according to the method used.

We will focus on a commonly used mechanism involving a free radical. Our example polymerization will combine ethylene (ethene) monomers (CH2=CH2), so our product will be polyethylene. (Polyethylene is used to make food wrap, milk jugs, garbage bags, and many other plastic products.)

--- How the reaction gets started ---

If you looked at Part 3 of this tutorial, you have already seen the first part of the initiation step of addition polimarization chain reaction. A peroxide molecule breaks up into two reactive free radicals. Light or heat can provide the energy needed for this process.

We can write an equation for this process:

The second part of initiation occurs when the free radical initiator attacks and attaches to a monomer molecule. This forms a new free radical, which is called the activated monomer.

We can write an equation for this process, too:

--- How the reaction keeps going ---

During a chain reaction, most of the time is spent in the propagation phase as the polymer chain grows. In the propagation phase, the newly-formed activated monomer attacks and attaches to the double bond of another monomer molecule. This addition occurs again and again to make the long polymer chain. ( )

Once again, we can write an equation for this reaction:

The "n" stands for any number of monomer molecules, typically in the thousands.

--- How the reaction stops ---

This chain reaction cannot go on forever. The reaction must terminate, but how? A growing polymer chain joins with another free radical. We watched a peroxide break up to form two radicals. It makes sense that two free radicals could join to make a stable bond.

The equation representing this step of the chain reaction can be written simply as:

Remember: The R and R' groups here can be the original free radicals, the growing polymer chains, or even one of each. Termination reactions can, however, be more complicated looking.

An Important Note:
Chemists can control the way a polymer does each of these steps by varying the reactants, the reaction times, and the reaction conditions.

The physical properties of a polymer chain depend on the polymer's average length, the amount of branching, and the constituent monomers.

This is an exciting and useful field of chemistry!

In Summary:
Recall the three steps in an addition polymerization chain reaction:
how the reaction gets started (INITIATION)
how the reaction keeps going (PROPAGATION)
how the reaction stops (TERMINATION)

Part 5: A Simulation of Addition Polymerization

In Part 4 of this tutorial, you saw that there are three steps in an addition polymerization chain reaction. You also saw that there are only two kinds of molecules in the chain reaction: the initiator molecule and the monomers. Polymerization begins at the initiator, and reaction continues until there are no more monomers to add to the growing polymer chain. The chain grows only at the reactive end, the end with the unpaired electron.

The simulation you will see displays this process graphically. Click on the button below to view the Simulation window. (If nothing happens, click here.)

The larger box in this window is the area where you'll see the polymerization of monomers, represented by black balls. The initiator molecules are in red. You input the number of initiators, press START, and the monomers will add onto the initiators linearly. As the average chain length increases, you'll see it displayed graphically in the smaller box. The graph is a bar graph of the average size of the polymer chain versus the reciprocal of the number of initiators (a red bar represents the active or most recent polymerization; a blue bar, the past polymerizations).

You may not see the full length of the chain, but the numbers you see in and below the graph are correct for the given number of initiators.

Some Assumptions:
First, we assume that the red initiator molecule is the activated monomer that you saw in Part 4. Second, we assume that there are only 200 monomers in the polymerization. In real life, the number of monomers are on the order of 1023. Despite the low number of monomers in the simulation, it does show the correct, real-life trend of how the number of initiators affects the average chain length. Third, polymerization is terminated when the monomers run out. There is no visual coupling of free radicals; there are as many polymers as there are initiator molecules.

View the simulation several times with different numbers of initiators to see a trend in the bar graph. The more initiators, the shorter the chains (if there is a constant number of monomers).

Addition polymerization is not the only mechanism by which polymerization can occur. Let's look at another.