Polymers

Macromolecules, molecules composed of thousands of atoms, are called polymers (from the Greek for many parts). Polymers are made up of a large number of simpler units (monomers) bonded together. The molecular mass of some polymers can exceed one million amu! There are naturally occurring polymers (polysaccharides like starch and cellulose, proteins, and nucleic acids) and man-made polymers (elastomers, fibers, and plastics). Synthetic polymer production is a multi-billion dollar industry. There are more chemists working in the polymer industry than in any other field of chemistry. Each year over 14 million tons of polyethylene are manufactured in the United States alone (and thats just one polymer example). Plastics production world-wide has increased from 360,000 tons in 1940 to over 100,000,000 tons in 1990. The process of forming polymers is called polymerization. There are two different reaction types involved in producing synthetic polymers: 1) Chain-reaction polymerization (also called addition polymerization) ex. free radical type, cationic type, anionic type, coordination type 2) Step-reaction polymerization (also called condensation polymerization) Chain reaction polymerization In all types of chain-reaction polymerization, the basic process involves converting many units of a substituted-alkene (the monomer) into a chain of repeating substituted alkanelike units. ex.

(Teflon)

Some important chain-growth polymers and their uses are shown in the table below: Chain Growth Polymers and Their Uses Monomer Repeating Unit Polymer Name Uses ______________________________________________________________________ CH2 = CH2 CH2 CH2 polyethylene film, toys, bottles

CH2 = CH Cl

CH2

CH Cl

poly(vinyl chloride)

pipe, siding, flooring

CH2 = CH CH3

CH2

CH CH3

polypropylene

molded caps, margarine tubs

CH2 = CH

CH2

CH

polystyrene

egg cartons, hot drink cups

CH2 = CH CN

CH2

CH CN

poly(acrylonitrile) [Orlon, Acrilan]

rugs, blankets

CH2 = C CH3 COOCH3

CH2

CCH3 COOCH3

poly(methyl methacrylate) [Lucite, Plexiglas]

signs, skylights

Free Radical Polymerization

O O

initiator: a free radical from a source like peroxides

ex. -

alkene: requires a substituent that is able to stabilize the growing radical species by electron delocalization ex. alkyl groups (Note drawing below)

where R is the radical initiator and R is the electron-donating group reaction conditions: 1000-3000 atm pressure and 100-250oC temperature mechanism:

Branching in Polymer Chains If a hydrogen is abstracted from an interior carbon in a growing polymer chain, a branch grows off the chain at that point. For example, a butyl free radical can abstract a hydrogen from a hexyl polymer chain and then the 2o hexyl free radical formed can attack an ethene molecule to form a branched chain. The mechanism for chain branching is shown on the next page.

Long unbranched chains or chains with few branches produce high-density polymers like HDPE, high-density polyethylene. This type of polymer is semi-rigid and can be used in applications like semi-rigid plastic bottles.

Highly branched chains produce low-density polymers like LDPE, low-density polyethylene. This type of polymer is much more flexible and can be used for trash bags and dry-cleaning bags.

Free radical, anionic, and cationic chain-reaction polymerization schemes all have a tendency to branch extensively. This is a problem if a more dense, rigid plastic is desired. Later in the course we will discuss a coordination type polymerization with transition metals involved with organic compounds that can minimize the problem. Also later in the course, we will discuss step-reaction or condensation polymerization. This method is responsible for materials such as Nylon, Dacron (a clothing fabric), Mylar (magnetic recording tape), and Kevlar (bullet-proof vests). Cationic Polymerization initiator: an electrophile (Lewis acid) ex. sulfuric acid, BF3, AlCl3

alkene: requires an electron-donating group substituent (like an alkyl group) to stabilize the carbocation intermediate ex. propene, 2-methylpropene (isobutylene), styrene (Note drawing below)

where Y is the cationic initiator and R is an electron- donating group reaction conditions: many reactions occur at room temp. or below mechanism:

Anionic Polymerization initiator: a nucleophile (to form an anion as a propagating site)

..
ex. butyl lithium

-1

+1

CH3 - CH2 - CH2 - CH2

Li

or sodium amide (NaNH2)

..

alkene: requires an electron-withdrawing group substituent to stablilize the negativelycharged carbon atom intermediate ex. vinyl chloride or vinyl cyanide (Note drawing below)

where Z is the anionic initiator and G is an electron-withdrawing group reaction conditions: many reactions occur at room temp. or below mechanism:

An alkene with two electron withdrawing groups is especially susceptible to anionic polymerization. Even a moderate nucleophile can initiate the reaction. For example, super glue (methyl -cyanoacrylate) can be activated by the mild nucleophilic proteins of the skin to cause your fingers to be stuck together if the glue accidently gets on your fingers.

methyl -cyanoacrylate

(both CN and COOCH3 are electron withdrawing groups)

Anionic polymerization leads to what are called living polymers. After an initiation step, each time another monomer adds to the growing chain, another anion is generated allowing another monomer to be added. In this way the polymer chain grows. This adding of monomer after monomer is called propagation. In many cases, the only thing that stops the growth of the chain is that eventually there is no more monomer molecules left in the vessel to add remember though, one end of the chain is still an anion. If more monomer is added later, even years later, the polymerization process will begin again. In this sense, the polymer is still alive. This gives the scientist better control over the molecular mass desired for the polymer. Adding a substance like water can end the process because water reacts with the active site: the anion end of the polymer. Cationic polymer chains and freeradical polymer chains are generally killed when a monomer is exhausted. Cationic types are terminated by proton transfer from the polymer to the cation. Free radical types are terminated by radical recombination. If a mixture of two or more monomers is allowed to undergo polymerization, there is obtained a copolymer: a polymer that contains two or more kinds of monomeric units in the same molecule. For example:
CH3 CH2 CH CH3
initiator

CH2

C COOCH3

CH2

CH

CH2

CH COOCH3

Styrene

Methyl methacrylate

Through copolymerization there can be made materials with different properties than those of either homopolymer, and thus another dimension is added to the technology. Consider styrene, for example. Polymerized alone, it gives a good electric insulator that is molded into parts for radio, TV, and automotives. Copolymerized with butadiene (30%) adds toughness; with acrylonitrile (30%) increases resistance to impact and to hydrocarbons. If the butadiene is raised to 75%, the resulting polymer is the principal rubber substitute produced in the U.S. The monomer units can be distributed in various ways depending on the technique used. They can alternate along a chain, either randomly or with varying degrees of regularity. One interesting variation of these copolymerizations is the formation of block polymers. If a certain monomer runs out, a different monomer could be added to the vessel and polymerization will continue again. This creates a look like the following (where R is the initiating anion, A is the first monomer, and B is the new monomer):

Block arrangement:

R A A A A A A A B B B B B -1

Other typical monomer arrangements are the following: Random arrangement: Regular arrangement: R A B B A B A B B A A A B -1 R A A B B A A B B A A B B -1

Polymer plastics can be recycled. Plastics are labeled with a number code (1-7) that indicates the ease with which they can be recycled (the lower the number, the easier to recycle). The symbolism used looks like the following:

Recycling Code Numbers 1 2 3 4 5 6 7 PET HDPE V LDPE PP PS polyethylene terephthalate high-density polyethylene polyvinyl chloride low-density polyethylene polypropylene polystyrene all other plastics soft drink bottles, films milk and water jugs shampoo bottles, pipes shrink wrap, trash bags bottle caps, toys Styrofoam cups plastic lumber, playground equipment