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A world of plastic
How many different uses of plastic can you spot?
The word polymer comes from the Greek words poly (meaning many) and meros (meaning parts).
Polymers: Introduction
Polymer: High molecular weight molecule made up of a small repeat unit (monomer).
A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A
Monomer: Low molecular weight compound that can be connected together to give a poymer Oligomer: Short polymer chain Copolymer: polymer made up of 2 or more monomers
Making polymers
How are monomers turned into polymers?
Polymer Synthesis
Step-Growth polymerization (condensation reaction): Monomers react together to make small oligomers. Small oligomers make bigger ones, and big oligomers react to give polymers.
Chain growth is exponential Maximum molecular weight is obtained late in the reaction
Addition
Example Empirical formula How grows
Polystyrene No change from monomer. One monomer at a time
Condensation
Nylon Changes as byproduct (often water) is given off. Monomer + dimer, hexamer + octadecamer, etc.
Molecular weight
Synonym
Addition Polymerization
In* A Initiation In A*
Addition Polymerization
Propagation
A Initiation In A A* In*
Addition Polymerization
Propagation
A In* Initiation In A A A*
Addition Polymerization
A In* Initiation
nA
In
A A A A*
Propagation
In
A A A A A*
n
*A
*A A A A A
m
A A A A
m
In
A A A A A
n
In
A A A A A
n
In
A A A A A
n
A A A A A
m
B A A A A Disproportionation
m
Combination
MW
MW
0 % conversion 100
Ph C3H7 Li
n Ph
C4H9 Ph
n
Li+ Ph
C4 H9
Radical
n
PhCO2 Ph
PhCO2
Ph
Ph
PhCO2 Ph
Cationic
Ph
Ph Cl3Al OH2
n
H Ph HOAlCl3
Ph
H Ph
HOAlCl3
n
Ph
Addition polymerization
Polyethene (sometimes called polythene) is a polymer made from ethene. The process by which polyethene and other polymers is made is called addition polymerization. This is because many monomers (ethene molecules) are added together.
monomers
addition polymerization
polymer
Common Polyolefins
Monomer
Ethylene Polyethylene H3C
Polymer
CH3
n
Repeat unit
CH3
n
Ph Polystyrene Styrene Ph Ph Ph Ph
CH3
n
Ph
Ph
Ph
CH3
n
Cl
Cl
Cl
Cl
F2 C
Cl
F2 C
Cl
F2 C
Cl
C F2
C F2
C F2
C nF 2
C F2
C F2
CF3
Polymer
O H2 H2 O C C O H
n
Ester
O
4
HO 4 Adipic Acid
N H O
N 4 H Amide H N
H
n
H N H
n
OCN
H2 C
NCO
4,4-diisocyantophenylmethane O HO H N H2 C
Urethane linkage
Natural Polymers
Monomer Polymer
Isoprene Polyisoprene: Natural rubber
n
H OH HO HO HO OH H H -D-glucose
O H3N O Polyamino acid: protein H3N R1
H OH H OH Poly(-D-glycoside): cellulose O HO H HO H OH H OH
n
H N
O Rn+1
n
H N
O OH Rn+2
R Amino Acid
O O P O O O Base
DNA
O O P O O O O Base
OH Nucleotide Base = C, G, T, A
DNA
Cooked spaghetti is solid when cold, but soft when warm. The strands can slide past each other. It is the same with many polymers.
weak intermolecular forces these let the chains slide past each other
Plastics made of these polymers are stretchy and have a low melting point. They are called thermosoftening plastics.
Plastics made of these polymers cannot be stretched, are rigid and have a high melting point. They are called thermosetting plastics (or thermosets).
What makes plastics different? The properties of a plastics depend greatly on how the
polymer chains are arranged: branching chains make plastics light, soft and easy to melt (e.g. lowdensity polyethene) lined-up chains make plastics dense, rigid and harder to melt (e.g. highdensity polyethene).
Nylon-6,6
O Cl O NaOH
4
O Cl
O
4
Cl
H2N
NH2
Adipoyl chloride
1,6-Diaminohexane
N H
N H
O
4
HO
N H
N H
H
n
6 carbon diacid
6 carbon diamine
Nylon-6,6
Nylon-6,6
Since the reactants are in different phases, they can only react at the phase boundary. Once a layer of polymer forms, no more reaction occurs. Removing the polymer allows more reaction to occur.
Rodlike polymers are used for very high strength, liquid crystals, photonics, efficient viscosification and control of phase relations.
Rodlike because of linear backbone
N * S S N
n
23
The UK has 4,000 landfill sites and it is predicted that the largest of these will become full in less than 5 years.
Landfill is a convenient method of waste disposal but it is only designed to bury rubbish, not to break it down. Most plastics are made up of tightly bonded molecules that cannot be decomposed by micro-organisms. These will remain buried at landfill sites for thousands of years without rotting.
This is because the polymer chains become damaged or contaminated with food or other types of plastic.
What are biodegradable plastics? One of the problems with traditional plastics is that they do not
break down when thrown away. Biodegradable plastics are plastics that can be broken down. They are converted into carbon dioxide, water and minerals by micro-organisms. Biodegradable plastics are increasingly being used in carrier bags, bin bags and food packaging. Biodegradable plastics, such as polylactide, are plant-based polymers. They are often made from starch that has been modified to become more stable.
Glossary
biodegradable A substance that can be naturally
broken down by micro-organisms.