POLIMER

Muslih Anwar, M.Sc

PELATIHAN OLIMPIADE KELAS XI SMA KESATUAN BANGSA

A world of plastic
How many different uses of plastic can you spot?

What are polymers?

Polymers are very large molecules made when hundreds of monomers join together to form long chains.

The word polymer comes from the Greek words poly (meaning many) and meros (meaning parts).

Plastics are synthetic polymers that can be shaped by heat or pressure.

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

Random copolymer: A-B-B-A-A-B-A-B-A-B-B-B-A-AB Alternating copolymer: A-B-A-B-A-B-A-B-A-B-A-B-AB Block copolymer: A-A-A-A-A-A-A-A-B-B-B-B-B-B-B-B

Making polymers
How are monomers turned into polymers?

Polymer Synthesis

There are two major classes of polymer formation mechanisms

Addition polymerization: The polymer grows by sequential addition of monomers to a reactive site
Chain growth is linear Maximum molecular weight is obtained early in the reaction

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

Wide range: can be very high

Chain growth polymerization

Low (except biopolymers)

Step growth polymerization

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

A* Chain Transfer New reactive site is produced

B A A A A Disproportionation
m

Combination

Termination Reactive site is consumed

MW

MW
0 % conversion 100

k propagation k ter mination

Types of Addition Polymerizations

Anionic
Li+ Ph

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

Step-Growth / condensation Polymerization

Stage 1 n n Consumption of monomer

Stage 2 Combination of small fragments

Stage 3 Reaction of oligomers to give high molecular weight polymer

Common Polyolefins
Monomer
Ethylene Polyethylene H3C

Polymer
CH3
n

Repeat unit

CH3 Polypropylene Propylene

CH3
n

CH3 CH3 CH3 CH3 CH3 CH3 CH3

Ph Polystyrene Styrene Ph Ph Ph Ph

CH3
n

Ph

Ph

Ph

Cl Poly(vinyl chloride) Vinyl Chloride

F2C CF2 Tetrafluoroethylene F2 C F2 C F2 C

CH3
n

Cl

Cl

Cl

Cl
F2 C

Cl
F2 C

Cl
F2 C

Cl

F3C Poly(tetrafluoroethylene): Teflon

C F2

C F2

C F2

C nF 2

C F2

C F2

CF3

Polyesters, Amides, and Urethanes Monomer

O HO2C Terephthalic acid CO2H HO Ethylene glycol OH Poly(ethylene terephthalate HO

Polymer
O H2 H2 O C C O H
n

Ester

O NH2 OH H2N 4 1,6-Diaminohexane Nylon 6,6 HO

O
4

HO 4 Adipic Acid

N H O

N 4 H Amide H N

H
n

O HO2C Terephthalic acid CO2H H2N 1,4-Diamino benzene NH2 Kevlar HO

H N H
n

OCN

H2 C

NCO

4,4-diisocyantophenylmethane O HO H N H2 C

OH HO Spandex Ethylene glycol O H2 H2 H N O C C O H

n

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

oligonucleic acid DNA

DNA

What are thermosoftening plastics?

What do polymer chains and spaghetti have in common?

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.

What are thermosetting plastics?

Some polymer chains cannot slide past each other. strong intermolecular forces (cross-links) these hold the chains firmly in place

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

Adipoyl chloride in hexane Nylon 6,6

HO

N H

N H

H
n

6 carbon diacid

6 carbon diamine

Diamine, NaOH, in H2O

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.

Adipoyl chloride in hexane Nylon 6,6 Diamine, NaOH, in H2O

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

Used in stealth bomber ? Maybe. Rodlike because of helix

23

Why is this important?

Tacticity affects the physical properties

Atactic polymers will generally be amorphous, soft, flexible materials Isotactic and syndiotactic polymers will be more crystalline, thus harder and less flexible

Polypropylene (PP) is a good example

Atactic PP is a low melting, gooey material Isoatactic PP is high melting (176), crystalline, tough material that is industrially useful Syndiotactic PP has similar properties, but is very clear. It is harder to synthesize

How much waste plastic?

In the UK, 3.5 million tonnes of plastic packaging is thrown away each year! There are three ways to dispose of waste plastics: landfill incineration (burning) recycling Each method of disposal has its own advantages and disadvantages. Why has the issue of dealing with waste plastic in a cheap and environmentally-friendly way become more important?

What happens to plastics in landfill sites?

Plastic bags are a major source of waste at landfill. British shoppers use over 8 billion of them a year!

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.

How are plastics identified for recycling?

Most plastic products carry a symbol that shows which type of polymer they are made from. Usually, the only types of plastic to be recycled are PET, PVC and HDPE. Many plastic items look and/or feel similar to each other but they are actually made from different materials, e.g. margarine tubs (polystyrene) and plant pots (polypropene). If different polymers are mixed together during recycling, it can reduce the quality and value of the final recycled plastic.

Recycling symbols for plastics

What is the effect of recycling plastics?

Recycling plastic uses less water and energy resources than in producing new plastics, and produces fewer greenhouse gases. One problem with recycling, however, is that is reduces the strength and versatility of the plastic over time.

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.

cross-link A chemical bond that joins one polymer chain

to another.

monomer A molecule that is the building block of a

polymer.

polymer A long chain molecule formed from many

monomers joined together.

polymerization The reaction used to convert

monomers into a polymer.

thermosetting A type of plastic that is hard, rigid and

has a high melting point.

thermosoftening A type of plastic that is flexible,

stretchy and has a low melting point.