THE CHEMISTRY

OF POLYMERS
A guide for A level students

KNOCKHARDY PUBLISHING
2008
SPECIFICATIONS
 KNOCKHARDY PUBLISHING

POLYMERS
INTRODUCTION
This Powerpoint show is one of several produced to help students understand
selected topics at AS and A2 level Chemistry. It is based on the requirements of
the AQA and OCR specifications but is suitable for other examination boards.
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be used for classroom teaching if an interactive white board is available.
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 POLYMERS
CONTENTS
• Prior knowledge
• Types of polymerisation
• Addition polymerisation
• Polymerisation of propene
• Condensation polymerisation
• Peptides
• Hydrolysis of peptides
 POLYMERS
Before you start it would be helpful to…

• know the functional groups found in organic chemistry

• know the arrangement of bonds around carbon atoms
• recall and explain electrophilic addition reactions of alkenes
 POLYMERISATION

General A process in which small molecules called monomers join

together into large molecules consisting of repeating units.

There are two basic types

ADDITION all the atoms in the monomer are used to form the polymer

CONDENSATION monomers join up the with expulsion of small molecules

not all the original atoms are present in the polymer
 ADDITION POLYMERISATION

• all the atoms in the monomer are used to form the

polymer

• occurs with alkenes

• mechanism can be free radical or ionic

 POLYMERISATION OF ALKENES
ADDITION POLYMERISATION

Preparation

Often by a free radical process involving high pressure, high temperature

and a catalyst. The catalyst is usually a substance (e.g. an organic peroxide)
which readily breaks up to form radicals which initiate a chain reaction.

Another catalyst is a Ziegler-Natta catalyst (named after the scientists who

developed it). Such catalysts are based on the compound TiCl4.
 POLYMERISATION OF ALKENES
ADDITION POLYMERISATION

Preparation

Often by a free radical process involving high pressure, high temperature

and a catalyst. The catalyst is usually a substance (e.g. an organic peroxide)
which readily breaks up to form radicals which initiate a chain reaction.

Another catalyst is a Ziegler-Natta catalyst (named after the scientists who

developed it). Such catalysts are based on the compound TiCl4.

Properties

Physical vary with reaction conditions (pressure, temperature etc).

Chemical based on the functional groups in their structure

poly(ethene) is typical; it is fairly inert as it is basically a
very large alkane. This means it is resistant to chemical
attack and non-biodegradable.
 POLYMERISATION OF ALKENES
ADDITION POLYMERISATION

Process • during polymerisation, an alkene undergoes an addition reaction with itself

• all the atoms in the original alkenes are used to form the polymer
• long hydrocarbon chains are formed
 POLYMERISATION OF ALKENES
ADDITION POLYMERISATION

Process • during polymerisation, an alkene undergoes an addition reaction with itself

• all the atoms in the original alkenes are used to form the polymer
• long hydrocarbon chains are formed

The equation shows the original monomer and the repeating unit in the polymer

n represents a ethene poly(ethene)

large number
MONOMER POLYMER
 POLYMERISATION OF ALKENES
ADDITION POLYMERISATION

The equation shows the original monomer and the repeating unit in the polymer

n represents a ethene poly(ethene)

large number
MONOMER POLYMER
 POLYMERISATION OF ALKENES
EXAMPLES OF ADDITION POLYMERISATION

ETHENE POLY(ETHENE)

PROPENE POLY(PROPENE)

CHLOROETHENE POLY(CHLOROETHENE)
POLYVINYLCHLORIDE PVC

TETRAFLUOROETHENE POLY(TETRAFLUOROETHENE)
PTFE “Teflon”
POLYMERISATION OF ALKENES
SPOTTING THE MONOMER
POLYMERISATION OF ALKENES
SPOTTING THE MONOMER
 POLYMERISATION OF PROPENE - ANIMATION
AN EXAMPLE OF ADDITION POLYMERISATION

PROPENE MOLECULES DO NOT ALWAYS ADD IN A REGULAR WAY

THERE ARE THREE BASIC MODES OF ADDITION

ISOTACTIC
SYNDIOTACTIC
ATACTIC
POLY(PROPENE)

ISOTACTIC
CH3 groups on same side
- most desirable properties
- highest melting point

SYNDIOTACTIC
CH3 groups alternate sided

ATACTIC
random
most likely outcome
 CONDENSATION POLYMERS

• monomers join up the with expulsion of small molecules

• not all the original atoms are present in the polymer

Examples polyamides (nylon) (kevlar)

polyesters (terylene) (polylactic acid)
peptides
starch

Synthesis reactions between diprotic carboxylic acids and diols

diprotic carboxylic acids and diamines
amino acids

ESTER LINK AMIDE LINK

 POLYESTERS - TERYLENE

Reagents terephthalic acid HOOC-C6H4-COOH

ethane-1,2-diol HOCH2CH2OH

Reaction esterification

Eliminated water

Equation n HOCH2CH2OH + n HOOC-C6H4-COOH ——> -[OCH2CH2OOC(C6H4)CO] n- + n H2O

 POLYESTERS - TERYLENE

Reagents terephthalic acid HOOC-C6H4-COOH

ethane-1,2-diol HOCH2CH2OH

Reaction esterification

Eliminated water

Equation n HOCH2CH2OH + n HOOC-C6H4-COOH ——> -[OCH2CH2OOC(C6H4)CO] n- + n H2O

Repeat unit — [-OCH2CH2OOC(C6H4)CO-] n —

Product poly(ethylene terephthalate) ‘Terylene’, ‘Dacron’

Properties contains an ester link

can be broken down by hydrolysis
the C-O bond breaks
behaves as an ester
biodegradable

Uses fabrics an ester link

 POLYESTERS – POLY(LACTIC ACID)

Reagent 2-hydroxypropanoic acid (lactic acid) CH3CH(OH)COOH

ALCOHOL CARBOXYLIC ACID

END END
 POLYESTERS – POLY(LACTIC ACID)

Reagent 2-hydroxypropanoic acid (lactic acid) CH3CH(OH)COOH

ALCOHOL CARBOXYLIC ACID

END END

Reaction esterification

Eliminated water

Equation n CH3CH(OH)COOH —> −[-OCH(CH3)CO-]n − + n H2O

Product poly(lactic acid)

Repeat unit — [-OCH(CH3)CO-] —

 POLYESTERS – POLY(LACTIC ACID)

Reagent 2-hydroxypropanoic acid (lactic acid) CH3CH(OH)COOH

ALCOHOL CARBOXYLIC ACID

END END

Product poly(lactic acid)

Properties contains an ester link

can be broken down by hydrolysis
the C-O bond breaks
behaves as an ester (hydrolysed at the ester link)
biodegradable
photobiodegradable (C=O absorbs radiation)

Uses waste sacks and packaging

disposable eating utensils
internal stitches
 POLYAMIDES – KEVLAR

Reagents benzene-1,4-diamine benzene-1,4-dicarboxylic acid

Repeat unit

Properties contains an amide link

Uses body armour

 POLYAMIDES - NYLON-6,6

Reagents hexanedioic acid hexane-1,6-diamine

HOOC(CH2)4COOH H2N(CH2)6NH2

Mechanism addition-elimination

Eliminated water

Equation n HOOC(CH2)4COOH + n H2N(CH2)6NH2 ——> -[NH(CH2)6NHOC(CH2)4CO] n- + n H2O

 POLYAMIDES - NYLON-6,6

Reagents hexanedioic acid hexane-1,6-diamine

HOOC(CH2)4COOH H2N(CH2)6NH2

Mechanism addition-elimination

Eliminated water

Equation n HOOC(CH2)4COOH + n H2N(CH2)6NH2 ——> -[NH(CH2)6NHOC(CH2)4CO] n- + n H2O

Repeat unit —[-NH(CH2)6NHOC(CH2)4CO-]n—

Product Nylon-6,6two repeating units, each with 6 carbon atoms

 POLYAMIDES - NYLON-6,6

Properties contains a peptide (or amide) link

can be broken down by hydrolysis
the C-N bond breaks
behave as amides
biodegradable
can be spun into fibres for strength

Uses fibres and ropes

 PEPTIDES

Reagents amino acids

Equation H2NCCH2COOH + H2NC(CH3)COOH ——> H2NCCH2CONHHC(CH3)COOH + H2O

Product peptide (the above shows the formation of a dipeptide)

Eliminated water

Mechanism addition-elimination
 PEPTIDES

Reagents amino acids

Equation H2NCCH2COOH + H2NC(CH3)COOH ——> H2NCCH2CONHHC(CH3)COOH + H2O

Product peptide (the above shows the formation of a dipeptide)

Eliminated water

Mechanism addition-elimination

Amino acids join together via an amide or peptide link

a dipeptide

2 amino acids joined dipeptide

3 amino acids joined tripeptide
many amino acids joined polypeptide
 HYDROLYSIS OF PEPTIDES

Hydrolysis
+ H2O ——> HOOCCH2NH2
+
HOOCCH(CH3)NH2

The acid and amine groups remain as they are

Hydrolysis is much quicker if acidic or alkaline conditions are used.

However, there is a slight variation in products.

 HYDROLYSIS OF PEPTIDES

Hydrolysis
+ H2O ——> HOOCCH2NH2
+
HOOCCH(CH3)NH2

The acid and amine groups remain as they are

Acid
hydrolysis + 2HCl ——> HOOCCH2NH3+Cl¯
+
HOOCCH(CH3)NH3+Cl¯

The acid groups remain as they are and the amine groups are protonated
 HYDROLYSIS OF PEPTIDES

Hydrolysis
+ H2O ——> HOOCCH2NH2
+
HOOCCH(CH3)NH2

The acid and amine groups remain as they are

Acid
hydrolysis + 2HCl ——> HOOCCH2NH3+Cl¯
+
HOOCCH(CH3)NH3+Cl¯

The acid groups remain as they are and the amine groups are protonated

Base (alkaline)
hydrolysis + 2NaOH ——> Na+ ¯OOCCH2NH2
+
Na+ ¯OOCCH(CH3)NH2

The acid groups become sodium salts and the amine groups remain as they are
 HYDROLYSIS OF PEPTIDES

Hydrolysis
+ H2O ——> HOOCCH2NH2
+
HOOCCH(CH3)NH2

The acid and amine groups remain as they are

Acid
hydrolysis + 2HCl ——> HOOCCH2NH3+Cl¯
+
HOOCCH(CH3)NH3+Cl¯

The acid groups remain as they are and the amine groups are protonated

Base (alkaline)
hydrolysis + 2NaOH ——> Na+ ¯OOCCH2NH2
+
Na+ ¯OOCCH(CH3)NH2

The acid groups become sodium salts and the amine groups remain as they are
 PROTEINS

• polypeptides with large relative molecular masses (>10000)

• chains can be lined up with each other
• the C=O and N-H bonds are polar due to a difference in electronegativity
• hydrogen bonding exists between chains

dotted lines ---------- represent hydrogen bonding

THE CHEMISTRY
OF POLYMERS
THE END

© 2009 JONATHAN HOPTON & KNOCKHARDY PUBLISHING