THE CHEMISTRY OF POLYMERS A guide for A level students KNOCKHARDY PUBLISHING 2015 SPECIFICATIONS

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. Individual students may use the material at home for revision purposes or it may be used for classroom teaching if an interactive white board is available. Accompanying notes on this, and the full range of AS and A2 topics, are available from the KNOCKHARDY SCIENCE WEBSITE at... Navigation is achieved by... either clicking on the grey arrows at the foot of each page orusing the left and right arrow keys on the keyboard POLYMERS KNOCKHARDY PUBLISHING

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 POLYMERS

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 POLYMERISATION

all the atoms in the monomer are used to form the polymer occurs with alkenes mechanism can be free radical or ionic 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 TiCl 4. 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 TiCl 4. Properties Physicalvary 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

POLYMERISATION OF ALKENES 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 ADDITION POLYMERISATION

POLYMERISATION OF ALKENES 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 ADDITION POLYMERISATION The equation shows the original monomer and the repeating unit in the polymer ethene poly(ethene) MONOMER POLYMER n represents a large number

POLYMERISATION OF ALKENES ADDITION POLYMERISATION The equation shows the original monomer and the repeating unit in the polymer ethene poly(ethene) MONOMER POLYMER n represents a large number

POLYMERISATION OF ALKENES ETHENE EXAMPLES OF ADDITION POLYMERISATION PROPENE TETRAFLUOROETHENE CHLOROETHENE POLY(ETHENE) POLY(PROPENE) POLY(CHLOROETHENE) POLYVINYLCHLORIDE PVC 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 ISOTACTIC SYNDIOTACTIC ATACTIC PROPENE MOLECULES DO NOT ALWAYS ADD IN A REGULAR WAY THERE ARE THREE BASIC MODES OF ADDITION

POLY(PROPENE) ISOTACTIC CH 3 groups on same side - most desirable properties - highest melting point SYNDIOTACTIC CH 3 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 Examplespolyamides(nylon)(kevlar) polyesters(terylene) (polylactic acid) peptides starch Synthesis reactions between diprotic carboxylic acids and diols diprotic carboxylic acids and diamines amino acids ESTER LINKAMIDE LINK

POLYESTERS - TERYLENE Reagentsterephthalic acidHOOC-C 6 H 4 -COOH ethane-1,2-diolHOCH 2 CH 2 OH Reactionesterification Eliminatedwater Equation n HOCH 2 CH 2 OH + n HOOC-C 6 H 4 -COOH ——> -[OCH 2 CH 2 OOC(C 6 H 4 )CO] n - + n H 2 O

POLYESTERS - TERYLENE Reagentsterephthalic acidHOOC-C 6 H 4 -COOH ethane-1,2-diolHOCH 2 CH 2 OH Reactionesterification Eliminatedwater Equation n HOCH 2 CH 2 OH + n HOOC-C 6 H 4 -COOH ——> -[OCH 2 CH 2 OOC(C 6 H 4 )CO] n - + n H 2 O Repeat unit— [-OCH 2 CH 2 OOC(C 6 H 4 )CO-] n — Productpoly(ethylene terephthalate)‘Terylene’, ‘Dacron’ Propertiescontains an ester link can be broken down by hydrolysis the C-O bond breaks behaves as an ester biodegradable Usesfabricsan ester link

POLYESTERS – POLY(LACTIC ACID) Reagent2-hydroxypropanoic acid (lactic acid)CH 3 CH(OH)COOH CARBOXYLIC ACID END ALCOHOL END

POLYESTERS – POLY(LACTIC ACID) Reagent2-hydroxypropanoic acid (lactic acid)CH 3 CH(OH)COOH Reactionesterification Eliminatedwater Equation n CH 3 CH(OH)COOH —> −[-OCH(CH 3 )CO-] n − + n H 2 O Productpoly(lactic acid) Repeat unit— [-OCH(CH 3 )CO-] — CARBOXYLIC ACID END ALCOHOL END

POLYESTERS – POLY(LACTIC ACID) Reagent2-hydroxypropanoic acid (lactic acid)CH 3 CH(OH)COOH Productpoly(lactic acid) Propertiescontains 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) Useswaste sacks and packaging disposable eating utensils internal stitches CARBOXYLIC ACID END ALCOHOL END

POLYAMIDES – KEVLAR Reagentsbenzene-1,4-diamine benzene-1,4-dicarboxylic acid Repeat unit Propertiescontains an amide link Usesbody armour

POLYAMIDES - NYLON-6,6 Reagents hexanedioic acidhexane-1,6-diamine HOOC(CH 2 ) 4 COOH H 2 N(CH 2 ) 6 NH 2 Mechanismaddition-elimination Eliminatedwater Equation n HOOC(CH 2 ) 4 COOH + n H 2 N(CH 2 ) 6 NH 2 ——> -[NH(CH 2 ) 6 NHOC(CH 2 ) 4 CO] n - + n H 2 O

POLYAMIDES - NYLON-6,6 Reagents hexanedioic acidhexane-1,6-diamine HOOC(CH 2 ) 4 COOH H 2 N(CH 2 ) 6 NH 2 Mechanismaddition-elimination Eliminatedwater Equation n HOOC(CH 2 ) 4 COOH + n H 2 N(CH 2 ) 6 NH 2 ——> -[NH(CH 2 ) 6 NHOC(CH 2 ) 4 CO] n - + n H 2 O Repeat unit—[-NH(CH 2 ) 6 NHOC(CH 2 ) 4 CO-] n — ProductNylon-6,6two repeating units, each with 6 carbon atoms

POLYAMIDES - NYLON-6,6 Propertiescontains 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 Usesfibres and ropes

PEPTIDES Reagentsamino acids Equation H 2 NCCH 2 COOH + H 2 NC(CH 3 )COOH ——> H 2 NCCH 2 CONHHC(CH 3 )COOH + H 2 O Productpeptide (the above shows the formation of a dipeptide) Eliminatedwater Mechanismaddition-elimination

PEPTIDES Reagentsamino acids Equation H 2 NCCH 2 COOH + H 2 NC(CH 3 )COOH ——> H 2 NCCH 2 CONHHC(CH 3 )COOH + H 2 O Productpeptide (the above shows the formation of a dipeptide) Eliminatedwater Mechanismaddition-elimination Amino acids join together via an amide or peptide link 2 amino acids joineddipeptide 3 amino acids joinedtripeptide many amino acids joinedpolypeptide a dipeptide

HYDROLYSIS OF PEPTIDES Hydrolysis + H 2 O ——> HOOCCH 2 NH 2 + HOOCCH(CH 3 )NH 2 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 + H 2 O ——> HOOCCH 2 NH 2 + HOOCCH(CH 3 )NH 2 The acid and amine groups remain as they are Acid hydrolysis + 2HC l ——> HOOCCH 2 NH 3 + C l ¯ + HOOCCH(CH 3 )NH 3 + C l ¯ The acid groups remain as they are and the amine groups are protonated

HYDROLYSIS OF PEPTIDES Hydrolysis + H 2 O ——> HOOCCH 2 NH 2 + HOOCCH(CH 3 )NH 2 The acid and amine groups remain as they are Acid hydrolysis + 2HC l ——> HOOCCH 2 NH 3 + C l ¯ + HOOCCH(CH 3 )NH 3 + C l ¯ The acid groups remain as they are and the amine groups are protonated Base (alkaline) hydrolysis + 2NaOH ——> Na+ ¯OOCCH 2 NH 2 + Na+ ¯OOCCH(CH 3 )NH 2 The acid groups become sodium salts and the amine groups remain as they are

HYDROLYSIS OF PEPTIDES Hydrolysis + H 2 O ——> HOOCCH 2 NH 2 + HOOCCH(CH 3 )NH 2 The acid and amine groups remain as they are Acid hydrolysis + 2HC l ——> HOOCCH 2 NH 3 + C l ¯ + HOOCCH(CH 3 )NH 3 + C l ¯ The acid groups remain as they are and the amine groups are protonated Base (alkaline) hydrolysis + 2NaOH ——> Na+ ¯OOCCH 2 NH 2 + Na+ ¯OOCCH(CH 3 )NH 2 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 © 2015 JONATHAN HOPTON & KNOCKHARDY PUBLISHING