After studying this Unit, you will be able to + explain the terms - monomer, polymer and polymerisation and appreciate their importance: + distinguish between various classes of polymers and different types of polymerisation processes: © appreciate the formation of polymers from mono- and bi- functional monomer molecules; ‘+ describe the preparation of some important synthetic polymers and their properties: ‘+ appreciate the importance of polymers in daily life. 15.1 Classification of Polymers *“Copolymertsation has been used by nature in polypeptides which ‘may contain as many as 20 different amino acids. Chemists are still far behind”, Do you think that daily life would have been easier and colourful without the discovery and varied applications of polymers? ‘The use of polymers in the manufacture of plastic buckets, cups and saucers, children’s toys, packaging bags, synthetic clothing materials, automobile tyres, gears and seals, electrical insulating materials and machine parts has completely revolutionised the daily term polymer is defined as very large molecules having ‘These are also referred “high molecular mass (107-107) (o 2ERSMOISEWIES, which are formed by joining of ‘There are several ways of classification of polymers based ‘on some special considerations. One of the common. classifications of polymers is based’ on Souree from which polymer is derived. Under this type of classification, there are three sub categories, | Natural polymers These polymers. are (GRIST Anis? Examples are (SSCEIOSErStareSOmEreSiS ‘and rubber, 2020-2115.2 Types of Dolymerisation Reactions 15.2.1 Addition Polymerisation or Chain Growth Polymerisation 15.2.1.1 Mechanism of Addition Polymerisation Chemistry side Cellulose derivatives as @ellulosé acetate (rayon) and cellulose (GHWRIE etc. are the usual examples of this sub category. A variety of ‘synthetic ‘fibres. nd pre examples of man-made polymers extensively used in daily life as well as in industry. ed molecular Polymers can also be cl ‘forces or Intext_Questions 15.1 Wha are polymers ? ‘There are and In this type of polymerisation, the molecules of the same monomer or diferent monomers add together on a large scale to form a polymer. The Saaerageaes ‘This mode of polymerisation leads to an increase in chain length and chain growth can take place through the formation of either free radicals or ionic species. However, the free radical governed addition or chain growth polymerisation is the most common mode. 1. Free radical mechanism A variety of alkenes or dienes and their derivatives are polymerised in the presence of a free radical generating (ii? | (i 7S0@ benzoyl peroxide, acetyl peroxide, tert-butyl peroxide, ete) For exsunple._ the polymerisation of ethene to polythene consists of heating or exposing to light a mixture of ethene with a small amount of benzoyl, (peroxide initiator, The process starts with the addition of phenyl free radical formed by the peroxide to the ethene double bond thus generating a new and larger free radical. This step is called @Hi8 (GUBEGRGIEIED As this radical reacts with another molecule of ethene, another bigger sized radical is formed. The repetition of this sequence with new and bigger radicals carries the reaction forward and the step is termed as GSS SFOPSZSERENSISP Ultimately, at some stage the product radical thus formed reacts with another radical to form the polymerised product, This step is called the CSE Eiat SEED) ‘The sequence of steps involved in the formation of polythene are depicted as follows: Chain initiation steps Rat 2 oH, -C-08-C-c,, ——> 2¢,,-C-6 ——> 26,4, Benzoyl peroxide Phenyl radical C\H+ CH=CH, ———> C,H,-CH,- CH, 2020-21C\H,-CH,~ CH, + CH, = CH, ———> C,H,-CH,- CH, CH, - CH, | Cul -4¢CH,- CH,4,0H1,- 2H, For termination of the long chain, these free radicals can combine in different ways to form polythene. One mode of termination of chain is shown as under: C,H, + CH,- CH,+; CH, - CH, . |. > C\H,- CH, - CH,4, CH, ~ CH,~CH,-CH,+CH,- CH,C,H, C,H CH,~ CH,4, CH, - CH, Polythene for example liscussed above is a which is formed by is an example of formed by addition polymerisation. Tr nCH,= CH - CH = CH, +n C,H,CH=CH, ———> ~(CH,-CH=CH-CH,-CH-CH)}; 1, 3-Butadiene Styrene Butadiene-styrene copolymer (Buna - S) 18.2.1.2 (a}Polythene Some Important Addition Polymers These are capable of repeatedly (hardeniig/on coolingjand are thus There are two types of polythene as given below: ao Itis obtained by the GHRMEEN uncer atmospheres at a in the presence of ETS Ta TTS PENI CIATAOR (GEEED The low density polythene (LDP) is obtained (hrough the free radical addition and H-atom abstraction es as shown below. a ee Low density polythene is and (6ugRybEE Texte an: SOOEOMEUGOEOESRAIA Hence: used 1d) Polyme 2020-21 LExample_15.1 Solution hemistry his Ee in the ‘of squeeze bottles. toys and flexible pipes. (i) CT ENERED 1t is formed when addition in the presence of a High density polythene (HDP) thus produced, consists of linear molecules as shown below and has a high density due to ‘lose packing. Such polymers are also called| High density polymers are alsé and NN NS OS Se Ne aN ee (> Wolytetraftuoroethene (Teflon) Teflon is manufactured| vith af It a Scie Gert ana It is used in making id also used for ( Catalyst NCR.=CE gi pressure” £%~ CF J, ‘Tetraluoroethene ‘Teflon (. Polyaerutonterite ‘The addition in presence of a Jeads to the formation of polyacrylonitrile, oN Polymerisation i nc Polrmenisation, fcr, CH CH= CHEN gmae tant FoR oH Acrylonitrile Polyacrylonitile Polyacrylonitrile is used_as a Is +CH,-CH(C,H,) +, a homopolymer or a copolymer? It is a homopolymer and the monomer from which it is obtained is styrene C,H,CH = CH,. 2020-2115.2.2 Condensation Polymerisation or Step Growth Polymerisation This type of polymerisation generally involves a ‘These polycondensation reactions m the Sari Be) to the formation of (ioc sess In these reactions, produces a distinct functionalised species and is independent of each other, this process is also called as step growth polymerisation; ‘The formation off by the interaction of @EEa53 is an example of this type of polymerisation. Oo Oo i r nHOH,C-CH,OH + nt00c-<_)- coon —+ focu,-cH-0-6-<_Y- CF Ethylene glycol Terephthalle acd ene or daeron (Ethane-1, 2 - diol) (Benzene-1,4 - di Teryl 7 oe | © a3 Some Important Th i : on Goad waa hese polymers possessing({@iiGGMMGKAZES:re important eoiemer examples of S¥fithétie"fibFés and are termed as The iv general method of preparation consists of the or or Nylons @ QF 1. is prepared by the condensation polymerisation of under high pressure and at high temperature. Tee ee og nHOOC(CH,,COOH +n HN (CH),NE, Age fiend}, Nylon 6,6 +nHO It posses: Nylon 6. 6 is fibre forming solid. high tensile ‘This characteristic can_be attributed to the Strong earners tae iia ipdngen boning ‘These strong forces also lead to close packing of chains and thus impart Nylon 6, 6 is used in making QS SSUES SHES and in textile industry. (i) CHO 11s obtained by heat AAT at a high temperature. dd Polyme 2020-21H 1 H, ae ceo Ny a; | HC CH, 833. 543K_, C -(CH)),- N oe aaa Hc —CH, = Nylon 6 is used for the manufacture of [2569 and ropes. >) CaS These are the polycondensation products of (79 ‘is the best known example of polyesters. It is manufactured by heating a mixture of (8 (GUSGIGNANGREPINNANGA):« 420 to 460K In the presence of earlier. Dacron fibre (terylene) is and is used entre mates sey primes ee ©) ‘These are obtained by the condensation reaction of in the presence o The reaction starts with the initial formation of (GERBEEED (0 form compounds having rings joined to cach Ofer Lead Th TD could be a Tinea product + on ou on ou . CH,OH CHOH HOH, CHOH +cH,o —Ety + + oH Gi.0n Gu,0n OH OH OH OH 4 on ont, —cH, Crore tr ~ Novolac to form an 2020-21ou On ou HC: ‘CH, CH, cH, — CH, CH, CH, HC CH, CH, ‘CH, OH OH OH Bakelte (@) Melamine formaldehyde polymer ie formed by the condensation polymerisation fae TT x N. HNSAS NH, Han AY nutcH,o11 ie + HCHO ———> ir NH, NH, Melamine Formaldehyde oo Polymerisation HN. as .NH-CH, Foye Y NH Melamine polymer ltis used in the oie ace. 15.2 Write the names of monomers of the following polymers: t wt 2 g 7 0 fx- (cHy),-N-C-(cHy,-C} + &-(cry,-n + Ww ftor.-cr. F, 15.3 Classify the following as addition and condensation polymers: Terylene, Bakelite, Polythene, Teflon. 15.2.3 Copolymerisation is a polymerisation reaction in which a mixture of Copolymerisation more than one monomeric species is allowed to polymerise and form ‘a copolymer, The copolymer can be made not only by @IEEGZESw) Dut by St@pRFewhi/polMMeRSALONTalso, It contains multiple units of each monomer used in the same polymeric chain, 1d Polymers 2020-21 CFor example, ‘an form ‘a. copolymer. Ankur of TTT TTT 1, 3-Butadiene Styrene Butadiene - styrene copolymer Copolymers have properties quite different from homopolymers. For camp, TAT TST 's quiestough 2c is al Ttis used for the manufacture of, 15.2.4 Rubber @ Natural rubber Rubber is 2 EAT and possesses elastic properties. It is also termed as elastomeric polymers, the are introduced in between the chains, which Rubber has a variety of uses. This his found in (sii) Natural _rubber_may be considered as a (SOP ASCLANSMTAMIEH) arc is also called as 4 polyisoprene._ H HC. 2 HCY UH 6, cH cu, : mH SCH Ne ca Oe Re? Hy Natural rubber cH, i The cis-polyisoprene molecule consists of various chains held H,C-C-CH-CH, together by and has a Isoprene (Structure) Thus, elastic properties. Natural rubber becomes and It K) and shows| ‘a process of This process consists of (5 (ACTUEMMIGHE anc an appropriate additive Chemistry sy 2020-21at a (peFALFE FARE EUVEERTS7SIKAGTANS I On vulcanisation and thus the 5% of sulphur is used as a The probable structures of vuleanised rubber molecules are depicted below: cH, CH, —O- CH ~CH, = ss s i CH, - CH ~CH, = CH= CH = CH CH, cH, Synthetic rubber is any Wuleanisable Fubber Ke polymer, which is However, it ‘hus, synthetic rubbers are’ Preparation of Synthetic Rubbers ae a cl n CH,-C-C Chloroprene 2-Chloro-1, 3-buta-1, 3-diene It has It is used for manufacturing > Buna=N You have already studied about Buna-S, in Section 15.1.3, Buna -N is obtained by the copolymerisation o GGUREIGRAD 11 the presence of a cn cN L, Copolymerisation I H+ ncH,cH Lepelmertsation, Foy c-cH-CH,-CH,-CH 1LsButadiene Antonie | 11, Poomereatin, Fou, beci-cus, Neoprene H-CH=¢ Buna-N {cis resistant tothe action of petro, lubricating oll and organic solvents. ICs used in making TTS idly Polyme 2020-2115.5 Arrange the following polymers in increasing order of their intermolecular forces. Nylon 6.6, Buna-S, Polythene. Intext_Questions 15.4 Explain the difference between Buna-N and Buna-S. 15.3 Molecular ‘Polymer properties are closely related to their molecular mass, size Mass of ‘and Structure, The growth of the polymer chain during their ass | Seuthesis = dependent upon the availability of the monomers i Polymers the reaction mixture. Thus, a Re Se Sn ERE 15.4 Biodegradable Dolymers (GegradationEprocesse9 and are rept ‘cause acute environmental problems and remain undegraded for quite a long time. In view of the general awareness and concern for the problems created by the polymeric solid wastes, certain (TEGO ave been designed and Uieveloped. These polymers contain fanetional groups similar {© {be anal ough oant le Bepatoner are one of the important classes of Waentate eee Some important examples are ven belo + Poly Bhydroxpbutyrate = co:B-hydroxy valerate (PHBY) It is obtained by the copolymerisation of AD 71150 1s usec in SERED ‘packaging, orthopaedic devices and in controlled release GHEEED PHBV undergoes GAOETAIMEEACAMOR 1n-the environment. ya OH I CH-CH-CH,COOH + CH,-CH,-CH-CH,-cooH —> {0- CH-CH,-C-O-CH-CH, c} CH = CHCH, 3-Hydroxybutanoic acid —_3-Hydroxypentanoie acid PHBV -fNglon2=ngton"6 1s on TSAI and is (Biodegradable Can you write the structure of this copolymer? 2020-215 Dolymers of Besides. the polymers already discussed, some other © ‘ql commercially important polymers along with their structures and ae uses are given below in Table 15.1. Importance Table 1541: Some Other Commercially Important Polymers Ree ao Cts Perea Polypropene Propene I Manufacture of ropes, toys, pipes, fibres, ete. Polystyrene Styrene [As insulator, wrapping material, manufacture of toys, radio and television cabinets. Polyvinyl chloride | Vinyl chloride I ‘Manufacture of rain (pve) coats, hand bags, vinyl flooring, water pipes. Urea-formaldehyle | (a) Urea For making unbreak- Eni-co-nt-cn, } Resin (b) Formaldehyde able cups and laminated sheets. Glyptal (a) Ethylene glycol] €ocr,-cu,00c. co}, |Manufacture of (b) Phthalic acid paints and lacquers. Bakelite (a) Phenol ee For making combs, (b) Formaldehyde te we ,_|electrical switches, handles of utensils and computer discs. Summary Polymers are defined as high molecular mass macromolecules, which consist of repeating structural units derived from the corresponding monomers. These polymers may be of natural or synthetic origin and are classified in a number of ways. In the presence of an organic peroxide initiator, the alkenes and their derivatives undergo addition polymerisation or chain growth polymerisation through a free radical mechanism. Polythene, teflon, orlon, etc. are formed by addition polymerisation of an appropriate alkene or its derivative. Condensation polymerisation reactions are shown by the interaction of bi - or poly functional monomers containing ~ NH, ~ ‘OH and - COOH groups. This type of polymerisation proceeds through the elimination of certain simple molecules as H,O, CH,OH, etc. Formaldehyde reacts with phenol and melamine to form the corresponding condensation polymer products. The condensation debits Polym 2020-21polymerisation progresses through step by step and is also called as step growth polymerisation. Nylon, bakelite and dacron are some of the important examples of condensation polymers. However, a mixture of two unsaturated monomers exhibits copolymerisation and forms a co-polymer containing multiple units of each monomer, Natural rubber is a cis 1, 4-polyisoprene and can be made more tough by the processof ‘vuleanisation with sulphur. Synthetic rubbers are usually obtained by copolymerisation of alkene and 1, 3 butadiene derivatives. In view of the potential environmental hazards of synthetic polymeric wastes, certain biodegradable polymers such as PHBV and Nylon-2- Nylon-6 are developed as alternatives. Cyercises 15.1 15.2 15.3 15.4 15.5 15.6 15.7 15.8 15.9 15.10 15.11 15.12 15.13 15.14 15.15 15.16 15.17 15.18 Explain the (erms polymer and monomer. What are natural and synthetic polymers? Give two examples of each type. Distinguish between the terms homopolymer and copolymer and give an example of each, How do you explain the functionality of a monomer? Define the term polymerisation. Is ( NH-CHR-CO ),, a homopolymer or copolymer? Why do elastomers possess elastic properties? How can you differentiate between addition and condensation polymerisation? Explain the term copolymerisation and give two examples, Write the free radical mechanism for the polymerisation of ethene. Define thermoplastics and thermosetting polymers with two examples of each. Write the monomers used for getting the following polymers. @ Polyvinyl chloride (i) Teflon (i) Bakelite Write the name and structure of one of the common initiators used in free radical addition polymerisation, How does the presence of double bonds in rubber molecules influence their structure and reactivity? Discuss the main purpose of vuleanisation of rubber. What are the monomerle repeating units of Nylon-6 and Nylon-6,6? Write the names and structures of the monomers of the following polymers: ( Buna-S (i) Buna-N (ii) Dacron (iv) Neoprene Identify the monomer in the following polymeric structures. 0 £ dicen) ¢-ni-(eny,-wu Chemistry sdebdly 2020-21a 15.19 How is dacron obtained from ethylene glycol and terephthalic acid ? 15.20 What is a biodegradable polymer ? Give an example of a biodegradable aliphatic polyester. Answers of Some Intext Questions 15.1 Polymers are high molecular mass substances consisting of large numbers of repeating structural units. They are also called as macromolecules. Some examples of polymers are polythene, bakelite, rubber, nylon 6, 6, etc. 15.2 (i) Hexamethylene diamine and adipic acid, () Caprolactam. (iil) Tetrafluoroethene. 15.3 Addition polymers: Polyvinyl chloride, Polythene. Condensation polymers: Terylene, Bakelite. 15.4 Buna-N 1s a copolymer of 1,3-butadiene and acrylonitrile and Buna-S is a copolymer of 1,3-butadiene and styrene. 15.5 In order of increasing intermolecular forces. Buna-S, Polythene, Nylon 6,6. 2020-21Note Chemistry sdefiéy 2020-21