" (CH=CH) —> Cir CH>, Polyethylene, PE” krone) Polymer where nis degree of polymerization, itcan be 10" or more. 2.1. Functionality Functionality means the rumber of bonding sites in a monomer. The double bond in vinyl monomers (CH, = CHX) can be considered as a site for two free valencies. When the double bond is broken, two single bonds become available for combination. (CH, = CHX —+ ...CH,-CHX. Thus, vinyl monomers can be considered as bifunctional because they have {wo reactive (or bonding sites. Fora substance to act asa monomer, it must have at least two reactive (or bonding) sites. Functionality and structures of polymers : () When the functionality of monomer is two, linear or straight-chain polymer molecule is formed. Examples of Bifunctional monomers. All vinyl monomers, Hexanatiylone di amine, Adipic acid, Terephthalic acid, Ethylene glycol, Amino-acid, etc (2 When te fuectionaliy of monomer i three, thre dimensional network polymer: Examples of Trifunctional monomers. Phenol, Melamine, etc. (ii) When a trifunctional monomer is mixed in small amounts with a bifune- tional monomer, a branched chain polymer is formed, (io) When a bifunctional monomer is mixed in small amounts with a trifunc- tional monomer, a three-dimensional network polymer is formed, POLYMERS AND POLYMERIZATION Linear hu osmation ee+oO0 foncseal monones & ‘aight chin polymer molec 1 Polymeric materials can be classified into several ways as described below : 1, Baed on Siracureape. A polymer molecule may be Linear, Branched or cro linked. Their structures tions examples are given below Polymer Stractare Examples, tome ee |r nee | reer Te | Ore ate) Crmotinin FE, [ee reaetpayinrn, faeon tamer Rubbers etc.) or Semi-Crystalline (¢g., HDPE, Nylon, Polyesters). : 4 eet3. Based on its ehviou he eae tials are broadly divided into tw arian ino wo categories on PE.PP, PVC, Nylon, PETetc)andthesmonstes POLYMERS AND POLYMERIZATION §, Based on Origin. Polymers may be Natural (¢g., Carbohydrate, Proteins ete.) or Synthetic (¢., Plastics, Rubbers, Fibers ete.) on this basis. Based om Conductance. Polymers are mostly insulator (eg. mostly all) but they can be conducting (¢., Polyaniline, Polypyrrole etc.) also. 8-Based on Exzziramment friendly nature, Polymeric materials can be durable (¢.x., mostly all) or biodegradable (eg., Starch based PE). —_ ‘9. Based on Type of monomers. Polymers can be polar (¢., PET, Nylon etc.) or non-polar (¢g., PE, PP etc). 40. Based on Number of monomers. Polymers ean be homopolymer (eg. PE, PP, PVC etc) or copolymer (e¢.. styrene acrylonitrile copolymer, SANTetc) when the router Conducting i a en ‘Biegradabie anbie SS =, ofMonomer Pole Nowpaar Bassioe Nese J}, ‘fMomower rr = I [organiepotymens | [nrganiePotnen] [Rendon Growth Medonion T al ‘Sip growth pyre | [Chan growth per number of monomers are one and twa respectively.vex 80° aman coenisTe OLYMERIZATION Mess the process by which simple (me aot y Lge (polymer) molecules. Hene eater sivmers is termed as Polymerizati anes There are thre different ways © Print ) By opening a double nh > ~0-cH 3, Pare (0) By opening ‘ 2 { 0-(auiy,-€ k . f=0 — 10-1 +o Sralerlactone ms, (OBy using molecuses navang two runctonas groupe, <3, "HOC (CCH) COOH +n HN-{CH)e NH, —s Heaney ‘a ° I ~ CHIEN CIN : | H Nylon 66 These Polymerization reactions can be broadly classified into Addition and. ‘Condensation Polymerization. There are discussed below = where His the enthalpy of polymerization, ‘AS is the entropy of polymerization (= Entropy of a polymer = Entropy of a monomer), and Tis the polymerization temperature. Generally, AH values are negative since polymerisation reactions are exother- mic. The AS values are also negative as there is a change from disorder to order in polymerization [(ic. the entropy of a polymer (5p) is less than the entropy of monomers (Sy) and 4S = Sp -Sy= Negative)). An increase in polymerisation temperature increases T AS term whereas AH does not change significantly. This decreases the magnitude of AG and ata certain temperature a condition is achieved when AH =T.S, ie, OG =| 0. The polymerisa- tion reaction is now said to be in a state of dynamic equilibrium, iz, the rates of POLYMERS AND POLYMERIZATION. ymarizalon and depolymerization ae the same-The temperature at whe a = a aden ope feimerization can ocr. The cling temperatures for some commonly rae ee eee ee E Methyl methacrylate Styrene aemethylaryrene x a 20 zane = 0 eee a it referred to as the floor tempera- ture (Tj below which no appreciable reaction occurs. The optimum temperature for polymerisation reactions fall between the T, and T, 4.1. Addition Polymerization, Tolmer gibi by ndion pomerization ho £ > een amnirica & Polyvinyl Chloride 4.2 Condensation Polymerization * te takes place by the condensation of two different bic or poly functional ‘monomers having functional groups which have affinity foreach ober. For ecan- le ~ COOH and ~ OH or ~COOH and — densation polymerization. >. ¢ as aa Italway nysacconenies with fe itnaton of ‘of small molecules like H, O, HCL ‘tc For example: eH ob ples. n HOCH) OH —— “Terephaalic acid 2nH,0 Ethylene glycol [otenw Prefer pees ‘rized below in Table 2‘ith afinity foreach other Noby products formed. Generally aby producti formed. Homochain Polymer, generally a | Hetero- Polymer Monomer in step-growth polymeiaton capa of combining wih tel cx with any ber pts preset with eal athe ndeappens ean erection The degree of polymerization an enc the lesa weight ofthe pljne cscs ead vp the econ Te sec govemed byte Renal groups. Longer reaction time is essential for getting higher molecular weight polymer. Itcan be either addition or condensation polymerization. For example + (Addition step-growth) polymerization a, cH, 0 1 =C=0 | so ROH -C-O-R’0- N-C-0-R’-0- io N=c=0 Disocyanite Dat Polyurethane (®) Condensation (step-growth) polymerization ar) -_/ 4 a-c Cl + HO{CH,)-OH ——> aH Benmyldhide Ethylene gyal ° [LOtooarel,‘A TEXT BOOK OF ENGINEERING CHEMISTRY POLYMERS AND POLYMERIZATION The lowing points con econ fom the mechanism : = \) A single monomer can also undergo condensation polymeri, [provided it has two different functional groups at its ends like tha dimer or tetramer. (9 Condensation Polymerization proceeds in a step-wise ‘molecular weight increases slowly throughout the course For obtaining a high molecular weight polymer, longer reactior are required, (ii) During condensation, small molecules are always eliminated pron ° 1 ‘empirical formula of polymer differs from that of monomer. (ie) We always end up with linear polymer when the reactant is bifune- tional. But ifthe functionality of the monomer is greater than two, a branched polymer or cross-linked, three-dimensional polymer can be obtained. Hence, both Thermoplastics and Thermosets can be synthe- ‘ized by condensation polymerization. 4.8 Addition (Chain-growth) Polymertzation It takes place with compounds having the multiple bonds such as vinyl ‘monomers . CEG Sc ‘where SG is substituent group, itcan be ~H,-CH, -C.-CN,-CyHgete. "Generalized mechainism : ‘The Polymerization proceeds in three distinct stages: ( Chain initiation step(s) : Interaction of monomer (M) with initiator (In) forts activation and generation of reactive particle (M’) occurs inthis step. @Ga5—-e mere [ om (Chain propagation steps : It consists of a series of consecutive reactions to ‘cary the chain-growth process by the interactions of M” with other monomer T HOOC (CHayCOOH 8 - _4 i M>—+M" t 9 =o molecules, = ° 1 N. D H Timer rd Forinstance: — M'4M—> Mj 2 Mi+M—> Mj 8 mY Mj+M —+ My , , (1) umber of il stepa to generate My My-1+M ——+ My MRED Co) S) ED Hobe on > ox on HO 7 oo ~ Te ee ee _ oe/ ee fa een eee pee ee eee eee Plmon inmedatly ater the tart of fe feat: Lente es | /nave a litle effect on molecular weight, but gives higher yield. (Thus, number of polymer molecules continuously increase with reaction time). At any stage, either | ¢ unreacted monomer or high molecular weight polymer is there. (@) Free radical initiators eg, Benzoy| peroxide (6) Cationic initiatorseg, HY AT (© Anionic initiatorseg, RNa" or {d Hetrogeneous (Zeigler Natta) initiators ‘Chain growth polymerization can be either addition or condensation poly- ‘merization. () Addition (chain-growth) Polymerization. High molecular weight polymnerscan be synthesized from vinyl monomers by carefully conducted radical or ionic polymerization. Examples of Vinyl monomers which can be polymerized by this method are: CHy=CH,, (CH;=CH y= cH l Y x Ethene cgsinvinyl corde eg. nmethy| methacrylate =c X=CHyand Y= COOH (4) Condensation (chain-growth) Polymerization < ‘Friedl Crafts! s a -Ocne = Ost {O)-crs — timer N N e Diner an ts POLYMERS AND POLYMERIZATION fon Moteclar weight —— et a 445. Condensation (step-grow) Polymerization tproceeds by stepwise intermolecular condensation. The product formed at ‘each step, when bifunctional reactant molecules react together, stil has the func- ‘tional group for futher reaction and thus the reaction will ontinue until one ofthe ‘monomer is completely consumed. When this happens, we generally get a big, polymer, molecule. For example, let us consider the synthesis of Nylon 66 starting from its monomers Adipic acid HOOC (CH,),-COOH and hexamethylene diamine HN (CH,NHy It can be seen from the above mechanism that carboxylic acid and amino functional groups areat the ends of dimer () and tetramer (If). Hence tetramer will bihave ikea dimer and thus the chain wil grow in the same fashion, til we get a polymer molecule Hence, if we condense m molecules of adipit acid with m molecules of hhexamethylene diamine a Polymer (Nylon 66) of the fllowing structure wll be obtained. o 0° 1 i mHO-C4CH,)-C-OH +n HANCHy)-NH, L fo 0 y f | 4 CAC HA CNACH NE |= + 2 HU 4\ | i om _Gy Free radical polymerization ; By Tonic polymerization (a) Cationic and (b) Anionic polymerization ; G8) Coordination polymerization. i ‘These are briefly discussed below : 1. Free-radical Polymerization. free-radical polymerization, monomer is activated by its transformation into ee by te thn of gh a ee Bor yradiations (asin radiation initiated) or ‘chemicals, known as iniiators(as initiated) in ng che wn as iniators, (as in chemically Inititors are the compounds which readily decompose into free radicals so ‘hat monomer molecules can interact with these free-radical for their activation. Examples of well known initiators are benzoyl peroxide and azobis iso butyoniie (AIBN). They generate free radical according tothe following ec ©, 0 1 r Orts2iO—Olaclo senoypemnie — 2G, +200, cH CH, cH L ii 1 ao H,C-C-N=N-C-CH, — 2H,C-c-+n, 1 1 ow by A Asai byrne ATEN) such reactions can be writen in general as In where In isa initiator molecule and Ris free radical eat 7B abo known to initiate some fre radical ethylene polymerization reactions. It occurs at higher temperatures by the thermal decomposition of the Peroxides and hydroperoxides formed from the monomer, POLYMERS AND POLYMERIZATION The mechanism offre radical polymerization : Chain initiation Ttinvolves two steps viz. decomposition of the initiator h2R and the ain ofthe int vig toes CH= CH molecule to the fee kc radical (R) and the formation of (1) as intermediate. &+ah CH BH ‘SG SG o where SG is substituent group Chain propagation Itis accomplished by the addition of monomer molecules to (7) leading to the | formation of macro-radicals In general R chain transfer reactions) and ~The ppier chain can be terminated by eee of combination of two radical either ~CH,-CH + CH-CHh- SF Arg cA- ce . SG & so &c ce orin + arene reore “thay ie Se ei y recombination”| | | | t aan cera 92 Depropertionstion : It involves the transfer of a hy poet Sra sete te remains sae a Sate rot os 1 7 AChE + CO ch, Cott + > cxcH- L 1 Sf ssc cA ae RaTS, PMMA tnd vinyl acetate chains terminate mainly by ispeoportionation”™ {tt Reaction with Polymeriaton inhibitors: Growing polymer chain can slo be ‘cmicated by is racton wilh Polmerzaion nhbieh tie and anisrsbsazene, Oxypen is also powerful inhibitor a it reacts with radials to form the relatively unceactive peroxy radical (M; +O, -»M,—O.~ 0) that reacts trith telf or another propagating radical by coupling and dlsproportaneeay reactions to form inactive product (probably pronides and hydnereecsaeny (G>) Reaction with the solvent molecules (lke catbon tetrachloride) H 4 1 -cH, + c+ oc oot 6 5c aa ti 7 a “CC +00, —4 CC ti aa J Chain transfer reactions in free radical . aco te xighal growing fee radical chain is termined by the reaction withthe oes ‘molecule and anew chain i initiated, peectios ‘monomer i H : 1 Che + OheGt —s ch GH + Lok £ i 4 Be a cacct cH io — cece cy 1 sc Tie Ff 4 es 4 is Hence, these will be no change in the overll rate of Polymezization but the | | ' oe 2 = FLYERS AND POLYMERSEATION z ede edition polymerization 0, Linking during the fre radical bs AIG) famed by the propagators of eral polymer reais ‘can take place, leading to the abstraction of hydrogen atom (ce eS ft muddle of he ham Ths ads othe was aay ofthe active centres from the grow ing end of the polymer chain to the middle cof the chain (ii) f° -CH,-CH —> —- ae ‘There is also the possibilty of reaction-between two molecules gf type (i), leading othe formation ofcose-inkages. PE _Miiomers which can be polymerized by fre radical aditon polymerisation are int The mechanism of a simple free radial initiated addition polymerization ie rewtien below 4 | u — oe 5 oi : wee —"—+ mie "amir | Propeaion 5i 4 Tex 100% oF EnoncenNG cutee { rersimpity, suming trminatonty combination ener an 5 oe ee ~woa— send a te ant tere | ® In ve mechani Equation (6) also indicates that the R, ~ {M]. But experimentally devia- onnanecers Meera dt M and P indicate moncmes, initiators and tions w.rt. [M] are found. ar area eee Let/is the action of ica Yelding two radicals dependency off on IM] particularly at low efficiencies and in solution polymeriza- ant ate faction trast which tate chins teat sree hve ays ea be y= As oe “The average kntc chain length 1), Its defined as the number of monomer units : consumed per active centre formed. 2. decomposition of in is rate determining step for initiation. Thus, initiation, R, is given by “ Thus, the rate of paecoeky o R= 2k Lln) os ROR ‘The rate of propagation R, is governed by the concentration of growing chains From equations (1) and (6, the above equation becomes [M"] and of monomers [M}. This is also, in effect, the rate of a, (Inj? q 50 R, alo becomes the overall rat of pajncncten nn oneation = ECA a | R=4 bat —ay an pb, o { Ok, ky? (inl The termination ratein mutual termination i dc:ermined by the concentration of radicals is. as two radicals arei (DF D.1 growing ‘This reaction is of second order as two radicals are involved in The number average degree of polymerization (DP,). It's defined as the average cach termination chain. R=hi—My we) | mmbsefmenomer nie pr polar It is found in practice that the concentration of radicals quickly reaches a ‘Thus, DP,=r (if termination is by disproportionation) ‘constant value and the reaction takes place in the steady state. This is known as and DP,=2r (if termination is by combination). ‘steady-state approximation and is used for finding | ~ M’] ! ‘Thus, we can conclude from above relationships and equation (6), that while ‘Thus, the rate of radical formation (R) becomes equal tothe rate of radial -'|-~«—=«amincreasein [in] increases the polymerization rate, Rt decreases ther, ot DP, disappearance, (R,). ft or molecular weight. Bdfd a 4 2 Jonic Polymerisation. From equations (1) and (3), the above equation becomes | “These are dependent on formation and propagation of ionic species. Relatively kali}. | low or moderate temperatures are also needed to suppress termination, transfer, Cl and other chain-breaking reactions which destroy propagating centers. =" ey omic re 2 vs 2 (—aj=V 78m (A) Cationic Polymerisation. Monomers with electron releasing substituent ‘ (9), (@udvas OCH, ~ OC; Hy and ~C, Hy etc) undergo cationic polymerization in This value of (M']is then substituted in equation (2), we get the presence of Lewis acids and Friedel Craft catalysts (like Al Cl,, BF, Sn Cl, etc). 2 : ‘They add on to the monomer forming a carbonium ion. An essential feature of cae el cationic addition polymerisation is that it takes place at very high rates, evenat very low temperatures. Monomers ike .~ methylstyrene, nd isobutylene are prefera- 0. ATT 200K OF BGEERNG cHesteY POLYMERS AND POLYaaERIZATION aca (@ anionic Polymerisation. Monomers with ecron butigacra, eof adam orpe an Htc undergo anise fin mg Subs es Pe flowing ‘portant points canbe concluded from the generikzed an- presence of sodium or potassium amide, alka ae ‘onic mechanism forthe formation of PMMA. diate ‘po exam of nan aren Spices pre tg oe em aco ae seme an ns rh a Se tet en po maton eae crowing sen ee {a added. polymerization proces sgain sats: Tha the palma ne ee ciple, vue With the monomers having sete nee {pnt pros ahh macaw popsy nc Polymerization. ¢ N Ne an matt ania canbe explained by considering th steps forthe formation of adding alternatively the required monomer with predceoomedoe cee, polymethyl sethacylate (PMMA) staring rom methyl etecoing, aii ) Lig pment Sr pymeriains n whch propagating centr do not Propagation: andere ite telerik a oy, Diao NCH, ee These pomersation rection are catalysed by Zeigler Natta ctalyta en aaa rere fonmed between triethyl aluminium Al(C, H,) and titanium halide Tcl, A Initiation: in the initiation step, x ~ cloud of alkene overlaps with an empty d y cotta of Senin hen there o Recon of acne ce see nmeH H NZ c year UE oy nN Gh-cH, ———", sh Hoo, 71S chic, sil. ah at- a o a : As intramolecular rearrangement again genérates a vacant siteon titanium, esch time one monomer molecule can be added in the same fashion. a ey cH, ‘Significance of Coordination Addition Polymerization permits stereochemical control. For example, propylene when polymerized by ad cea ta ee e In 7 methyl groups are on the same side, this stereoregular arrangement 8 higher meling point ardnesand superior properties Incontnt ae , methyl groups attached tothe polymer backbone are distributed at random. Hence te St pepe ‘is soft and elastic cc ee Sane virtually free from any branching ‘These unbranched PE molecules pack more efficiently, and this result higher density and higher melting points of this polymer than the one obtained by Semin aon postin. Sterosletioe synthesis is also possible with coordination catalysts since ey pee a are eT For example, isoprene can be polymerized by using Zeighr-Natta catalyst «ds, (polyisoprene, which is a material virtually identical with natural 4.7 Copolymereation Copolymerisation has been wed by nature in polypeptides which may so many a 20 diferent amino aids Chemists ar sil far bein but copolymers of twomenomers, or terpolymersof three monomers are now being widely produced ‘Copolymerisation is a polymerisation of two or more monomeric species together. For examples, Pare oN CH-CH} (“ae ot | ny aan chloride a @ moysCH + nCh=CCH-G_ 1 ‘The resultant copolymers possess some advantageous properties which are seule frend we Force styrene butadiene ibe BR) hasbothe tigidity and toughness. Moreover, it has good oil and petrol resistance: