ad = Polymer: Poly + mers tn Greek: Many + p, = Polymers: Polymers ai macromolecules con; — Monomers: The simple molecules which Combine to give polymers are called monomers. — Polymertsation: The process by which the ‘simple motecules 1.e. monomers are converted Into polymers ts called as polymertsation. CR. RCH, = CH, folmerisation, £CH, - CH, }5 (A) Classification of polymers on the ba Polythene Polymers) po TTS {ised on source Based on Based on inter | [ Based on modi No. of 7 sed on inter lased on mode No. 0 i abil eongin pemucrure | [molecutar forces} |otpetymerization| | movorers| |Bideeradability Linear Elastomers ‘Addition Homopolymers ‘Synthetic Branched chain | Fibres ‘Condensation ‘Copolymers: Biodegradable Semisynthetic ‘Cross -linked [> Thermoplastic “Ring opening Non-biodegradable ‘Thermosetting of sources or origin | Natural Polymer Depolymer which are obtained from Mural sources are sald to be “srl polymer, Fant polymer These are obtained from plant *& Cotton, linen Natural Rubber fsa Polymers ¢ are derived from animal a. “€ wool, silk. ta) hare derived fom The payers sa polymer ara died di 0 ‘Semlsynthetle Polymer ‘Synthetic Polymer ‘The man made polymer which are artificially prepared by polymerisation of monomers in laboratory: Sfiaoce nitrates secon 1 , m as regenerated © Nylon, Terylene, Neoprene, Bakelite. PVC, Teflon, Polythene synthetic rubber, (b) Subtypes of synthetic polymer are| It Is also kn fibre. on: | — Fabre ved In preparation of 1 teu memsnie photographic Mims | — systematic rubber a ns, varnishes ete = Plastic 43)ned from two or SE | The pam BY mmonerers fare called #3 copotymes)| iflerent PCS © Heteropolymes The pohner which are formed trum only one tYPe of homopolymer monomers are called Faipie acid + Hexamethylene Ethene E-caprolactum Propylene Vinyl chloride diamine 7 abutadiene and Styren Potypropylene — rye = of structure (a) Linear Sy cinwifcation af palymers on the be aioe io Oe eset a be ae or tnking of penta cB, fo) Branches fsten: Sd Kees Monomers of ponrmners {c} Cross-| . (Chain configuration) ee in monomers a Examples pe we SLID [These are the polymers 10 Bien i ell packed they , Wr ioined [© High density ah tenalle streng OR Petraes moteete® are Jone | a Nate | Cr dt chain | together to form long and linear ¢ Thigh density | polymers sett ay BEADED Se hmelingpant | e [eie attained from bifunctiona | monomers or alkenes FAs these polymers are ch [> baw denstt ch irregularly packed they These are the polymers in whi pene are te Pelrcuten are joined | polythene (LDP) (2) Branched + Polypropylene have polymers Together to form long chains with aide tS cai Nranches of different | Starch —low density chains o br hes of differen — tow tensile strength + Monomers having 3 functional wow | —low MP or already having aide chatns, Saxe are the polymers in which [+ Melamine 7 Due to network ] Tay Cross linked These are the Pi seeamerie units are cross-linked to | + Bakelite structure. They or mononee ciimensional network. [+ Vuleanization of | —Hard Meswork + Cross linkin results from Rubber —Rigid polymers polyfunctianal monomers — Brittle Tp) clanaification of polymers on the baals of Intermolecular forces Intermolecular forces — Mechanical (Tensile strength in polymers Properties Toughness, Elasticity) (—+ Elastomers On the basis of Intermolecular forces __}-—+ Fibres Polymers are classified as |—+ Thermoplastic {_, Mermosetting polymers Tiastomers Fibs ] tore Var der Waal betwen the chains and have | intennotecutar fordes ike Hydrogen bonding. 19° | etched by external forces and (2) Due to strong intermolecular forces these Nt) shape on release of that forces. possess high tensile strength which 1s 2 1% bel (3) Elastomers have have reatstance to breaking, under tension ad Paveak vant der waals <> Permite the polymer | (9) Praca guint ature, | intermolecular forces to be stretched Wores have lens elanticity. + Few cromlinked Help the stretched | between the chain polyiner to returned to | {ts ofginal position when | applied stress ts removed, |7 vakcantved rubber, Bana Sp (are. “NS. Neoprene, ete yy are soft. stretchy and tse rs are tn Ing rubber (ee Pay raes Rion 6 Thvester revlon £5) These polymers are fone ind oh thin and Uheead tke and ised in textile and al dustties. strong ropes, tyre cord, Thermoplastle Polymers prnese are the polviners Which are; eottening on heating and hardensn, tne change in their properties, able of repeated HON cooling with Iymers possess |a) These poly ‘ss moderate strong inte forces that are intermediate between sere eet fibres. leg. Polythene, Polystyrene, een elastomers and Polwinyts ete Ja) Mey can be remoulded, recast reveled, isiThey are soft, less brittle and soluble in some ongante solvent Thermonetting Polymers WW) These are the poly ef ier which can be moulded 1 different shapes on heating but they get hardened ble while hot once hardened these becomes tnfu cannot be soltened by heating (2) These polymer possens a extensive cross linking by covalent bonds which ts formed tn the moulds during hardening /setting process while hot (3) eg. Bakelite, urea formaldehyde resin ete (4) They cannot be remoulded and resh: (5) They are hard, rigid, byrtitle and Insoluble tn organic solvent [E) Classification of polymers on the bi of mode of polymerization ‘Addition Polymerization Condensation Polymerization Ring opening polymerization ] [lit is the process of formation of polymers by addition of monomers: without loss of any small molecules. poly! eliminatio molecules tke ammonia, HCL (2) eg. (Nylon-6.6) ete lajeg. Polythene, PVC. Polypropene ncH+¢H ———> cucu cl a nilo-CH,-CH (Vinyl chloride} 0) They are formed from ut compounds. It ts also referred as uinyl polymerization as majority of monomers are from vinyl ErouP- saturated ere y chain mers. Feactive end of growing mono jes of plecules [11 Its the process of formate netional monomers with Ethylene glycol ts also known ross the double bond. feo) is a rv 8 involves a This process takes place wih" poly fat condensatzon reaction of any molecules: fetween mo! ace ie ink petwronal group With functor, of small molecules clue vith Loss sys tal proce’ (i) The process in which cyclic monomer yield a monomeric untt which ts acylie or contain fewer cycles than monomer tr of water ete ‘Tenylene, Bakelite. some HL methanol ymertzation of eg P caprolactam, Ons (3) Cyelle compounds Ike lactams. Cycle ethers, lactones ete polymerize by ring opening polymerization phthalic acid fee Uke CH, = CH - Cl. er ton proceeds cu = cH- CN wofcn,-cHs-0-COL OPT 4 | Miia ot stad a lay oie volves one on (out never of longer units) to the! Generally it Invol Terylene growing chain motecules. in this Monomer. are formed from sense ring opening polymerization | Polymerisation as tt tpi : volves two or more | condensation poltmertzation Tadltiee et rmamomeric units a | (gy generally as step growth kes plur rAn's XIl Che 14 __— anism for Addition of hal ton Free Hadteal at krowtte potymert A vartety of unsaturated compo' alkenes or dienes or their derivatives are polymertzed by tinting free radical mechatt! jon tty addition: ain reactio Free radieal mechanintn fs corm polymerisation it in also called ¢ which involves 3 steps — fea ehratn propagation and Fearky toy, R-cH,-Ct ivinyl nono ew Ra RCH, | cht, -Gn-y VI, step the above continuous chain Step 1 Chali Initiation WW) Chath reaction ty initiated by a free radical — An initiator (catalyst) auch ax benzoyl peroatdes, acetyl peroxide tert-butyl peroxide tte can be used to produce free radical Example - Acetyl peroxide generates methyl radical as shown below ° ° " " cn,-¢ -02.Co—c- cu, tcetyl peroxide) + ° Ili co, 2cn, £0» "cH, (Methyt free tadicall (0) This free radical (Say 72) attaches ttself to olefin (vinyl monomen and produces new rudical RU + CH, =CH-¥ — R-cH,- cit-¥ (tree Winyt (New Radical) Radical) Monomer) Step-2: Chale prop — The new midical formed in the inttlation step reacts with another molecule of vinyl monomer, forming another still bigger atzed radical, which in turn reacts with another monomer molecule. — The repetition of this very rapidly. 15:3 SOME IMPORTANT | POLYMERS: (1) Rubber Elastomers are popularly known as rubbers, equence takes place Natural Rubber (QyNataral rubber ts 8 high molecular mass linear polymer of isoprene (2-methyl-1, S-butadiene) (2) Renetion: Polymerisation cH, | 2-Methyt-1, 3-butadine) fae CH-cH, ¢ b cu, I (Polyisoprene/ Rubber nCHy=€-CH = CH, Je atages At sore ‘can be stopped or terminate by stopping reaction ci mimornees DY addition of wspury the san ya eo ew cay aden te rep is known an chain termination 2R- (*" cH cu,-cH-¥ i R ong ft} T ¥ Ine y oR R-FCH,-CHI-FCH,-CH we fore iR PP eT ee (F) Classification of Polymers on the basis of biodegradability Biodegradability 1s the ability of organte substances and material to be broken down into simple substances through the action of enzymes from microorganisms. >——_, Biodegradable Non-Blodegradable Polymers Polymers R Vulcanization of Rubber (I Vulcantzation ts the process of heating of natunl fubber with sulphur to improve tts properties a! which a network of cross links are introduce’ {nto natural rubber (2)Reaction: ont 104 potyinprene Eprinen wuleanised rubbergeen to Doluner eta nates 1 hy weak forves andl Was eatled structure yirean be stretched Ike i antic: properties. gieis sat and sticky: ei jp has tow tensile strength Mics soluble tn solvents. ty feuachloride, petrol, etc spr and exhibit ke ether, arbon fa} Polythene: (Polyethylene) bef C11, cu} [iiee Density Polythene (LDP) Uy) Resetlon: LDV ts obstatned by polymerization of ethylene under high pressure (1000-2000 atm ) and temperature (350-570K) tn presence of traces of O, oF peroxide as initiator nCH, = CH, 250-570 cH oy cH, CH, ‘ 1000-2000 (Ethylene) peroxide LP, {ee cH, Its obtained through free radical addition and Hatom abstraction. This latter results in branching, Rhtoperties of LDP ~ Flexthle, but tough Chemically inert ~ Moisture resisitant ~ Due to branching, shows low d ~ Moderate tensile strength. ng tt has low melting point Cet of LDP “in the manufacture a flex! insulation to electric cables ™ {WA ty used! an auibanarine cable HAMITTON SUM ts used in producing extruded tutnly for packaging Mite used an manufacture of US fe density ble pipes and squeeze bottles ner used in prepare! eg reetistene (CF, = cr ee radical uyttiater * tit Petipa Pee op, Fd : _Bolymensationy {C1 age cr, SR at efi ten thene igh pesmit® ypotvtetra ry During vulcanization. sulphur forms eros petwern po and Wt improves the Pieperties of natural rubster 1) He tas nats (HN ts that ane tines atic ky (1M haw tigts tensile trenicths (110s tnsatubile tn all enn (1 By conteotiing amount of sulphur proprries of natural rutite rd lke 20-40% So Hard Hubber 9 Used in battery ease rubber 10% S o> Lite Harder => Used in making tyres 1.3% So Soft Rubber -> Used tn Rubber bands Mere are two types! (O) High Density Polyethylene DPE _——«d () Reaction: HDF is obtained by polymers ethene in presence of Zieglar Natta catalyst (rtethy! aluminium and titanium tetra chlorides ata temperature of AIK to 43K and a pressure of 6.7 atm ACH, = nCH, cu feu (DP, linear polymer and therefore molecules are closely packed wth (2) Properties of HDP er and tougher than LDP — more resistant to chermical tha LDP Due to close packing (linear polymert tt shows high density has high tensile strength We has high Melting Pout (3) Uses of NDP Ins used in manufacture of toys and household articles ltke buckets. dustitins bottles ptpes — more h ete It ty used to prepare laboratory wares and other objects where high tenalle strength and stillness ed Tough = Chemically inert A by corronive rragent fas © F boot ts very di few to berak and remuin tnaficcted ty corroene alkatl organ aobeny Dees: It is used tn making noo stick cookware off seals, gankets eteig XII Chemistry Papers So (4) Polyacrylonitrile OR PAN OR Orlon OR Acton Preparation uses - 2 fs used as woot iepacaie rare aon a | 8 a rm nc, = cn Pameneaten, (" ra uy tes used in 8 aking blankets, cloths, by ee ox |, arpets ete —— (Polyacrylonitrile) (5) Polyamides polymer — Polyamide polymers are generally known as Nylons — Palgamide Contains -CONIT. group as the snter unit Unk — Two tmportant polyamides are Nylon-6, 6 and Nylon Preparation peated with water itt ization] (1) Properties and uses Properties: ‘The name nylon-6 ty given on the basis of ste Polymers (A) Nylon: When epsilon (e) Caprolaet res ring opening poly high temperature at under amin group an 0 give the polyamide polymer called nylon 6. ungroupand — | to give the polyamide polymer called arbon atoms present carboxyl group 7 eae in the monomer unt present in the sume] CI ca ‘ molecule reacts | al HO, Lan qenia,codg | ti) has huh emt intermoteeuatly ch ch, SI sHR strength and luster the resulting amide |S. — ch, invton-61 Uses: It is used for Is cyclic Is called ee maniafacture of tyre cords lactam {e-Caprolactam) fabrics and ropes (HyNyIon-6.6 The monomers adipic acid and hexamethylenediamine | Properties: on mixing forms nylon salt, which upon condensation (i) The mumeral 6, 6 1s th polsmertzation under conditions of high temperature and name of this polymer pressure give the palvamide fibre Nylon 6.6 stand for the number of earbor bifunctional monomers Le. Adiptc avid and hexamethylene dia niooc-{cit,}, coon + nlt,8-{CH,}: 8H, cs 18 089 Adipic acid) [Mexamethylene diamine) une (ego {W Nylom 6.6 16 high alo -¢-{.cit,},c-0- Kit,€en, molecular mass linear —oae condensation polyine Wn) Tt possesses high ~ n,0 | 553K, high pressure tensile strength ¥ (iv) 1 does not soak i on water LE ceng,l beemget alain : Te ~ cn,}, th sheets, bristles for brush) tivon 6,6) stirgical sutures, textile (6) Polyesters Terylenc OR Dacron fabrics. ete Preparation The polyentcr have cater linkage Temlene also called ax Dacron Jrelene fs obtained by condensation pol ion polymerization o Ctnpiene yeah and teepithale acd In presence ot catalyst at high temperature. “ nHO-CH,-CH,-OH + nHo-c c-oH {Ethylene glyeot) u N ° ° Merephthatic aeid) Properties and uses Properties: (TC has high melting point U0) It fs resistant to eb tw hemical (Wis used for making wrinkle free fabrics bY blending with cotton (teryeot) Werywoot) - and and woolee to Polymer chemise ee ES t cH, cH, -9 {VET tthe poneaer used for makin Packing contat (1 Patye arbonates are if Many articles Uke bottles, jars] are high melting the 17 polyethylene terephthalate 0 a kind of polyesters and] osetting resins, Preparation thermosetting alynt, ‘ Bakelite the of phenet oF base eat, polymer oh ned from reaction len presence of acid Prep, eee Of Bakelite involves 3 stages dlertvatives ue te oe at/0r p-hydrany beesaleoho! a wtion between phenol and formaldehyde (Phenol, ou on on chon oo” on cron cH0n cH,OH Stage-II: Condensation of o hydrayymethy! phenol or P-hydromethy! phenol gives a linear polymer that ts Novolac ou cH,on i n 9] on oH ou wey” oo Lae ay cross Hits ah state fare formed which 1 Properties and uses Properties (1) Tes insoluble a infusibte (W) Te has high tensile strength Wun) tes hard water resistant iv) Its good insulator Use (It serves as su for ass (0) Its used for making articles like telephone instruments, kitchenware electric insulators stitute (Bakelite mouttds, a Ay potymeric material called bakelite formation ¢ — — = awe CH on, Aen, cH, : CHO heat ye HEIDI, oe cH, cH, cH, Nothydronytbenzy! alcoho!) puppets 1,0) i . " 4. cHy cny CH, wee Sip-hydroxylbenzyl alcohol ae eT on onie Tape ke formes jecorative tab ena ad moisture fare mate from heat formaldehyde pla — When the 4 formaldehyde polymerisation, st forms €F? jomer, aetamine formaldehyde. Preparation resistant uunderyoes co - oD roNcHNN mA er ] T +H-c- > By N. N Formaldehyde ii-cHO} NH(CH,OH) Nn, (Mtetamine) [0° og XII Chemistry Papers § yrras’s Soliton Propertics and usey Uses: It is used In maksy crockery. THESE are use for making CUpS and pa, which are quite durabe | and hard aie dinner ware 1 thermosetne, relic triammine yeter ylenisation akedd MeL’ NH(CH,OH) NH - CH, n Cross linked melamine formaldehyde resist (8) Buna-S rubber Preparation Properties and uses = Buna S is an elastomer which fs a copolymer of styrene with butadiene. + Its trade name 1s SBR (Styrene-butadiene rubber) + Buna-S ts obtatned by Addition polymentsation of 75 parts of butadiene and 25 parts of styrene 1 ts vulleanved witht sulphur. 13 iene cH cH, —CH, - CH = CH- CH, -CH- cH, — (SHR) (Duna-s) ()__ Neoprene [ Preparation = Neoprene, a synthetic rubber, Ws a eondensatin polymer of chloruprene (2-chloro-1. S-butadiene) Chloroprene polymerizes rapidly in presence of axyiten. nch+¢ CH = cH, Munereation, CH,-C» CH-cH, i oy (Chloroprene) Neoprene 7 Duna-S is superior to natural rubber with regard tomechanical strength and has abrasion resistance Hence is used in tyre industry. = Properties and uses =e) vegeabne oa 2atleularly resistant to petrol able olls. light as well as heat Neoprene ts i rae $8 used tn, Making hoseptpes for a ne and making waskets190 Mts Used for Jackets ne ot MNUTNCtrtng tnwulator cable, for power transmisaion and conveying, a Tyecme tayon a seminyMheNAUE hich 1s regenerated cell —Cebulose tn the form of wood pulp Is wannorned eee am —Celuilose ts a Linear polymer of glucose unit and has molecular lormala (C,11,.0), ~Sodified molecular formula of cellulose ts Cell - Off “es anction: (eBulose tn the form of wood pulp ts treated with concentrated NaOH solution to get fully alkall cellulose Cel-OH + NaOH — Cell-ONaw + 1,0 (Cebulose (alias cettalose) Falp wood) Mn cellulose {s then converted into xanthate by treating it with carbon disulphide Cel -ONa® + CS, ——> Cell-O “§ - Sha 5 | {Cellulose xanthate) x mixing with dilute NaOH tt gives viscose solution which Is extruded through epinnerates of spring maching |e acid bath when regenerated cellulose fibre precipitate a8 -0-C-SH+ Non Cet -0-C-S'Na’ + HO —> Cell -0-F 4 s _onec Ct -0-c-sH+H,0 —* Cl cies fi score 1 s — Most of the Mechanical properties of polymers depends upon their molecular mass. iF arse ey hay u baste siomnaee Polymer —? Mass) High molecular Mass Monomer Molecular Low Molecular Mass 0 Doe Mase) igh Melee ce |e ener oe ~ ts a complex mixture These are lable to be Ifa polymer is allowed to A polymer ts Occur MAS erage of "pitie an have low attain very fih molecular of different mo ts ana eb etrength tides 1 becomes tough and —~ Molecular mass of potter molecules | mechani unmanageble ecu ca af consttuery A po the ~ Motecng nase of pater P= tion (Umer uns HH | Both the ends are undesirable degree of polymere one — DP ts the number © § polymer moleculeSS Lar mass more = Apotymer must posses a matecu! nay jer to extibit minimum value tn ord) apuryrte acd (-hyerony Durante cig ear vei ange acid Le. S-bydrOXyPentarcac and 1 acid Boo CH - CH, - Coo than cert . tent the properties needed for 2 particular a va[tto application, Tuo by cus? cooH — This minimum molecular mass correspond 1 ‘t cH, - cH, fal degree of polytnertzation CH cael (v-hydroxy Valenc es contaming hydrogen bonding the “degree of polymerization Is fower (hare ining weak Intermolecular forces: there « 18:8 BIODEGRADABLE POLYMERS The polymers terobes due 10 nd stay in the aehiel cannot be degraded by 1 ng ehemteal bond in tt a chivironment for very long pertod of time assing pollution proble eg. PVE, Polythene, Polystyrene, Teflon ¢ rs whtch are Biodegradable polymers: The pol 4a suitab led by mnleroorganinins Wi led! products do not cause pertod ny serious affects on the environment eat, PHBY [Polyhydrosy butvrate-co-B:- hydroxy valerate! Nylon-2-Nylon-6 PGA (Polyglycolte acid PLA (Poly IA) PHBY (Polyhydroxy butyrate-CO-f-hydroxy valerate) — PUBY ts degraded by miter environn — PHBY ts a copolymer of two biftinetional hydroxy carboxylic acids nately le acid) vhydroxy DUO [0 | 0-CH-CH - €-9- cH -CH, bn, © CH,-CH, J, IPHBY) pupy used in controlled release of drues and in medicinal implant and repalr te used in specially packaging orthopaedic devices Nylon-2-nylon-6 Rulon 2-Nylon-6 #8 a polyamide copolymer of iwo amino acids namely glycine and e-amino Caproie actd. 114s biodegradable polymer Reaction: CH, * COOH + HN - (CH,},~ COOH IGiyeane) {camino eaproic acid) il nH,O - HN -(CH, (o aH u ° 1 I 4n-cn,-¢ (Xylon-2-Nyton-6) . RIOT ‘Table 15.1 : Commercially tmportant polymers Trade name ‘Monomer Polymer structure ai Perspex/acrylic | methyl methacryta cH : seat Fw cH, lenses, paint, security ~ coone few, ee barrier, LCD sereen. te shatter resistant glass Buna N ia cH ~CH,~CH,-CH I adhesives, rubber belts. shoe soles, O-rings. I by |, | easkets PVC (poi water pipes ten, . ond, rain uate, Nooring every ianide feu, ‘conn, Gui 4 cont, Polyacrylamide gel used In electrophoresisction to Polymer chemist el idehyde} (a) urea ies (0) formaldehyde +E Nu-co-mn- cH, 4, unbreakable dinner | ware, decorative @ ethylenegiycar Taminates b. phthalte acid paints and Tacquers electrical and telecommuntcation hardware, food grade plastic containers Fpemmocol (made | Styrene non-biedegradable eal thin fon-arg, secre ea each when walled beads of heated. Therefore it ts. [pystyrene banned