9 (4) the system rust be frec’frem ‘side reactions thet might selectively censume functienal greups md thereby. destry the equality f£ the X\ nol gr up e-neentraticns. “Bemree of P: lymorisati », Degree of polymerisaticn in s\eentn nechnisn'is defined as the ratio of the tctal number cf oer miecules 1t time zero to the total number of molecules vt any cther time t. If the orginal cone. of the menomer (HOROH) is 0; and its conc. at ony time t is C, then the extent of reacticn or frieticnrl yield i.e., fraction of nclecules that has reacted at time t cculd be repre~ sented by P, Therefrre, we cruld describe Ps equal to the pro- sability that a molecule cf mnener has rexcted in tine t. Methenrtienlly, we define Hence 28 1 nole rnd it decrensed e.g, if thecriginal ernc, of HjNRNE, to 0.05 in 120 seconds Therefore extent of reaction (P) = | a i.e, P = 95 percent yield. Degree of polymerisation (DP) is defined as the raticn of origin. number of mclecules of monomer to the number cf unrercted molecules xt time t. H 0, DP = ym410 In preparative organic chewistry, » yicld of 98 percent is consider ~ excellent but when applied to polymerisvtion reaction may not be acceptable. DP = (1 = 4 =e T= 0.98 f- 2% A DP of 50 is very low to give polymers (e.g. polyesters) of any commercial use, Hence to achieves de :ree of polymerisation of 1000, it is neccessary to hnve Beas of extent of reaction (P) of 0,999 ise. 99.9% conversion. This situavion is in complete contrast to that obtained in most chain giowth polymerisation where high molecule weight polymers is present : 4 the lowest conversion, initiation step lealing rapidly te a high tolecular wesght chain, Reatures of step srovth polymerisation (a) Monomer disappears catly in reaction. at DP = 10 less than 1% monomer remains. () Any two molecular species present can react. (c) Polymer yield is independent of reect..on tine. (a) Activation energies are derately hi 1 and reactions are not excessively exothermic. (e) Long reaction times are essential to uitein high molecular, weight. (£) Polymer molecular weight risos s ye the react! KDUTIOS OF STEP GROWN roINMARTANTCE It has been found experinentally tht the groups is independent of molecular weight. ivity of functiou Let's consider the kinetics of a miecular ‘iol (glycol) that lead to the formation of polyester. It hi been found conelus: that the pelycondensaticn is catalysed by acic Thus, we shall derive the kinetic relationshi; between gquinolar concentrations @f diacid and diol unde: these :onditions: (a) Presence of catalyst. In the poly risation (b) Absence of catalyst. revwticns. x 5oh) (2.03 OE Guan - th the absence af added streny acid, the dircia nust functicn ns the acid catalyat. Therefere HOROM + [OOGR' coor Plyester ~ woter a (1loo3R"ccor) = RCaror)®(o) ~~ tHith equinelnr ccne. cf onrboxyl att hydrexyl gr-up at th start of the reacticn represented by cnc. © macs Ke (2) we ' mac Ki =o 2 kat seceae GD oo Integrating equation (3) gives . = | 7Fa0 = Kat ge = Ke + constant “w © 4. = 2lb + constant ee At t= 0, 0= te Constant Equation (4) becomes Kt = 4. - 4 ae = 2 Sy 4 4 Relating this te the extent of reaction (fracti-n-l yield) P Pa G, = ¢ So. OF OF = 9, 61 - B) 0 Equation (5) becomes.see (6) ww 2)? Hence = plot of 4 2 versus tine t as in equation (=P) A (6) is lenenr With sicpe equivrlent t> 2Kc® (>) USB OF ACID CATAL . ) TF acid catalyst XS aca af Ghd b lymerisation reaction of equimolar cone, of cerboxyl and dicl epee -a0 -=82. (con) =k" (cog) (on). sinilerly, 280, “*yyg2 eeceeoe at : d= Kat “ee g@ ae = Kt at Integrating eq(3), we obtain - 4 = Kt + nstant 4 erase Att =0,0%0,, omstent «4 q 42 ee t m= Pos Kt = - 41 ae «4 ' 3 eee 7 1) ay mh 4 = 14 KCt wer soccceccee CF) crEy ° : A plot of | against tine t gives a liner olet with > eey slope equal to KC ye 813 : goss linking It is possible to intercennect individual stress of condensation polymers and the peoduct obtained @ cross linked polymer e.g. Bakelite - A polymer formed fret phene - formal dehyde benzene. Folymer of thés type are rigid end completely insoluble material, the reaction for the c6@GG@ formation cf bakelite is basicelly the friedel - crafts reacticn. the reaction is control ablz and wher a moleculer weight of about 1000 is reached, it is soluble, this is filled, coloure and hexamothylene tetrammer added (adamixco). This provides @ source of formaldehyde produces by heating and which course further cross - linking, Bakelite is’s thermosetting podymer. Synthesis of Bakelite: | cH cat14 ; ae C6 BA BAKEHTE > €rosslinking can be Temoved and the chair become free, they #re e held together however by vandal ~ weal forces, the process of crosslink&gg may be exemphted by the vulcanization of rubber where sulphor crosslinks the chairs and a scft thermoplantic is the se shosn converted to a hard themoset, reclaiming 2 rub er is the reverse process converted the thermosetting plastics to 2 thermoplastics materials: ise. opening up of the crcsslinks, thereby wm CHS CH CH CH, =A OS 4,2, bedtedene, aot we eH CE. LF item ged abb er MEASUREVENT CF _R-TS OF FOLYMERTS TICK ‘The overall polymerisation rate can be monitored througs the change in a physical or chemlicél property of the system. For example , chemital method or isclation and we.ghing of polymer : can be used to measure the-rate of polymerisation. Usually, most vinyl monomers posses doulble bonds an! thus titration with bromine to measure the rate of disappearance of doub)- ‘ends would a£Zord @ meana of following the reaction. However, sor> difficulties arise espectially if oxggen acts as an inkibicor , f-1 example A choice of @ physical property is more desirat .e. For example , changes in refractive index, density, infra rec etsorption etc Could be used to follow the rate of polymerisation. Therefore, the two commonly used methods of measuring the exte of polymerisacion are;15 (a) Weighing of the polymer forned, th . %, (b) The change in volume of tho rexction cixtbure due to polymerisation. In the first method, the polyner nay be isolated by filtration if 4 insoluble in the reaction nediur: or by filtration following precipitatic frou the reaction medium by th addition of pier solvent for the constity ent technique since the density the resection medium, The nensurerent of density is usunlly the nest sentive and convenient techniques since the density of the polymer is normally grater than that of the total monomer ond volume contractions as-large as over 20” of $he total have beon obtained in the literature. A The dilatometre is a vessel oquipped with 2 espilli-ry tube in which the liguid level can be measured preciscly. The rexctants are normally scaled in a dilatonetre which comprises cf: large bulb, tisually made of glass, to which is attached a glace espillary tube, The dilatometre is ns sealed that at the tonperstur’ of the ronetizn the nenisbuss may be viewed in the capillary stem and its changing position followed as redction proceeds, It is beat te carry cut the measuronent at’ low degrees assumed of conversion (5% polymer} whete the initial concentration may be to be constant. If Ip do the height of the initial level of dilatometer Ly the height after time t L the height on completian of the reaction “* qgeinst time t i: neaegse@® iincar ea ‘Then a plot of Log; if the reaction si first order in the nononer. The slope is % CB Ee KB. » - & SM seme co16 Methods (Techniques): for producing Folymera: There are four techniques utilitged both in th: laboratory” and indusrially to produce (synthesize) Polyners for several applications, These include (2) Bulk (masa) (b) solution (c) Suppension and (4) Emulsion Polymerisations BUIK (WAS3_)_ Por! SsWwenk ae It uses pure monomer or mixture cf monomers in their pure ete Liguid-phewe. Usually small amount of initiaters /catalyst may be added, Batoh or contineous reactors may be used and ache agra! the polymerising mass may be homogeneous or heterogenous phase mixture, Bulle polymerisation is used generally for G) petremely high moledul@fweicht polymers ard (44), maximum clarity. Problems associated with pulle polymerisation: (a) With increased conversion, The reaction mass becomes very viscous which creates difficulties in mixing and heat trasfer, (>) ‘The impooper mixing and beat transfer leads to a broadening of molecule weight distribution which is not desirable in terns of mechanical properties of the polymer. (ce) Due to the high rate of reaction, bulk polymerisation of Vinyl type monomers by chair growth reaction is very difficult. tis the t Ree ges, awe cee arrest cies ta) " reaction mechanism, With this technique, monoues, catanyet/ (ala initiator and solvent ave stirred together to ferm a solution ‘The polymer formed may be either solubic or insoluble in the solvent, Tr mest Sutable for lenid prtymers17 Jdyantnges:, Ment transfer in nolution p lymerdovti n ns c~nparea with bulk prlymerisnticn in botter md ensior becnuso of the reagea thht the visersity of polyner formed, 7— + reactirn procoeds in liwor as ecripared to wiseréity in case of bulk pelynerisation. (b) Handling of solution polymerisnticn jkéla@ is more ensy than in other cases beerise its methyd goner ‘lly proditces Tower molecular weight pelynrs ns covpared vith other techniques. (ce) Gontrol_ of temperature and renctien rate is cfton ensicr with solutions. . Disadvantages: (a) The product of soluticn pelymerisatin «ften has to be separated from its solvents for sile ind subsequent use. Solvent hindling ‘and additional tnnkege; unle-ding and transfer fagilitics involve extra Inb ur, nnintenance, design and cost. (b) Complete removnd of sclvent is difficrlt in seme cases. (c) With certain nonoriers (acryl~tes), sclutien p-lymerisatic: leads to relatively low renctinn rate and to lew molecular weight polymers compared with emilaicr, nd suspension polymerisation, fa With @@npanaaaeRee non ~ agueous solver ts, equipment clean.ny and disposal of solvents create problems in s lution polymerisaticn. SUSPENSION POLYWARTOATTON: refers t-o polytieriscticn in on egme-us system with mon ae a dispersed phase, resulting in polymer as . disperscd salid phase. ‘The initiator is dissolved i the monomer phase. this is the mo :t widely used polynerisation method. Commercixl?y, polystyrene, PVC, FYMA, RE, ete &e made by this nethcd. It may alec initiate the polymerisation of one or more monomers by disp2rsion in the fot™ @ of droplets of varicus sizer in a nen- dissvlving liquid. Iv is a type of bulk (mass) polymerisation process i: which small droplets of liquia nononers are dispersca in ultrvpure iter and caused 0 polymerise to solid sphericnl particiies. The dispersinn of the nononer in water is nchieved by vignrous rgitotz-n, in the presenc: of small anounts of suspension and dispersin ng nts.18 ‘The catalysts (initiaters) nre diss-1ved in tho nonorer if the monomer is 2 liquid er included in the renetion mediun if a eos monomer is used. In order to disperse the monomer in « suspension system, it must be immiscible or f-irly insoluble in the reaction mixture. PMUSION POTNMERTSATTON:, One or more moncmers cold bo pelymeris‘od in emutcion, Monomer(s) (nre) brought together in the icen of qi, rqueous emulsicn with the help of seaps, detergents nd enulei: ying agents. The polymér cbtained is in the fora ~f Intex w, ich oni be used as such or it is isolated by adding xcids or salts or by centrifuging to form lumps of the final orcduct. Used only for chain growth (addition) pclymerisitin cchanion. I. differ from suspension in twe way's the initivtor is vented fa the aquous phase nnd the polymer particles predurod “ro typically of the order of 0.1 micre = meter in dianot +, seme ten times smaller than the snllest encountercé in susventicn nalynorisnt. copelymerisation of styrene nd butediene sl.-wn below: FRA US EOC Prapncy Pym A dle Maiber Irroolry Somponents Earty by ight Butadiene 73 Styrene 2h Water 186 Soap (emuisifier) Set Torol mereaptain (transfer agent) 0.0 Potassium persulphate (wnter ‘soluble 0:20 initiator) The emulsifier, influences the pelyneristi the properties of » tho Intex including pnrtic. sive, parvis size distributicn and stability. daw wl19 (a) ‘The surface active agents used in 211 producing esulsicn polyners are water seluble, which results in sane degree of water sensitivity of the pelymcr itsolf. (b>) ‘The presence of icnic miterinls which are intr-duced in the polymers by usc of stirface active ngents ond inorganic salts, results in pror electrics1 prcperties in finn product. (c) Only free radicrl type initiator can be used, preebuding the possibility of producing streé regular -pelymers. Molecular Weight Determ: Molecular weight measurenent nry be bzsed on whether the contribution of eacli molecules to-2 mensured preperty is proportionnl to the number cf menorers, su : ion: nensurerent leads to the so called number average melecul~r weicht [ih which can be defined nethematically in Weight of molecules No of melecules Where ni = no fracticn cf nelecules with M! Mi. The no average MY measurcnent is cbtrined usuclly by measuring- the cealigative properties of dilute slutinn cf the pelyner, Thig includes Boiling point depression, vpour pressure lowering ,boiling print d@@Bese2G0 clevaticn nd osnctic-pressure. By determination of the end group. It is pA@? pessible to count directly the no of molecule involved. In general the chrice of method tobe adopted depends Inrgcly =n the nature of the meterial in most erses expect when modified, it has been found that most vaprur pressure l-wering mexed “no insoltable because it involves lng cquilibraticn tines. One mijor difficulty is the use of osmctic pressure is the prevdrtinn ef suitable menbran: that is peanable to the solvent but net to th. s"lute and which 4s fast enough to ollew attainient of cquilibru , ¢ ndvantnge of the nethed lies in the mye xf no rverrge uoleovlar weight namely Mo20 0,000 -- 1000000, Tur rt olevviet he Ye enprica 2 aE BAAsy will ave ot by cSoviezl er 2 Tl brs the avern2 of IN, di 4- 25,700, it to cf th crews the’ of ether tinue’ The ot} (a) The wei, reeves on 1 or beth ods ower hor sxorag oe wed iW! evn de “etrines porizient md ultracenricy neitive md reelicdle xsmult eva 30 cbt epbevicle ond -nerxiion, Titensit, ot tie enky; is wepertis le for sevttering. ne the the -quaxe of ths JRC Hence laree erin. Both solute ct! score solution dog ndomly could pelpiers. Meee SNe2 2 average Mi is given by thd ezprensiono: whis is cbtained frcm the measurenent of radical distribution of Fefractive index gradiant in equilibrun vitraceatripa.iwict. ‘ho sis of these method is that the preporticna’. ecntributicn of +... eight of each molecule is nuch greater thin ix tho case of tho wight average nethod. Polymers with homogenous roleouler sige : stributien Nin Nir = Na Beterogenous, Mn <. My < MI PRz becomes most accurnte in the hetrregenous 1’! pelgner. BiScosity enent: This is the quikest an‘ sinplest 14! dizageristic tochnique, it suffers o major disadvantages ‘in thot it must t> conplinentod 1. thor type of MY determination to Imew the acturl Hf). “ho oporetinn * -indlon to other viscosity nedsurenent experinent where! the soluticn of the svmple is allowed to flow threugh a ceppillary visectioter and tho flow tine determined ané compared to th: flow ti > of tho solvont used i+ making the solution. ‘The flow tine dote:wited re. ted to specific tomp and cone usually in @#@I68 c.ml or g/l. Tho rer.1t obtrined is a relitive viscosity (no unit). Some of the viscosit'* tarn in ured oro inted below with the correct TUPAC terns. fh Hine, 6 lu. qwrac relative viscosity flow tine of nol-.nt — Soln/en}. via0o avecific viscosity vive ityne reduced * ’ Anheront patna epee ieaeaes eo intrinsic * 1+ iting nm22 A uscful enperical fcrimlar relating intrinsic. Viscoaity to MM is given by (ring log of both sideo s plot of log ogainst log Il, gives K = intercept a = slope of linc, (a) lies between 0.5 # 1,0 but usuclly between 0.6 ~ 0.5 a= 4, the nolecular weight » weight av ce viscosity average is close to weight POLYMER , SOLUTION. Low molecular weight substance readi: ge molecular weir re We j undergo dissolution, polyer takes a long time to do so polyrer molecules are grint 1” which are made up of hundreds of seguents, they ~ve not inform of extended straight chain but they are in forn of tightly folded r coil. There are various degrees of cohesive and nttractive foreu --tween different segments, of tke saue moleculir cell 2s well icighbouring cell because of these large size and celled structi solvent molecules takes tine to establish interaction between the The first stage of in polymer dissolution is charccterised by low penetration of the solvent molecules into the interstics of she polymer coil ond forcing them to "Swell", During the swellin “"39@#@@ polymer matric increases, the solvent molecules leaves he solvent phase and diffuse into the polymer matric. As the -olling continuos more and more segenent of the polyner molecw. olventied and lososened out, after a leng reaction tine, the Atargled polymer nolecules diffuses out into the colvent. The ‘diffusion cf polymer molecules into the solvent phase can b by agitation when the polymer is swellen.