Chapter 8 Copolymerization | INTRODUCTION As indieated in Chapter 1, the polymerization of organi 1th century, However if Was not un about 1910 that & copolymerization) was investigated when i was discovered that copolymers of olefins better elastomers than either polyolefins or polydienes alone. ‘The pioneering work 1930s and the developmen of synthetic eubber to meet wartime needs opened the ‘ompounds was frst reported about che mid ‘simultaneous polymerization of ex at me monomers (0 and dienes prod ‘of Staudinger in the field of copolymerization, Copolymers constitute the sas majority of commercially important polymers. Compositions of copolymers may vary ‘tam only a small percentage of ene component 10 eomparble proportions wt both monomers. Sach & wide varistion in composition permits the production of polymer pmaduers with vastly different properties for a variety of end uses, The minor eonstitent of the eopalymer- mays, far example, be a diene intoduced into the polymer structure to provide sites for such polymerization Feaction as valeanization; it may also be & eifunetional monomer incorporated into the polymer to ens {rosselinking. or possibly it may be a menamer eontaining carboxy! graups so enhance proavet soll ddyeabity, or some other desired property. Copolymerization reactions may involve Avo or more Mon mers; however, our diseussion bere is limited to the ease of two monomers, Il THE COPOLYMER EQUATION ‘Some observations are relevant so the consideration of copolymerization kineties are + ‘The number of resetions involved in copolymerization of hve oF more monomers increases geomet cally with the mumber of monomers. Consequently. the propagation step in the eepolymerization of two monomers incces far reaction + The number of radials to be considered equals the number of monomers. The terminal meaemer unit unre afte preceding ng chain determines almost eelusvely'the reaction characterises the ica inflenee ow the reaction pa + Thereire rv radicals inthe copolyietiation of hoa somomers. Consequently, three termination steps need to be considered + The composition and sirictare of the resulting copolymer are determined by the relative rates of the lfferent chain propagation reaction [By designating the Po monomers as M, anid Myand sheie correspond Mz, the four propagation reiesions and the assoeiated rate equations in the monomers may be written as follows hain ragieals as My: and ‘copolymerization ob 18 Reaetion Ree equation M.][M] Jp] wn M;+ MOM. & Mee MOM, ky MetM OM. i [M][M] [ [ [ [ MytMoMy [Me] [ab] 2m ops aby ene etHere the frst subscript inthe rate constant refers to the roacting radieal, while the ssoond sulaseripe designates the monomer, Nowy iis reasonable to assume that at steady Safe, he eoneenttasions of My sand! My remain eanstant. This implies that the r ‘equal, [follows therefore tha the cate of conversion wt My to Me necessarily eguals that of eanversion fof My tn My. Thus from Equation 8.1 jneration ancl consampnion at these raceals ae [oJ e6.[sJ0.] 62 The rates of disapp My and Myare given by Tsclls Fei fst-]ia] 63) =] wu, JIM. J [din] ea) By using Equation 8.2, one of the radicals can be eliminated. By dividing Euvation 8.3 by Equation 84 swe obtain of) [MJ ePyepy : a] MIM rs ee e monomer reactivity ratios defi (S.0) Beton =e[ai feat fo) on Siar epreseoting the mole reins of unreacted Ma Main hemor fs by and ho as) 69 Il, TYPES OF COPOLYMERIZATION [By definision, and 1 represent the relative preference ofa given radieal hat is zading sts own monomer lo the other monomer. The paysical simficsnwe of Reuation 8.9 ean be illustrated by considering product of the reaczivity ratios, kik hee (8.10) io ops aby ene etThe quantity sy represents the ratio ofthe produet of the rate constants For the geaction of with is own kind @? monomer to the product of the fate constants for the exassereuezions, C lassie inca theee categories depending on whecher the quantity rf is unity, ser thay unity ization may sherefore b A. IDEAL COPOLYMERIZATION (rf. = 1) nnek then ° uy HEY y oF ky fk In this ease the copolymer equation reduces to of] nfo ae au] ae ket ut 6.13) “Tne niet In is evident that for ideal copolymerization, each radical displays the same preference for aééing one monomer over the ether. Also, the end eroup on the growing chain Goes not influence the rate of addition For the ileal copolymer, the probability of te aecurrence of an MI, unis immedirely tollowing an My ay MI unit afer another My uni. Theretoce, the sequence of monomer nits ian ideal copolymer is necessarily random, The relative amounts of the monomer units fo the ebain are d monomer and the feed composition, To illustrate this, we note thas the requirement shat satisfied under tro conditions d by the reactivities of th Teun be se. one of the menomets is more reactive than Is. the eopalymer will conan 2 greater Cave Tey Land 6 Torn Land 1 tn this the other toward the propagating species. Conse proportion oF the more reactive monomer the random sequence of monrer unis, An inaportant ifficulty 1s expesienced a the practical consequence of ideal eopolymerization is that incre Production of copolymers with significant giuatties of hoflt monomers as the difference in rcivities of the Cho monomers ceases Case 2:4) 1, Vier these conditions, the growing radicals eannt distinguish between the S60 monomers. The eompesition af the copolymer iste same as tha of she fed snd said ove the monomers are arsanged randvaly along the chain, The copolymer equation hecomes Redtiag (4) B. ALTERNATING COPOLYMERIZATION (r, When 4 = fy 8 (oF fay 1), each radical eaets exeldsively with che other monomer; that is neither radieal ean regenerate Self, Consequently, the monomer units are arangeedalteacely ala invespective of the feecl eamposition, In ths ease che eopalymer reduces to oh], as ops aby ene etTable 8.1. Reactivily Ratios of Some Monomer Monomer 1 Monomer? ty T eC) Acslo Siivaciene one w Sets mthaerle 15 si Sie om i Vins ae a2 so Ving! envi n7 “0 1 sien Mes! melierslane 6.78 Sirene 138 088 Sh Mey! mekaerlawe | Sgrene has 032 a Vins ae 2 ans Vin! erate Wor a ny! ride room 6 Vin eeite Vinyl lence votes a From Young. Ld Hanis, 2 Brae, 4 cy & Sons, Nee York, 1975, Wats por Polymerizasion continues until ane of the monomers is used up an! chen stops. Pereet alternation eceurs sehen bath 5, and ryare zero, As the quantity fry approaches zero, there isan inereasing tendeney toward alsemation, This has practical signitcar use it enbanees tae possibility of prodveing polymers with appreciable amounts of both monomers from wide cange of feed compositions C. BLOCK COPOLYMERIZATION (r,> 1, > 1) TF ranxl are both greater than unity, then each radical would prefer adel addition of she same type of monomer would continue successively unl ther isa chance addition of the ether type at mone nd the sequence af this monomer is added repeatedly. Thus the resulting f= &) box aie no known where freapproaehes 1 ity 1), there 1. Indeed, the product sf is almost sl ways less than unity. Tale 8.1 polymer is block copolymer. In the estreme ease of this type of polymerization Monomers underao simulaneous and independent homapolymeszatian, bow ‘eases of this type of polymerization. Even though eases exis hiss th selivity raios for some monomers Example 8.1: The seactivity rats for the copolymerization of methyl methacrylate (1) and vinyl chloride (2) at 68° 6.1. To ensuce that the copolymer eamaains an appreciable «anny ( » this case) of the vin chloride, « chemist decided to carry out the copolymerization reaction with a feed composed of 8 inyl chloride, Will the chemist aehiove is ebjeetse? Hee 1G. 1G2NO.8) HEt2t hah 2F +02 S014 B= 1 y= 0286" Ir he difference inthe reactivities oF the nso monomers is large, i is impossible to increase the proportion of the les gotive monomer in the copolymer simply hy ineteasing ils composition inthe ed, IV. POLYMER COMPOSITION VARIATION WITH FEED CONVERSION Singe the reactivity ratios and rear h reactions, Consequently, the composition mnitudes, there are necessarily differences, ally of different in oe rate of possible g the feed, fi, and that of the ops aby ene et