3.3 Vinyl alcohol is an aleohol with chemical formula: ec a ‘This thermodynamically unstable monomer (enol) exists almost exclusively in the tautomeric form (acetaldehyde). For this reason poly(vinyl alcohol) (PVA) which formally derives from this monomer, can only bbe made via an indirest route and this involves polymerization of vinyl acetate ‘The mechanism will consists of initiation, propagation and termination steps, using a suitable radical initiator and vinyl acetate: boc, face Res GHC, GHC Followed by hydrolysis of the polyvinyl acetate. PVA is prepared by partial or complete hydrolysis of polyvinyl acetate to remove acetate groups. ‘Vinyl alcohol is highly crystalline and intra/inter H bonded. To dissolve it. these bonds must be broken and replaced by PVA-water H bonding, Leaving some of the acetate units unhydrolised sakes the polymer (in fact a copolymer in this ease!) less crystalline and casier to dissolve, (BIS First of all it is necessary to evaluate the decomposition rate constant ky at the required ‘temperature. From the Arshenius equation: tnk=in4-Ze where R isthe gas constant and Tthe temperature, it follows that the rate constant at T3 ean be obtained from the rate constant at T; if the activation energy is known, using the relationship: Values of rate constants at 323 K for the various initiators are tabulated below along with the half times, ty2 ealeulated from:36 ner Tas aa Benzoyl peroxide 490% 107 393, ‘Tert-butyl peroxide 72x10" 286400 Azobisbutyroninile 200x108 96 2.2" azobir2.4-dimethyl valeronitile 2.07% 107 93 Both benzoyl peroxide and azcbisbutyronitrile are suitable initiators while dimethyl valeroniitile has too short lifetime. For first order kinetics: The ratio ¥;' Vis proportional to the amount of initiator that has decomposed at time ¢. The fraction of initiator unrencted at time ris: Te _YaVe Va Va and, after substituting in the rate law equation for frst order kinetios: This evident that a plot of In slope ki. This is true for the data reposted by Overberger etal. and the graph shown below indicates that the decomposition, of the tor follows first order kinetics. The decomposition rate constant is 9.67 x10" <7. 4 3s In Viv VD © 10000 20000-30000 1/ seconds:(SP initiation is first order with respect to the initiator concentration, the rate of initiation is: 2a. sand if termination is second order with respect to the growing chains: 2k(MJIM']. ‘The rate of polymerization is given by: wpe hp aL} "7[M] ‘We therefore expect that the ratio of the rate of polymerization to the square root of the concentration of initiator should be constant: a kyla HM] uy? as verified by the tabulated data, The kinetic chain length is defined by:anu, since wer? and yx] ie follows that 7 and so the degree of polymerization ny should vary as [J]"®. The tabulated data indicate that x, tend to a constant value and so the relationship. should be of the form: quaniveal TH Mai mal” yl 0.098 11090 0070 11040 0.059 7250 007 $390 059 6150 oon $530 0.009 880 0088, 0.089) ose, 0089 0.099, 6.9005 a.0004 6.9003 oh 6.9002, e.0001 The experimental data points are fitted by the linear relationship: S104? +3 s.10-83.9 In steady state conditions, the sate of initiation equals the sate of termination, in this case from wall seaction and so: 2a (T Fat [RMoo] [PMs] = 2k] et Since yp= hp [RMeTIIM] pap 2ks(T] [MJ Kiva roa Feat in the above equation we obtain: vp= pot (MTC after substituting fy. 3.11 (a) The initial sate of initiation is: vy = 2a >ap Pet M main BOL 104 5.702 M mi 2 and: 49x10°.M min Ferm mF? 2-2 (b) the kinetie chain length is given by:= Inky ~0.Sink, =In4, ~0.5in4, -— Rx oat 27 ot ,-038)/ 1 Int. RQ@ —n0.67 = ONS = Ce 32: (cose, Sencsai Jot! 88.104 (e, -0.58,)=1' epee (@) The rate equation for propagation is: al] eal AW, tay all Pa, =k, Since initiation is a first order reaction: ai ~ MLE gl) aad Url -Le™* Aficr substituting and integrating, using-theinitie-eenditior A4— pirate ofa) efi) 2 1/2 5.72407 venta] | ] l-e S707 1 oo = In(l- p)=2 PQ mer hip wo | and = K sain 0. 24$¢3.12 The number average degree of polymerization needs to be calculated from the intrinsic viscosity values. The relationship: sq = (Uso + GISYEMI is then used to obtain Cs (by plotting I/xx versus [S][M]). Values of slope (C3) are 3.45 x 109 and 1.06 x 10* for methyl iso-buty! ketone and ethyl acetate. respectively. saleear TOT ia) iil acetate 1.076 0.980 2836 1614 0880 2427 2421 0.680. 1670 ‘6458 0.500 1069) setiylsocburl ketone 0492 0300 510 0738 0.240 369 1108 0.190 263 2958 0.095 96 0012 oor 0.008 0.006 0.004 ee Y> 1O6E-Oi + 2.60804 ; —_— o 4 6 8 [SVAf]