Tutorial question set 2 Week23 ‘Any queries contact ROR on R.K.O-Reilly @warwick.ac.uk 1. Write down the structures of the polymers expected to form in the following radical polymerisations? (were AIBN and BPO are radical initiators) This question is meant to make them think about the range of polymers you can form from a radical polymerisation. They should be able to draw BPO and AIBN and know how these are used to initiate a radical polymerisation. The final example is included to get them to think about the ability of different vinyl groups to stabilise the radical formed. con algu discuss ARN Blo Svodical Unitrators2. Inthe free radical polymerisation of 3-vinylbenzenethiol the polymer obtained as no pendent sulphur groups. Draw the structure if the polymer and propose a mechanism for its formation. SH Prparc Mpeah, ie | This polymerisation involves an intermolecular radical transfer process. In lectures we discussed the Use of thiols as chain transfer agents in radical polymerisations, (eee: ~ — ee Su < a7 4 eS ag Ce ater a 1" Fam a oe Rew mononrex Popegetein, Nee & gue Also conéide bes cheod Speces ct3. Predict the order of polymer molecular weight obtained (from lowest to highest) by solution {ree radical polymerisation of styrene in benzene, toluene, ethylbenzene, isopropylbenzene and t-butylbenzene. Assume each polymerisation is run under identical polymerisation conditions except for the solvent choice. Justify your answer. ‘The more stable the radical the more likely itis to form. ie a solvent that can forma stabilised radical will produce smaller polymer chains due to chain transfer and one which cannot will allow for higher molecular weight polymer to be formed. Fagheat Ma Vosest My lemene 7 b-boubjlbenrme > thee Vert Lee > bopepy benzene. EN = CRN a € a ee ian, Ep Po bemayti SaaS 2 pees lose S ree Stale eee Mes rackedh Crete) SbaXe She Useataey Fehicak V. Le Cihacn bonsterNe WW ; ae rt 2 ame) @° oe ie H oO = @h+ fase) = othe ag C ‘og a = 3 > a © AS oa K ASS \ page a Ts 28 0 A oS 3) ee toe ( iG =< Gavedo ae ae vay SK — aie car w Snvatle Gna 2»woyw? to oe —= <<] ( iene! poo sean ee A: pr Do08- eo! “suonestiawiAjod Sulmojjoy au 104 swsiueyaut paylerap MOUS “pyemundy => includes Cornmtinan Ole mame con attock aot Eber C in my Grd Hea sone prduct 1s olobarune A \ugh wy Sbawr Ud oxy to Per ashe Bingsity y a = eae hia ees?) ie hE @ | ca pat a5. Consider the radical copolymerisation of vinyl acetate (A) and vinyl TMS (8). ry=0.38 and t= 0.85 = ‘0 “A a A B ic Ta= 314K Tg=452K a) Plot using excel the copolymerisation curve (F versus f) for A? b)_ Ifyou start with 5g of A and 5g of B, what is the % of A in the copolymer? ©) What is the Tg of the copolymer formed in b)? 4d) What would be copolymerisation curve look like for A and macromolecular C (where the MW of Cis 6500 g/mol). Assume the reactivity ratio for the end group only. e)_ IF you start with 5g of A and 5g of C what is the % of A in the newly formed copolymer? a) see attached excel workbook —® Fa Geto From O- 1 Fgrl-Fa b) Using the copolymer equation Know fA and rg amm WA = te.) NN =0.0S% B= 1002 N= 005 Fro f mols F = moe focticn f Ma ti 9.05% In ‘n Feedst 2? See _ Reet 9,08 0.053 F204 Put tints copblyrves eqn FE 2 = OUSEI6 4 Fy OMe «)_ Use the equation . US.0% oF My & Wa exe! (or use plot) - Sy et ces 2 SE 4 9.5UG ie colt eon: Sto.5k 4) It would look the same as rB = rC Ss e) 5) <0.053 mols Gsoo = 0.000HW mols F C Faz 0.45 Eq= 0.013 3 & =0a9 942 & Ale polymer ‘This is not realistic as we have ignored all the other chains. 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