Macromolecular Chemistry

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1 Macomolecula Chemisty R R O H 2 C CH + CO CH 2 CH C Lectue 13

2 Fee Radical Co-polymeization Fee Radical Copolymeization ~ ~ ~ ~ ~ ~ ~ ~ Assume chain end concentations ae constant at steady state

3 If If 1 > 1 >1 this means that ~M 1 1 adds M 1 moe eadily than M means 2. If 1 is zeo then M 1 does not undego homopolymeization!! This impotant elationship can be expessed in tems of mole factions athe than concentations

4 Copolymeization Equation This gives the Instantaneous mole faction of M 1 in the copolyme

5 Finemann-Ross Equation Finemann Ross Equation

6

7 Let s actually calculate 1 and 2 fom some data We un the copolymeization fo a vey shot time stating with diffeent weight atios of 2 monomes. The assumption is that f does not change in this expeiment We isolate the small amount of polyme geneated and detemine the atio of monomes incopoated.by nm, fo example We apply the Fineman-Ross analysis and extact the eactivity atios. Chis

8

9 1 > 1, 2 < 1 o 1 < 1, 2 > If 1 > 1 (k11 > k12) and 2 < 1 (k22 < k21) then M 1 is moe active than M 2 whethe eithe ~M 1 and ~M 2. F 1 is always lage than f 1 and the cuve is always above the diagonal. The situation is simila fo 1 < 1, 2 > 1 but the cuve is below the diagonal.

10 Ideal copolymeization as 1 x 2 = 1 ( 2 =1/ 1 ), it becomes an ideal copolymeization d[m ] d[m ] 1 = 2 1 [M 1] [M ] 2 F In this case ~M 1 and ~M 2 have the same pefeence fo adding eithe of the two monomes. f

11 Condition unde which F, the mole faction of monome in the polyme and f, the mole faction in the feed emain constant though the whole polymeization.that is, these atios ae not a function convesion

12 1. Ideal copolyme Fa (polyme composition) A = styene B = butadiene a =.75, b = = 2 = fa (monome composition)

13 Fa (polyme composition) Altenating Copolyme A = styene B = maleic anhydide a 1 =.5, = b = 2 = fa (monome composition)

14 1. Rich in one monome Fa (composition of polyme) A = vinyl acetate B = styene a 1 =.1, = 2 b = 5 = fa (Composition of monome)

15 1. Quite typical copolymeisation Fa (polyme composition) A = Acylonitile B = Butadiene a 1 =.46, = 2 b = = Azeotopic Composition fa (monome composition)

16 F f

17 Poly(styene-alt-maleic anhydide) + O O O O δ O δ+ O Chage tansfe complex O O O [ ] n

18 Chage tansfe complex polymeization (altenating copolyme). R R O H 2 C CH + CO CH 2 CH C R R H 2 C CH + SO 2 CH 2 CH SO 2

19 1 > 1, 2 < 1 o 1 < 1, 2 > If 1 > 1 (k11 > k12) and 2 < 1 (k22 < k21) then M 1 is moe active than M 2 whethe eithe ~M * 1 and ~M 2*. F 1 is always lage than f 1 and the cuve is always above the diagonal. The situation is simila fo 1 < 1, 2 > 1 but the cuve is below the diagonal.

20 What is is constant hee??? This is is a bit discouaging!

21 Estimating Reactivity Ratios Estimating Reactivity Ratios measuement of 1 and 2 is possible by applying the Fineman Rose equation but it is a bit tedious!

22

23 Genealizations: Q and e This is a puely empiical elationship Q and e come fom measuements of 1 and 2 Ideal condition is same Q and e values Poceeds pooly if Q 1 and Q 2 ae vey diffeent Tends towad altenating if Q s ae the same and e s aelage but of opposite sign.

24

25 I+III, II+IV and same Χ Statistical Copolymes I+II o III+IV Poo Copolymeization Χ I+IV o II+III altenating

26

27 Conclusions-adical copolymes Co-polymes ae impotant Popeties depend on composition In geneal, these mateials ae heteogeneous Mayo equation allows calculation of composition knowing 1 and 2 Finemann Ross appoach allows detemination of 1 and 2 Alfey Pice allows estimate of 1 and 2

28 What about step gowth copolymes?? We discussed A B type step gowth polymes -ABABABA- A If is the numbe of A molecules at the beginning of the polymeization and is the numbe if B molecules, B We define, the stoichiometic imbalance as = A B If p is the convesion (as in Caothes equation) then faction of B at p is p A o p B and the numbe of uneacted goups A and B is A = ( 1 p) A B = ( 1 p) = (1 B p) A

29 At this point, the numbe of A and B end goups is A + B, but 2 ends pe chains the numbe of chains in the ja is. 1 = ( A + B ) 2 Which is. = 1 2 (1 p) A + (1 p) A A 1 O.. = 1+ 2 p 2 ow..the total numbe of epeat units, is. 1 = ( A + B ) One epeat unit fomed pe eaction 2

30 Remembe. B A = So. + = + = A o A o A DP is the numbe of monome units divided by numbe of chains + + = = p DP A A Which luckily educes to p DP = Supplementay Homewok Show Algeba To hee!

31 DP = p This is nice!!! ote that if thee is no stoichiometic imbalance, =1 and we get.. DP = 1 The Caothes 1 Equation!! p When A is totally consumed (p =1) then. DP 1+ = 1

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