Solutions to Final exam 1.

(i)

No Byproducts (ii) Addition Mechanism; Step Growth Process (iii) Micro-Suspension Process (oil in water homogenization) - part marks for stating suspension 2. Tg1 = the glass transition of homopolymer from monomer A + B Tg2 = the glass transition of homopolymer from monomer A + C Tgf = the glass transition of copolymer from monomer A + B + C Wb is weight fraction of monomer B Wc is weight fraction of monomer C Tg1 = 43.36oC = 316.36oK ; Tg2 = 60oC = 333oK ; Tgf = 75.2 oC = 348.2oK 1/Tgf = wb/Tg1 + wc/Tg2 ; wb + wc = 1 1/333 = 1/316.36 + wc(1/348.2 1/316.36) W c = 0.5465 ; W b = 0.4535 Mwb = 200g/ mole ; Mwc = 116 g/mole

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W = nMw ; nb = 0.002732 moles ; nc = 0.00391 moles For mole eq. 1/ (0.002732 + 0.00391) = 150.56 times above nb = 0.411 mole equivalents of monomer B nc = 0.589 mole equivalents of monomer C na = 1.0 mole equivalent of monomer A 3.

tsolvent = 30 sec
C (g /dL)
0 0.5 1 1.5

t (sec)
30 75 150 255

i
1.5 4.0 7.5

i /c
3 4 5

Plot

i /c Vs C and intercept gives []

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4. The resin displays; (a) An Endothermic transition with change in baseline at a temperature of 40.5 oC (onset) to 47 (endpoint) . This indicates a glass transition temperature with a midpoint at 43.36 oC. (b) An Endothermic transition with a broad melting and peaks at 62 oC & 68.61 oC. this indicates that it is a semi-crystalline resin (perhaps liquid crystalline) and becomes clear (amorphous) at 70 -72oC. (c) An exothermic transition on cooling, with a peak temperature of 45.87 o C. This is an indication of crystallization of the resin from the amorphous state.

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5. Heating the microcapsule to a temperature above its Tg and/or melting point (such as 70 to 75oC), may enable the pores of the shell to close or coalesce. 6.

7. The radical adds via a head to tail fashion; (Structure I) , which is resonance stabilized by the ester moiety (carbonyl group). In structure II, there is only inductive stabilization.

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8. Potassium persulfate is a water soluble initator utilized for emulsion polymerization. This process is a micro-suspension process that requires organic soluble initiators such as di-alkylperoxides. 9.

Mw = 254.4 g/mole ; [M] = 100 g / 254.4 g/ mole = 0.393 mole (note this bulk conditions = 0.393 mole/l) (Xn) = 850 ; (Xn)o = 1000 ; C = 0.135 X 10-4
[SH] = 5.1 moles/ l

10. The polymerization technique utilized for the core polymer is a freeradical process. The poly-dispersity of the core resin ( Mw/Mn = 2.30) is quite broad. The leaching of low Mw oligomers can be minimized or

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avoided if the polydispersity is decreased but keeping Mw similar; In other words, in order not to increase the Mw significantly, one would need to increase Mn or obtain a narrower polydispersity and keep the Mw at about 15,000. In order to do this, one could modify the process such that a controlled radical polymerization technique is employed resulting with narrower polydispersity (ie p << 1.5); such as NMP, ATRP, RAFT or group transfer.

11. For a more stereoregulated syndiotactic or isotactic polymer, a higher glass transition temperature would be expected and crystalline properties with a melting point may be obtained. The process could be modified, in theory, if a cationic polymerization process was utilized with Metallocenes. However, Metallocene polymerization process is predominantly utilized with electron releasing olefins (unsaturated monomers). The n-Lauryl methacrylate is an electron withdrawing unsaturated monomer and easily polymerized via free-radical or Anionic polymerization ,and unlikely via Cationic. Anioinc polymerization would not give a syndiotactic or isotactic polymer . Thus, it would be unlikely that the process of the present system

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could be modified to obtain a syndiotactic or isotactic polymer via Cationic process. 12. The Secant modulus is defined at 1% strain, = 0.01

13. The changes that could be implemented would be to either x-link the substrate or/and make it more crystalline .

14. The changes that you could suggest would be to modify Polyvinyl acetate (PVA) with a co-monomer that would increase the rigidity of the polymer. For instance styrene. Or you can substitute the PVA with a more rigid thermoplastic like polystyrene, or introduce x-linking.

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