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510.316 Biomaterials I, Fall 2009 Problem Set #1 Solutions & Grading Rubric 100 Points Total 1.

15 points total For each paper: 1 point for writing down the name and drawing (or describing) the chemical structure of the main biomaterial used. 1 point for briefly detailing the application that it is used for (2-4 sentences should suffice). 1 point for specifying the class of materials that it belongs to (ex. Is it natural or synthetic?). Given the many ways that one can classify materials, any method of classification used is fine. 2. 10 points total See Figure 1 in Appendix I. For each structure: 1 point for drawing the monomer correctly. 1 point for drawing the polymer correctly. 3. 19 points total Structure: 2 points: High density PE is composed of linear, unbranched PE chains. 2 points: Low density PE is composed of highly branched PE chains (causing entanglement). 2 points: Linear low density PE is composed of linear PE chains with very short branches, as opposed to the longer branches of low density PE. Properties: 2 points: High density PE high crystallinity (very strong intermolecular forces and high tensile strength) 2 points: Low density PE amorphous (much less intermolecular forces and lower tensile strength than high density PE) 2 points: Linear low density PE amorphous (intermediate intermolecular forces and tensile strength) Synthesis: 2 points: High density PE coordination polymerization along with the use of an organometallic catalyst such as the Ziegler-Natta catalyst 2 points: Low density PE free radical polymerization under high pressure and high temperature 3 points: Linear low density PE coordination polymerization along with the use of an organometallic catalyst such as the Ziegler-Natta catalyst; two different alkene species, one of which has a short alkyl group, are copolymerized (see Figure 2 in Appendix I for clarification)

510.316 Biomaterials I, Fall 2009 4. 20 points total Reactivity: The reactivity of carboxylic acid derivatives, from most reactive to most stable, is as follows: acyl halide > anhydride > carboxylic acid > ester > amide. Therefore, reaction c would be most favorable if we only consider the reactive nature of the reagents. Le Chateliers Principle: To increase the total amount of polymers (C) made, one can boil away the byproduct (D) in the reaction A+B C+D. Water boils at 100 C, methanol boils at 65 C, and hydrochloric acid can boil at a range of temperatures, depending on its concentration (although it is most likely to boil at a higher temperature than water or methanol). Since it is easiest to boil away methanol, reaction b would be most favorable if we only consider Le Chateliers Principle. Other factors: Running reaction c would be rather problematic because its byproduct is a strong acid. Since reaction vessels and pipes in industry are often made from metal (metal is cheap), reactions with acidic byproducts should be avoided. Even if one uses non-corrosive pipes, the problem of dealing with the leftover hydrochloric acida toxic wasteremains. In conclusion: Even though the carboxylic acid of reaction a is slightly more reactive than the ester of reaction b, the low boiling point and volatile nature of methanol makes it very easy to increase the yield of the product. Therefore, it is simplest to justify that reaction b is the best choice. However, as long as good logic is used in reasoning why one of the other two reactions is chosen, points will not be deducted. Please review Appendix II for extra clarification on #4. 5 points are given for discussing the reactivity of the reagents. 5 points are given for discussing the relevance of byproducts boiling points (Le Chateliers Principle). 5 points are given for any other relevant considerations. For example, one can discuss the acidity of HCl in reaction c. 5 points are given for choosing the best reaction scheme based on the considerations of the various factors above. 5. 10 points total Synthesis: Poly(SBS) is synthesized by anionic living polymerization, starting with an initiator that confers a negative charge onto a styrene monomer. This negatively charged styrene monomer then reacts and joins with another styrene monomer (thus giving it the charge). This process propagationcontinues until all of the styrene monomers are exhausted. We now have poly(S). Next, butadiene monomers can be added into the reaction vessel. The negative charge on the last styrene unit of a poly(S) chain reacts and joins with a butadiene monomer. Other butadiene monomers are subsequently added to the chain (propagation). Once the butadiene monomers have been exhausted, chains with a block of styrene units followed by a block of butadiene units are formed. We now have poly (SB). At this point, to finish off the reaction, one can simply add styrene monomers into the reaction vessel again, with styrene monomers adding to each chain and forming poly(SBS). A

510.316 Biomaterials I, Fall 2009 scavenger/terminator molecule can be added into the reaction vessel to remove the residual negative charge on the last styrene unit and terminate the reactivity of the living chains. Note: There are other reaction schemes that can be used to synthesize poly(SBS). For example, one can start with a difunctional molecule that can attach one butadiene unit on each end and initiate them both, resulting in anionic living polymerization proceeding from both ends. In other words, a chain of poly(B) grows from both ends at once. Once the butadiene monomers have been exhausted, styrene molecules can be added into the reaction vessel to attach styrene units onto both ends of poly(B), forming poly(SBS). Properties: Poly(SBS) is a rubbery thermal elastomer. It has regions of high crystallinity (styrene) and regions of low crystallinity (butadiene). Given a sample of poly(SBS) in room temperature (think about a block of rubber, which can consist of many poly(SBS) polymers packed together), the butadiene regions are rather amorphous, but the styrene regions remain rigid and crystalline. These rigid regions of styrene can serve as physical crosslinks that hinder the freedom of movement in the soft butadiene regions, thus conferring poly(SBS) the elastic nature so characteristic of rubbers. 5 points for discussing the synthesis of poly(SBS). To get full credit, you need to mention anionic living polymerization. 5 points for describing the elasticity of poly(SBS) and the origin of its rubbery nature. 6. 26 points total The equations used for this question can be found in pages 375-377 of your textbook. From the monodispersed PSt samples, we can derive the standard curve for linear polystyrene samples: LogMw = 12.213 0.2489*V, where V is the elution volume (ml) (log10 is used)
Mw 2000000 850000 470000 105000 52000 11000 LogMw 6.301 5.929 5.672 5.021 4.716 4.041 Elution volume (ml) 23.2
logMw

Standard Curve
7.0 y = -0.2489x + 12.213 R2 = 0.9807

6.0

25.4 26.7 29.3 30.3 32.2

5.0

4.0

3.0 20.0

22.0

24.0

26.0

28.0

30.0

32.0

34.0

Elution Volume (m l)

Using the standard curve and the linear equation above, we can then calculate the molecular weight (Mi) of each fraction as listed in the table. Note: the third column, wi, is calculated from RI i / RI i , which is essentially the intensity weight of the eluted species.

510.316 Biomaterials I, Fall 2009

Elution Volume (ml) 32.5 32 31.5 31 30.5 30 29.5 29 28.5 28 27.5 27 26.5 26 25.5 25 24.5 24 23.5 23 22.5 22 21.5 21 20.5 Sums:

RI (a.u.) 0.0 0.8 4.5 15.0 30.2 60.0 105.5 165.3 225.1 256.0 250.3 220.6 181.5 147.1 120.0 88.0 67.8 50.1 36.2 22.1 12.3 6.9 2.0 0.1 0.0 2067.4

wi 0.00000 0.00039 0.00218 0.00726 0.01461 0.02902 0.05103 0.07996 0.10888 0.12383 0.12107 0.10670 0.08779 0.07115 0.05804 0.04257 0.03279 0.02423 0.01751 0.01069 0.00595 0.00334 0.00097 0.00005 0.00000 1

log(Mi) 4.1238 4.2482 4.3727 4.4971 4.6216 4.7460 4.8705 4.9949 5.1194 5.2438 5.3683 5.4927 5.6172 5.7416 5.8661 5.9905 6.1150 6.2394 6.3639 6.4883 6.6128 6.7372 6.8617 6.9861 7.1106 (irrelevant)

Mi 13296.9 17709.2 23585.8 31412.3 41836.0 55718.6 74207.9 98832.5 131628.5 175307.3 233480.2 310956.8 414142.7 551569.2 734598.4 978363.0 1303016.8 1735401.6 2311266.4 3078222.4 4099680.4 5460092.5 7271935.2 9685008.4 12898820.5 51730090

wi/Mi 0.0000E+00 2.1851E-08 9.2286E-08 2.3098E-07 3.4917E-07 5.2087E-07 6.8767E-07 8.0900E-07 8.2718E-07 7.0634E-07 5.1854E-07 3.4315E-07 2.1198E-07 1.2900E-07 7.9014E-08 4.3507E-08 2.5168E-08 1.3964E-08 7.5759E-09 3.4727E-09 1.4512E-09 6.1126E-10 1.3303E-10 4.9943E-12 0.0000E+00 5.62E-06

wi*Mi 0.0000E+00 6.8528E+00 5.1338E+01 2.2791E+02 6.1113E+02 1.6171E+03 3.7868E+03 7.9022E+03 1.4332E+04 2.1708E+04 2.8267E+04 3.3180E+04 3.6358E+04 3.9245E+04 4.2639E+04 4.1645E+04 4.2732E+04 4.2055E+04 4.0470E+04 3.2905E+04 2.4391E+04 1.8223E+04 7.0349E+03 4.6846E+02 0.0000E+00 4.80E+05

wi*Mi

0 0.204132 1.370733 5.483785 13.25691 31.63279 66.82111 125.7791 205.7463 281.0981 330.154 349.5364 345.4785 336.3558 329.6092 290.4181 268.7258 238.5445 207.0857 151.8762 101.5493 68.47854 23.89064 1.47936 0 3774.575

Mw = wi M i = 4.799 105 g/mol

Mn =

1 = 1.778 105 g/mol w Mi i

[ ] =

w [ ] = K w M
i i i

PD = Mw/Mn = 2.70
a i

= 3.71 10-4 * 3774.47 = 1.40 dl/g

(Minor points may be taken off for numerical mistakes. You will mostly be graded for using the correct approach.) 5 points for generating a suitable calibration graph. It is preferred that you generate a logMW vs. Elution Volume graph (as it gives a nice linear fit), but a MW vs. Elution Volume graph is also acceptable, as long as the curve-fitting is reasonable (e.g. a power fit). 5 points for the weight average molecular weight. 5 points for the number average molecular weight. 1 point for the polydispersity. 5 points for the intrinsic viscosity. 5 points for clearly showing your work.

510.316 Biomaterials I, Fall 2009

Appendix I
Figure 1 (regarding #2):

Figure 2 (regarding #3):

510.316 Biomaterials I, Fall 2009

Appendix II
A few extra quibbles on #4: - To understand the reactivity ranking of carboxylic acid derivatives, please review the stability of leaving groups. The carboxylic acid derivative with the most stable leaving group is the most reactive (e.g. acyl chloride is very reactive because Cl- is very stable). - To neutralize the HCl byproduct in reaction c, we can consider adding a base into the vessel. However, by doing so, we may need to deal with residual salts and potential side reactions. - Methanol and HCl are both toxic chemicals, but methanol is easier to handle in an industrial setting. The volatile nature of methanol makes it very easy to be removed from the reaction vessel. - Bulk polymerization: no need for solvents (thus no need for solvent extraction from the product), easy to scale up, and results in large amount of heat given off in the reaction vessel (since theres no solvent to absorb the heat.) - Interfacial polymerization: organic solvent is needed (thus the problem of solvent extraction), may be difficult to scale up (reaction only occurs at the interface, so one needs to deal with extracting products from the delicate interface), and occurs very quickly - The cost of terephaloyl chloride (reaction c) is relatively high compared to the reagents used in reactions a and b.