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Evaluate this result and discuss its implications on the propagation mechanism for propylene oxide polymerization Brie y explain each of the following: a There is only one disyndiotactic structure for ( CHRCHR0 whereas there are , )n erythro- and threodiisotactic structures b Addition of aluminum trialkyl to a traditional Ziegler Natta polymerization system (eg, b-TiCl3 , propene) increases the polymerization rate up to a maximum after which Rp either remains constant or decreases c Hydrogen lowers the molecular weight of polyethylene and polypropene synthesized using traditional Ziegler Natta and metallocene initiators d Low temperatures enhance syndioselective polymerization e Metal polymer bonds are sometimes found in polymers synthesized using traditional Ziegler Natta and metallocene initiators C NMR analysis of polypropene sample A showed m 0:78, r 0:22, mm 062, mr 0:33, rr 0:05, mmm 0:44, mmr 0:27, rmr 0:06, rrm 0:04, mrm 0:13, rrr 0:01.



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(C.57)

Click the Tasks button in the Navigation pane to open the Tasks component. Click the New Task button. Outlook displays a Task window.

Polypropene sample B showed m 0:80, r 0:20, mm 071, mr 0:19, rr 0:10 What type of propagation mechanism (Bernoulli, rst-order Markov, catalyst site control) is indicated for the synthesis of samples A and B.

= -2 Rn + nll ,





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8-10 Methyl methacrylate polymerization was carried out using rac-C2 H4 (Ind)2 ZrMe2 with C(C6 H5 )3 B(C6 F5 )4 in the presence of triisobutylaluminum at 0 C [H. Deng, T. Shiono, and K. Soga, Marcomolecules, 28, 3067 (1995)]. 13 C NMR of the polymer showed the pentad structure mmmm 0:869, mmmr 0:0155, rmmr 0:0014, mmrm 0:0005, rmrm 0:0027, mmrr 0:0177, rmrr 0:0165, mrrm 0:0089, rrrm 0:0165, rrrr 0:0510. Show by analysis of the stereoerrors whether polymerization occurred by chain end control or catalyst site control. 8-11 Consider each of the following metallocene initiators: a. C2 H4 (Cp)2 ZrCl2

1 (-

b. rac-Me2 Si(H4 Ind)2 ZrCl2 c. meso-Me2 Si(H4 Ind)2 ZrCl2 d. Me2 C(Cp)(Flu)ZrCl2 e. Me2 Si(3-isopropyl-Cp)(Flu)Zr2 For each initiator, indicate the (1) type of symmetry, (2) symmetry elements, and (3) stereochemistry of polymer produced.

(C.58)

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The preceding chapters dealt with the synthesis of polymers by polymerization reactions. This chapter describes the synthesis of new polymers by modi cation of existing polymers using a variety of chemical reactions [Allen and Bevington, 1990; Fettes, 1964a,b; Moore, 1973]. These include the esteri cation of cellulose, crosslinking of polyisoprene, hydrolysis of poly(vinyl acetate), and chlorination of polyethylene. A second aspect of polymer reactions is the use of a polymer as a carrier or support for some component of a reaction system [Benham and Kinstle, 1988; Manecke and Storck, 1978; Mathur et al., 1980]. Examples include polymeric brominating and Wittig reagents, the Merri eld solid-phase synthesis of polypeptides, and polymeric catalysts.

n, that is,

9-1 PRINCIPLES OF POLYMER REACTIVITY Polymers undergo the same reactions as their low-molecular-weight homologs. Acetylation of the hydroxyl groups of cellulose is basically the same reaction as acetylation of ethanol, chlorination of polyethylene follows the same mechanism as chlorination of n-hexane. It is usually assumed that the reactivity of a functional group in a polymer and a small organic molecule are the same. This is the familiar concept of functional group reactivity independent of molecular size (Sec. 2-1), which is the basis for analyzing polymerization kinetics. However, in many instances, the reaction rates and maximum conversions observed in the reactions of polymer functional groups differ signi cantly from those for the corresponding low-molecular-weight homolog. Polymer reaction rates and conversions are usually lower, although higher rates are also found in some reactions [Morawetz, 1975; Plate, 1976;

(C.59)

Principles of polymerization, 4th edition, by George Odian ISBN: 0-471-27400-3 # 2004 John Wiley & Sons, Inc.

Rempp, 1976]. The reaction conditions under which polymer reactivity differs from that of a low-molecular-weight homolog are discussed below. 9-1a Yield

fJ:. e n9/211e 0,9/2.

3 4 5

Yield or conversion in reactions of polymers means something quite different from that in small-molecule reactions when the conversion is less than 100%. For example, 80% yield in the hydrolysis of methyl propanoate has no effect on the purity of the propanoic acid that can be obtained assuming the appropriate techniques are available to separate starting material and product. The 80% yield simply limits the maximum amount of pure propanoic acid that can be obtained to 80% of the theoretical yield. However, 80% yield in the corresponding hydrolysis of poly(methyl acrylate) does not result in 80% yield of poly(acrylic acid) with 20% unreacted poly(methyl acrylate). The product contains copolymer molecules, each of which, on the average, contains 80% acrylic acid repeating units and 20% methyl acrylate units randomly placed along the polymer chain. Unlike the corresponding small molecule reaction, the unreacted ester groups cannot be separated from the product since both are part of the same molecule.

(C.60)

0.8n

Noticing that exp(OO /2)0/2 and (0,/2) exp(nO /2) are the derivatives with respect to 0 of exp(OO /2) and exp(nO /2), respectively, we see that we can rewrite (C.60) as

0.2n

(C.61)

9-1

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