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This is generally the case for the typical polymerization of epoxides as well as other cyclic monomers, although the regioselectivity is not 100%. The degree of isoselectivity is generally decreased in proportion to the extent of ring opening at bond 2. There are no initiator systems that are even moderately isoselective subsequent to bond cleavage at bond 2. The extent of regioselectivity at bond 1 is greater than 90% for many anionic polymerizations. It is very dif cult to give a generalization that holds up well in this respect. In a number of polymerizations signi cant amounts of cleavage at bond 2 have been reported, such as propylene oxide polymerizations by Zn(C2 H5 )2 or Al(C2 H5 )3 with H2 O or Zn(C2 H5 )2 with CH3 OH, and styrene oxide polymerization by aluminum isopropoxide [Tsuruta and Kawakami, 1989]. The extent of regioselectivity depends markedly on reaction conditions in some systems. Thus, polymerization by Zn(C2 H5 )2 /H2 O proceeds exclusively by cleavage at bond 1 in many polymerizations but signi cant extents of cleavage occur at bond 2 in other polymerizations with the differences depending on the relative amounts of Zn(C2 H5 )2 and H2 O. Cationic polymerizations of epoxides are signi cantly less regioselective and isoselective compared to anionic polymerizations. Polymerization of racemic propylene oxide proceeds differently depending on the initiator. Polymerization by potassium hydroxide or alkoxide proceeds with better than 95% regioselectivity of cleavage at bond 1, but the product is atactic [Tsuruta and Kawakami, 1989]. Both (R)- and (S)-propylene oxide react at the same rate as shown by the invariance



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n) - :F(Q).





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of the optical rotation of unreacted monomer with conversion in a polymerization where the initial ratio of the two enantiomers was unequal. The atacticity of the product indicates that the initiator is unable to distinguish between the R and S enantiomers of propylene oxide and both enantiomers react at the same rate with complete cross-propagation. Polymerizations by Zn(OCH3 )2 and a, b, g, d-tetraphenylporphyrin (structure VI in Sec. 7-2a-1) proceed in a completely regioselective manner (cleavage at bond 1), but with only modest isoselectivity (67% and 68% isotactic dyads, respectively) [Le Borgne et al., 1988; Tsuruta, 1981]. For polymerization by a, b, g, d-tetraphenylprophyrin, the degree of isotacticity varied with the ratio of (R)- and (S)-propylene oxide in the feed. Polymerization proceeds as an asymmetric enantiomer-differentiating polymerization but with signi cant cross-propagation. The highest isoselectivity reported, (mm) 0.81, for a propylene oxide polymerization was achieved with an initiator derived from dialkylzinc and methanol [Hasebe and Tsuruta, 1988; Tsurata, 1986; Tsuruta and Kawakami, 1989; Yoshino et al., 1988]. The stereochemistry of ring-opening polymerizations of episul des, lactones, lactides, N-carboxy-a-amino acid anhydrides, and other monomers has been studied but not as extensively as the epoxides [Boucard et al., 2001; Chatani et al., 1979; Duda and Penczek, 2001; Elias et al., 1975; Guerin et al., 1980; Hall and Padias, 2003; Imanishi and Hashimoto, 1979; Inoue, 1976; Ovitt and Coates, 2000; Spassky et al., 1978; Zhang et al., 1990].

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Steps to convert excel document to PDF programmatically:
Steps to convert excel document to PDF programmatically:

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Steps to convert excel document to PDF programmatically:
Steps to convert excel document to PDF programmatically:

2 3 4 5

(C.23)

8-16

In vectorial calculus, such a directional derivative is given by the scalar product of the gradient with the unit vector that defines the given direction. Here, too, a quaternion gradient can be introduced in an analogous way. Viewing F(Q) as F(qo, ql, q2, q3), where Q qO+ql i+q2j+q3k, we can expand:F( Q+ n) = :F(qo+ no, ql nl, q2+ n2, q3 + n3) in a Taylor series around:F(Q) = :F(qO, q}, q2, q3) and rewrite (C.23) as

The polymer stereosequence distributions obtained by NMR analysis are often analyzed by statistical propagation models to gain insight into the propagation mechanism [Bovey, 1972, 1982; Doi, 1979a,b, 1982; Ewen, 1984; Farina, 1987; Inoue et al., 1984; Le Borgne et al., 1988; Randall, 1977; Resconi et al., 2000; Shelden et al., 1965, 1969]. Propagation models exist for both catalyst (initiator) site control (also referred to as enantiomorphic site control) and polymer chain end control. The Bernoullian and Markov models describe polymerizations where stereochemistry is determined by polymer chain end control. The catalyst site control model describes polymerizations where stereochemistry is determined by the initiator. 8-16a 8-16a-1 Polymer Chain End Control Bernoullian Model

The Bernoullian model (also referred to as the zero-order Markov model) assumes that only the last monomer unit in the propagating chain end is important in determining polymer stereochemistry. Polymer stereochemistry is not affected by the penultimate unit or units

~:F(Q) = lim :F(Q+ n)-:F(Q) on -+0 o 0F o = lim {nooo:F +n 1 :F +n2 :F +n3 +O( 2)} 0 Xl 0 X2 0 X3 -+0 Xo =S(nO):F(Q), (C.24)

8-85 8-86

= 1.

further back. Two different propagation events are possible meso or racemic (Eqs. 8-85, 8-86). Equations 8-85 and 8-86 are general in representing two cases: (1) where the stereochemistry of the polymer chain end units is determined relative to the penultimate unit when

(C.25)

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Dec 7, 2017 · See that example for information on how to open an Excel workbook, write data into it, and save it. Note that before you can use the Excel interop library, you need to open the Add References dialog, click the .NET tab, and select Microsoft.Office.Interop.Excel (or whatever version you have installed on your system.)












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