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where F == 'YF. Now let us try to obtain the properties of F without using the thermal equilibrium result (8.25) explicitly. The question we ask is: What properties must F have for this simple Langevin equation to be equivalent to the diffusion equation (8.20) deduced by Einstein The ensemble average of F can be given in terms of that of x by averaging (8.29):



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Although there are no reported polymerizations of simple cyclic sul des of ring size 5 and higher, polymerizations of 1,3,5-trithane (the cyclic trimer of thioformaldehyde) (LX), disul des such as 1-oxa-4,5-dithiacycloheptane (LXI), and trisul des such as norbonene trisul de (LXII) have been achieved [Andrzejewski et al., 1988; Baran et al., 1984; Moore et al., 1977; Zuk and Jeczalik, 1979].

(F(t))

The polymerization of LXIII, a stable isolable zwitterion, on heating or photolysis involves nucleophilic attack by phenoxide anion on the cyclic sulfonium ring [Hoyle et al., 2001; Odian et al., 1990]. The reaction proceeds as a step polymerization.

7-93

dt (x).





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To delete a table, select it in the Navigation pane and press . Access asks you to confirm the deletion before permanently removing the table, along with any data that it contains. Before attempting to remove a table, ensure that it does not contain any important data that you need.

7-8 CYCLOALKENES Cycloalkenes undergo ring-opening polymerization in the presence of coordination initiators based on transition metals to yield polymers containing a double bond, for instance, cyclopentene yields polypentenamer [IUPAC: poly(pent-1-ene-1,5-diyl)] [Amass, 1989; Cazalis et al., 2000, 2002a,b; Claverie and Soula, 2003; Doherty et al., 1986; Ivin, 1984, 1987; Ivin and Mol, 1997; Ofstead, 1988; Schrock, 1990, 1994; Trnka and Grubbs, 2001]. The

(8.30)

7-94

We can calculate (x) if we determine the probability distribution p(x, t) that obeys Einstein's diffusion equation (8.20). Assuming that the particle starts at the origin at t = 0, you can show (Problem 8.2) that the solution of (8.20) is given by

CH CH(CH2)3

(2.62)

polymerization is referred to as ring-opening metathesis polymerization (ROMP) by analogy to the ole n metathesis reaction, which results in a transalkylidenation between two alkenes:

q,(t) ::::::

7-95

A~vr cos (1ft) .

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Both ole n metathesis and ROMP require similar initiators and proceed by the same reaction mechanism. The initiating and propagating species are metal alkylidene (carbene) complexes. The original initiators used for ROMP were two-component systems, composed of a halide or oxide of an early transition metal such as W, Mo Rh, or Ru with an alkylating agent (Lewis acid) such as R4 Sn or RAlCl2 , which generate metal carbenes in situ. These initiator

In other words, the swing oscillates 90 degrees out of phase with our pushing. Our push is stronger when the swing is at its point of minimum height and weaker when it is at its point of maximum height. This is exactly what you experience when pushing a child on a swing. As the swing approaches you, you must decrease the intensity of the force so that it vanishes when the swing reaches its point of maximum height. Far away from resonance (i.e., Iw VA), q,(t) :::::: 0 and the swing does not move. Figure 2.6 plots the average of the square of (2.61) over one oscillation period against w for a value of / 100 times smaller than the natural frequency. Notice that it decreases quickly as the frequency becomes different from the natural frequency. The sharp peak in Figure 2.6 is typical of resonant phenomena. To solve (2.56) for any driving force, it is convenient to solve it first for an impulse force c5(t - t'). This solution is called the Green's function, G(tlt'), after George Green, a nineteenth-century mathematician from Nottingham, England. The equation for the Green's function is

systems have limitations the strong Lewis acids make MW control more dif cult, there is incompatibility with a variety of functional groups, the actual metal carbene initiators are formed in low concentrations, and temperatures of 100 C are needed. Since these initiators are relatively inexpensive, they still nd use in commercial applications. Better control of the reaction is achieved by using stable, isolable metal carbene complexes, such as the Schrock initiators based on molybdenum and tungsten (LXIV, Mt W, Mo) and the Grubbs initiators based on ruthenium (LXV). The Schrock initiators

You can rename fields in any table.To do so, double-click the field label and type a new name. When you finish, press .

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