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Combinations of a Lewis acid, protogen or cationogen, and a reactive cyclic ether (e.g., oxirane or oxetane) have been used to initiate the polymerization of less reactive cyclic ethers such as tetrahydrofuran [Saegusa and Matsumoto, 1968]. Initiation occurs by formation of the secondary and tertiary oxonium ions of the more reactive cyclic ether, which then act as initiators for polymerization of the less reactive cyclic ether. The reactive cyclic ether, referred to as a promoter, is used in small amounts relative to the cyclic ether being polymerized and increases the ability of the latter to form the tertiary oxonium ion. 7-2b-3 Termination and Transfer Processes



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13 Jul 2015 ... Convert PDF to Word Using C# The first step will be to get the PdfBox package using the Nuget Package Manager. Now, import the following DLLs into your .cs file: The third step will be to install the DocX NuGet Package from the NuGet Package Manager: Let's read a PDF file and try to get the text from it.

(7.131)

Under certain conditions, irreversible chain-breaking reactions are absent and cationic ROPs of cyclic ethers proceed as living polymerizations. These conditions are found for polymerizations initiated with acylium and 1,3-dioxolan-2-ylium salts containing very stable counterions such as AsF , PF , and SbCl or with very strong acids ( uorosulfonic and 6 6 6





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tri uoromethanesulfonic) or their esters whose anions may form covalent ester bonds but in a reversible manner [Jedlinski et al., 1985; Penczek and Kubisa, 1989a,b; Penczek and Matyjaszewski, 1976]. The rate and degree of polymerization are given by expressions described previously (Sec. 7-2a-1, Eqs. 5-49, 7-12). 7-2b-3-a Transfer Reactions. Transfer reactions occur in many instances by a variety of reactions, some of which are analogous to those in the cationic polymerization of alkenes. Chain transfer to polymer is a common mode by which a propagating chain is terminated, although the kinetic chain is unaffected. The reaction involves nucleophilic attack by the ether oxygen in a polymer chain on the oxonium ion propagating center, the same type of reaction involved in propagation, to form the tertiary oxonium ion XII. Subsequent nucleophilic attack on XIII by monomer yields XIV and regenerates the propagating species. The overall effect is an exchange of polymer chain segments with a broadening of the MWD from

f3(v, ry)

(CH2)4 + O (CH2)4

v -Wo + -V-a(v)8(v -

O(CH2)4

ry).

To return to a previous slide, you can click the Previous button ( ).

O(CH2)4

(7.132)

+ (CH2)4

To determine a(v), we substitute (7.132) in (7.126):

O(CH2)4

a*(v')a(v)

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(CH2)4

+ V 2 a*(v')a(v)

7-29

the narrow distribution for a living polymerization [Goethals, 1977]. The MWD in some reaction systems is close to the distribution expected for a step polymerization X w =X n $ 2 . Chain transfer to polymer also occurs as an intramolecular reaction as well intermolecular reaction. The intramolecular reaction, also referred to as backbiting, results in the formation of cyclic oligomers instead of linear polymer; in other words, the chain ends in XIV are connected to each other. The competition between propagation and chain transfer to polymer depends on several factors. Propagation is favored on steric grounds since attack by monomer is less hindered than attack by the ether oxygen in a polymer chain. The relative nucleophilic activities of the two different ether oxygens is important and varies considerably depending on monomer ring size. Finally, intramolecular chain transfer to polymer (but not intermolecular transfer) becomes progressively more important at lower monomer concentrations. The distribution of different-sized cyclic oligomers formed in cyclic ether polymerizations generally follows what is expected from the relative stabilities of different-sized rings (Secs. 2-5, 7-1a). The presence of a polymer cyclic oligomer equilibrium (often in addition to a polymer monomer equilibrium) is well documented in many different cyclic ether polymerizations [Bucquoye and Goethals, 1978; Dreyfuss and Dreyfuss, 1969, 1987; Dreyfuss et al., 1989; Kubisa, 1996; McKenna et al., 1977; Penczek and Slomkowski, 1989a,b]. Polymerization of an oxirane yields more cyclic oligomer than obtained from any other-sized cyclic ether. The relative nucleophilicity of a cyclic ether compared to a polymer chain ether is lowest for the 3-membered ring. Propagation for an oxirane involves an increase in bond angle strain on conversion of the sp3-hydridized oxygen in monomer to the sp2-hybridized oxygen in the oxonium ion. The cyclic dimer 1,4-dioxane is the major cyclic oligomer

+ a*(v')a(v)

formed in the polymerization of ethylene oxide (Eq. 7-30). In fact, 1,4-dioxane is the major product in the typical polymerization of ethylene oxide (>80 90%) with only minor amounts of low molecular weight (<103) linear polymer [Kubisa, 1996; Libiszowski et al., 1989].

8(v - v').

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7-30

v _ v'

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