Cationic Polymerization of Ethylene Oxide. II. Boron Trifluoride

Worsfold, D. J.; Eastham, A. M.

doi:10.1021/ja01561a033

Cited by 73 publications

(11 citation statements)

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“…When the concentration of catalystlinitiator complex is decreased with respect to TCPO concentration in order to achieve higher molecular weight products, side reactions become increasingly important. The divergence from the expected and observed molecular weight become pronounced at DPs greater than seven when using a diol/BF, initiator (5).…”

Section: Homopolymerizationmentioning

confidence: 79%

The polymer‐forming reactions of 3,3,3‐trichloropropylene oxide

Vogt

Davis

1971

Polymer Engineering & Sci

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3,3,3‐Trichloropropylene oxide (TCPO) is a monomer which has the combination of a highly reactive epoxide group and a stable trichloromethyl group. The epoxy group will undergo ring opening polymerizations with itself and with a host of other compounds to yield polymeric materials. Water, alcohols, phenols, amines, carboxylic acids and many other compounds react with TCPO with the aid of Lewis acid type catalysts. The electron‐withdrawing influence of the trichloromethyl group, steric effects and the oxirane ring have a strong influence on the course of reactions, which are often radically different from that encountered with the simpler alkylene oxide monomers.

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Section: Homopolymerizationmentioning

confidence: 79%

The polymer‐forming reactions of 3,3,3‐trichloropropylene oxide

Vogt

Davis

1971

Polymer Engineering & Sci

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“…9 Under the influence of boron trifluoride etherate in methylene chloride at 35°C, small amounts of 1,3,5-trioxepane are formed. 20 This indicates the existence of a "back-biting" reaction in the polymerization of dioxolane.…”

Section: Oxetanesmentioning

confidence: 98%

Cyclic Oligomers in the Cationic Polymerization of Heterocycles

Goethals¹

1976

Pure and Applied Chemistry

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Abstract-The cationic polymerization of heterocyclic monomers may Iead to polymers containing substantial, yet variable amounts of cyclic oligomers. This review gives a survey of the systems where such oligomers have been found. Oligomer formation is generally observed in the polymerization of oxiranes and thiiranes. The most frequently observed oligomers are the cyclic dimers and cyclic tetramers but other structures are also possible. It is not clear at the present which factors determine the structure of the oligomer.During the polymerization of aziridines also, cyclic oligomers may be formed. With these monomers, the nature of the catalyst, solvent and temperature are important factors. Of the four-membered heterocyclics, only oxetanes have been found to produce cyclic oligomers.From studies with oxiranes, thiiranes and some aziridines it follows that the oligomers are produced by degradation of first formed polymer and not directly from the monomer. The active species for degradation are the corresponding onium ions. From a thermodynamic point of view it is expected that polymers obtained from three-membered ring heterocycles degrade to form oligomers but it is not clear why in some cases dimers, andin other cases higher oligomers are formed. INTRODliCTION

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“…Cyclic ethers of ethylene and propylene oxide are well known and can be readily prepared by reacting the epoxides with anhydrous Lewis acids [1][2][3][4][5][6]. Treatment of propylene oxide with BF 3' OEt2 in methylene chloride solvent yielded a multitude of cyclic products (Figure 4).…”

Section: Synthesis Of the Odor Bodiesmentioning

confidence: 99%