Observations on the initiation of trioxane with boron trifluoride dibutyl etherate

Collins, George; Greene, R. K.; Berardinelli, F. M.; Garruto, William V.

doi:10.1002/pol.1979.130171008

Cited by 20 publications

(6 citation statements)

References 8 publications

(2 reference statements)

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“…The need for a high loading of BF 3 ⋅OEt 2 can be explained by the fact that trace amounts of water are crucial to initiate the polymerization. This can be supported by previous studies demonstrating that BF 3 etherate failed to polymerize trioxane in rigorous dry conditions . In addition, the achieved molar mass of the polymer is not linearly related to the amount of catalyst and no polymerization occurred at low catalyst concentration (entry 3 in Table ).…”

Section: Methodssupporting

confidence: 70%

Cellulose‐Derived Functional Polyacetal by Cationic Ring‐Opening Polymerization of Levoglucosenyl Methyl Ether

2019

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The unsaturated bicyclic acetal levoglucosenyl methyl ether was readily obtained from sustainable feedstock (cellulose) and polymerized by cationic ring‐opening polymerization to produce a semicrystalline thermoplastic unsaturated polyacetal with relatively high apparent molar mass (up to ca. 36 kg mol−1) and decent dispersity (ca. 1.4). The double bonds along the chain can undergo hydrogenation and thiol–ene reactions as well as crosslinking, thus making this polyacetal potentially interesting as a reactive functional material.

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Section: Methodssupporting

confidence: 70%

Cellulose‐Derived Functional Polyacetal by Cationic Ring‐Opening Polymerization of Levoglucosenyl Methyl Ether

2019

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“…This polymerization is carried out on an industrial scale using boron trifluoride etherate [Cui et al, 2003;Dolce and Grates, 1985]. The presence of water is required for polymerization as noted by the lack of polymer formation in the complete absence of water [Collins et al, 1979]. That 1,3,5-trioxane polymerizes in spite of containing the stable 6-membered ring is a consequence of the polymerization occurring with simultaneous precipitation of the polymer in crystalline form.…”

Section: -2b-4 Cyclic Acetalsmentioning

confidence: 99%

Ring‐Opening Polymerization

Odian

2004

Principles of Polymerization

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A wide variety of cyclic monomers have been successfully polymerized by the ring-opening process [Frisch and Reegan, 1969; Ivin and Saegusa, 1984;Saegusa and Goethals, 1977]. This includes cyclic amines, sulfides, olefins, cyclotriphosphazenes, and N-carboxy-a-amino acid anhydrides, in addition to those classes of monomers mentioned above. The ease of polymerization of a cyclic monomer depends on both thermodynamic and kinetic factors as previously discussed in Sec. 2-5.The single most important factor that determines whether a cyclic monomer can be converted to linear polymer is the thermodynamic factor, that is, the relative stabilities of the cyclic monomer and linear polymer structure [Allcock, 1970;Sawada, 1976]. Table 7-1 shows the semiempirical enthalpy, entropy, and free-energy changes for the conversion of cycloalkanes to the corresponding linear polymer (polymethylene in all cases) [Dainton and Ivin, 1958;Finke et al. 1956]. The lc (denoting liquid-crystalline) subscripts of ÁH, ÁS, and ÁG indicate that the values are those for the polymerization of liquid monomer to crystalline polymer.Polymerization is favored thermodynamically for all except the 6-membered ring. Ringopening polymerization of 6-membered rings is generally not observed. The order of thermodynamic feasibility is 3,4 > 8 > 5,7 which follows from the previous discussion (Sec. 2-5c) on bond angle strain in 3-and 4-membered rings, eclipsed conformational strain in the 5-membered ring, and transannular strain in 7-and 8-membered rings. One notes that RING-OPENING POLYMERIZATION RING-OPENING POLYMERIZATION

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“…Collins et al 23 reported that molten trioxane at 70°C initiated with BF3 -Bu20 did not polymerize at a low water concentration (< 17 ppm H 2 0 ) , and they concluded that the initiation of trioxane by BF3 * Bu20 in the presence of water occurs by rapid hydrolysis of BF3 to form protonic acids that protonate trioxane in the primary initiation step. Lu et alF4 reported proton NMR studies leading to the development of a more detailed mechanistic scheme for the initial process.…”

Section: Mechanism and Kinetics Of Trioxane Copolymerizationmentioning

confidence: 99%

“…Lu et alF4 reported proton NMR studies leading to the development of a more detailed mechanistic scheme for the initial process. Collins et al 23 reported that water is necessary for the polymerization using the BF3 ether complex as the initiator. On the other hand, there are several reports that denied the role of water as a cocatalyst using BF3 * OBu2.…”

Section: Mechanism and Kinetics Of Trioxane Copolymerizationmentioning

confidence: 99%

Development of a new advanced process for manufacturing polyacetal resins. Part III. End‐capping during polymerization for manufacturing acetal homopolymer and copolymer

Masamoto

Matsuzaki

Iwaisako

et al. 1993

J of Applied Polymer Sci

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SYNOPSISConventionally, acetal homopolymer or copolymer is obtained by the polymerization of formaldehyde or trioxane, following the end-capping using acetic anhydride or unzipping of the unstable polymer end fraction. First, Asahi Chemical developed a new process to obtain an end-capped polymer during polymerization of highly purified formaldehyde using acetic anhydride as the chain-transfer agent. Use of highly purified formaldehyde and endcapping during polymerization using acetic anhydride as a chain-transfer agent or an endcapping agent will provide a simple process for manufacturing acetal homopolymer. The polymerization mechanism was confirmed by infrared spectroscopy analysis and proton NMR analysis of the polymer obtained. Second, for the acetal copolymer, purified trioxane was copolymerized with ethylene oxide in the presence of methylal, which gave an endcapped polymer with high thermal stability. Two new intermediates from the initiation reaction of the copolymerization, 1,3,5,7-tetraoxacyclononane (TOCN ) and 1,3,5,7,10-pentaoxacyclododecane ( POCD ) , were isolated and a new initiation mechanism was proposed.

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Observations on the initiation of trioxane with boron trifluoride dibutyl etherate

Cited by 20 publications

References 8 publications

Cellulose‐Derived Functional Polyacetal by Cationic Ring‐Opening Polymerization of Levoglucosenyl Methyl Ether

Cellulose‐Derived Functional Polyacetal by Cationic Ring‐Opening Polymerization of Levoglucosenyl Methyl Ether

Ring‐Opening Polymerization

Development of a new advanced process for manufacturing polyacetal resins. Part III. End‐capping during polymerization for manufacturing acetal homopolymer and copolymer

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