Acetal Copolymer from the Copolymerization of Trioxane and Ethylene Oxide

Abstract

The copolymerization of trioxane and ethylene oxide in the bulk polymerization state using highly purified trioxane as the starting material, boron trifluoride dibutyl ether as the initiator, and methylal as the chain-transfer agent was investigated for the industrialization of the acetal copolymer, and the various important polymerization conditions were checked. The acetal exchange reaction during the copolymerization gave a uniform acetal copolymer with randomized comonomer distribution. To obtain the polymer with a high degree of stability, several checks were made. The important points were the high purification of the monomer and complete deactivation of the catalyst residue. Thus, the polymer as polymerized showed a degree of stability over 99.5%.

A Novel Branched Polyoxymethylene Synthesized by Cationic Copolymerization of 1,3,5‐Trioxane with 3‐(Alkoxymethyl)‐3‐ethyloxetane

“…A common method that has been industrialized is the end‐capping reaction of the terminal hemiacetals with acetic anhydride; however, the end‐capping process is very energy‐intensive, requiring high reaction temperature (≈170 °C) due to the poor solubility of POM . The other way to improve the thermal stability of POM is by copolymerizing of 1,3,5‐trioxane (TOX) with cyclic ethers such as ethylene oxide, 1,3‐dioxolane, 1,3‐dioxepane, and 1,3‐dioxep‐5‐ene . The random introduction of ‐[(CH 2 ) n ‐O] ( n ≥ 2)‐ units limits the unzipping of the chain and improves the thermal stability of the ‐(CH 2 ‐O) n ‐ units in the copolymer .…”

Analysis of ethylene oxide sequences of the acetal copolymer from trioxane and ethylene oxide

“…There are two routes for the production of polyacetal resin. One route is the polymerization of formaldehyde (acetal homopolymer),1–5 and the other method is the copolymerization of trioxane and ethylene oxide (acetal copolymer) 6–13. One of the writers of this article succeeded in the commercialization of both types of polymer—acetal homopolymer and copolymer—at Asahi Kasei6 and reported an industrial method for the polymerization of formaldehyde5 as well as the copolymerization of trioxane and ethylene oxide 7…”

Bulk copolymerization of 1,3,5-trioxane and 1,3-dioxolane in presence of phosphotungstic acid catalyst and tetrahydrofuran as retarder: crystallinity and thermal properties

“…POM thermal stability can be increased by capping the end groups by esterification, etherification, or copolymerization to obtain C-C linkages in addition to using antioxidants and stabilizers. [4,5] Copolymerization process takes place through the reaction of 1,3,5-trioxane (TOX) with cyclic ethers containing oxyethylene units such as ethylene oxide, [6][7][8][9][10] 1,3dioxolane (DOX), [11][12][13] and 1,3,5-trioxepane [13], specially DOX by random indwelling of oxyethylene units into the oxymethylene chains. The unzipping reaction of oxymethylene chains can be prevented, and thus thermal stability of the sample increases.…”