Synthesis of copolymer from 1,3,5‐trioxane and 1,3‐dioxolane catalyzed by Maghnite‐H⁺

Abstract

Copolymers (polyoxymethylene) were prepared by cationic copolymerization of 1,3,5‐trioxane (TOX) with 1,3‐dioxolane (DOX) in the presence of Maghnite‐H+ (Mag‐H+) in solution. Maghnite is a Montmorillonite sheet silicate clay, with exchanged protons to produce Mag‐H+. Various techniques, including 1H‐NMR, 13C‐NMR, FT‐IR spectroscopy, and Ubbelohde viscometer were used to elucidate structural characteristics properties of the resulting copolymers. The influence of the amount of catalyst, of dioxolane (DOX), temperature, solvent, and time of copolymerization on yield and on intrinsic viscosity of copolymers was studied. The yield of copolymerization depends on the amount of Mag‐H+ used and the reaction time. We also propose mechanisms involved in the synthesis of copolymer (polyoxymethylene). © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010

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

“…Thus, the copolymers with a similar level (±0.1%) of incorporation ratio of the different ROX units were compared. For instance, P(TOX 19 -co -EOX 1 ), P(TOX 90 -co -BOX 10 ), and P(TOX 80 -co -HOX 20 ) all have a similar incorporation ratio of ROX around 3.2%. The melting temperature of P (TOX 19 -co -HOX 1 ) is the lowest (166.3 °C), and that of P(TOX 97 -co -EOX 3 ) is the highest (166.9 °C), however, this difference is quite small, which indicates at the same low incorporation ratio, the length of side chain has little effect on the melting temperature of the copolymer.…”

“…[ 2 ] 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. [ 3,4 ] 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, [5][6][7][8][9] 1,3-dioxolane, [10][11][12][13] 1,3-dioxepane, [ 14 ] and 1,3-dioxep-5-ene. [ 15 ] 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.…”

Insights into the Nature of the Active Sites of Tin‐Montmorillonite for the Synthesis of Polyoxymethylene Dimethyl Ethers (OME)

“…The acid-treated montmorillonite (AT-MMT) was prepared as described in a protocol given by Beloufa et al [60] Crushed clay (30 g) was dispersed in 120 mL of Deionized water and the mixture was stirred for 2 h at room temperature in an Erlenmeyer flask. Then, 100 mL of a 0.5 M sulfuric acid aqueous solution was added.…”

Green Polymerization of 4-(Oxiran-2-ylmethyl)morpholine

“…Maghnite-H + is a naturally occurring catalyst with considerable advantages used in the polymerization of several heterocyclic and vinyl monomers [10][11][12][13][14][15].…”