Copolymerization with ethylene oxide

In a recent patent, Reuter (110) describes a polyurethane prepared from PTHF (mol. wt. 1000 to 3000), 1,4-butanediol, and OCN(CH2)6CN0. In another case Murbach and Adicoff (67) interrupted the regularity of PTHF by copolymerization with ethylene oxide before chain extension with diphenyl-methane-4,4 -disiocyanate. Dickinson (99) prepared a series of polyurethane elastomers from THF-PO copolymer diols and 2,4-tolylene diisocyanate. He found that the use of copolymers with approximately 75 wt.-% THF led to polyurethanes with very good properties relative to the use of propylene oxide homopolymer. 

In the patent literature, there are several reports of the cationic polymerization of tetrahydrofuran (THF) with Nafion-H. In most cases, small amounts of acetic anhydride were added so the initial polymer had a terminal acetate group that could be hydrolyzed to the free hydroxyl. THF has also been homopolymerized936 938 and copolymerized with ethylene oxide and propylene oxide in the presence of Nafion-... 

Copolymerization with Ethylene Oxide. Figures 2-6 show the NMR spectra of copolymerization of trioxane and ethylene oxide where the... 

These macromonomers were reacted with a halohydrin to yield phenyl glycidyl ether end-groups. Subsequent copolymerization with ethylene oxide or epichloro-hydrin, using the Vanderberg catalyst (triethylamine/water mixture) produced graft copolymers [187]. 

Interesting polymers have been produced by copolymerization of siloxanes with other polymers. For example, dimethylsiloxane was copolymerized with ethylene oxide and methyl methacrylate to create a series of polymers with controlled permeability to hydrophilic or hydrophobic steroids, enhanced mechanical properties, and improved adhesion to tissues [15-17]. 

For TOX copolymerization with ethylene oxide (EO), EO was first converted to low molecular weight copolymer and cyclic oligomers such as dioxolane (DOL) and 1,3,5-trioxepane (TOP) (4). For either EO and DOL as comonomer with TOX, they were found to be preferentially incorporated during the induction period (5). 

The major commercial use of propylene oxide is as a comonomer for copolymerization. The block copolymerization with ethylene oxide produces water-soluble detergents. The copolymerization of propylene oxide with non-conjugated dienes produces sulfur-vulcanizable, oil-resistant elastomers that remain rubber-like at low temperatures. The elastomers obtained by the copolymerization of propylene oxide with allyl glycidyl ether have only poor oil resistance, but have good ozone resistance and remain rubberlike at low temperatures. 

Although butyl rubber is by far the most important commercial elastomer to be synthesized by cationic polymerization, several heterocyclic monomers provide useful elastomeric materials via this mechanism also. Epichlorohydrin can be polymerized to high molecular weight using a complex catalyst formed from a trialkylaluminum compound and water as shown in Eq. (58) [64, 130-132], For copolymerizations with ethylene oxide, a catalyst formed from a trialkylaluminum compound, water, and acetylacetone is useful [64,130], The mechanism proposed for these polymerizations is... 

Alkyl isocyanates do not copolymerize with ethylene oxide. 

Tonhauser C, Alkan A, Schomer M, Dingels C, Ritz S, Mailander V, Frey H, Wuim FR (2013) Ferrocenyl glycidyl ether a versatile ferrocene monomer for copolymerization with ethylene oxide to water-soluble, thermoresponsive copolymers. Macromolecules 46 647-655... 

To demolish the crystalline structure of PEO, epichlorohydrin was first copolymerized with ethylene oxide to introduce a branch structure in order to increase the ion conductivity to 4.1 x 10 S/cm (Yu and Zhou, 2002). Although this copolymer was not decribed as a pure graft polymer, it at least revealed that the ion conductivity can be improved by incorporating the side chain to depress the crystalline tendency of PEO. 

Other interesting perfluoro ether stmctures can be obtained by copolymerization of hexafluoroacetone with ethylene oxide, propylene oxide, and trimethylene oxide with subsequent fluorination to yield the following stmctures (67) ... 

Random copolymerization of propylene oxide with ethylene oxide proceeded smoothly with the Nd(2-EP)3/AlEt3/H20 system at 80 °C [59]. From... 

An addition graft copolymerization is the reaction of /9-propiolactone with cellulose, which has been extensively studied by Daul, Reinhardt, and Reid [138). In a similar reaction cellulose adds ethylene imine, as shown by work by Cooper, and Smith (139), and ethylene or propylene sulfide, as described by Champetier (140). Also the well known hydroxy-ethylation of cellulose by reaction with ethylene oxide belongs to this class of reactions. 

Acetal Resins. Acetal resins (qv) are poly (methylene oxide) or polyformaldehyde homopolymers and formaldehyde [50-00-0] copolymerized with aliphatic oxides such as ethylene oxide (42). The homopolymer resin polyoxymethylene [9002-81-7] (POM) is produced by the anionic catalytic polymerization of formaldehyde. For thermal stability, the resin is endcapped with an acyl or alkyl function. 

In the copolymerization of trioxane with dioxolane, however, depolymerization and regeneration of dioxolane monomer is a faster and more effective way of converting soluble into crystalline copolymer with random distribution. A similar mechanism may hold true for trioxane polymerization with similar comonomers such as 1,3-dioxane, 1,3-dioxacyclo-heptane and in part even for copolymerization of trioxane with ethylene oxide which also involves formation of some dioxolane and soluble copolymer. 

Copolymers may also be produced with a catalyst containing both chromium oxide and nickel oxide supported on silica-alumina. It is well-known that nickel oxide—silica—alumina by itself makes predominantly butenes from ethylene. In the mixed catalyst, butenes that are formed on nickel oxide copolymerize with ethylene on the chromium oxide to form ethylene-butene copolymers. The fact that infrared shows only ethyl branching in the polymer indicates that the initial product... 

Polymers with LM in side groups can also be obtained by polymerization of other monomers. Thus, poly(ethylene oxide) containing LM (Table 1 LMg) is formed by copolymerization of ethylene oxide and 9-anthryaldehyde in the presence of a modified organoaluminum catalyst ... 

The synthesis and purification of polystyrene methacryloyl macromonomers (PS-MA) in the molecular weight range Mn= 1000-2000 g mol 1 by living anionic polymerization of styrene (S), termination with ethylene oxide (EO), and subsequent reaction with methacrylic chloride has already been described in detail elsewhere [180] (see also Scheme 16). In this context it has to be emphasized that the hydroxyethyl-terminated PS-MA macromonomer precursor (PS-OH) as obtained after purification of the crude PS-OH by silica column chromatography (cyclohexane/dichloromethane 1/1 v/v) and as charged in the PS-MA synthesis still contains up to about 15 wt-% of non-functionalized polystyrene (PS-H). This PS-H impurity of the PS-MA macromonomer does not interfere with the PS-MA synthesis and the subsequent TBA/PS-MA copolymerization and is easily and conveniently removed from the resulting PTBA-g-PS graft copolymer (see below). 

Stable acetal copolymers of formaldehyde, called Hostoform and Celcon were also produced commercially by the cationic copolymerization of formaldehyde with ethylene oxide — ... 

The present paper deals broadly with the copolymerization of ethylene oxide and tetrahydrofuran using cationic ring-opening polymerization catalysts. A comparison is made of EO/THF polyether glycol with PTMEG and their respective polyurethanes. 

Polymerization of 1,3,5-trioxane (TXN) gives linear polyoxymethylene (POM), a homopolymer of formaldehyde 39). This is the only polyacetal made on the technical scale. Two methods are used for the industrial production of stable, high-molecular-weight POMs. This is either the anionic polymerization of formaldehyde or the cationic copolymerization of the cyclic trimer of formaldehyde TXN with ethylene oxide or 1,3-dioxolane (DXL) ... 

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