Furan polymerization

Because Formula (2.45) is identical to the experimentally obtained Formula (2.41), it is obvious that the structural diagram (Figure 2.44) adequately describes the behavior of rubber concretes at compression and can be added to the basis of the creep equation of these materials. (The similar diagram corresponds to a number of plastic [rigid PVC, polyethylene] and furan polymeric concrete.)... 

As can be seen, most of the furfural produced in this country is consumed as an intermediate for other chemicals. Hydrogenation to furfuryl alcohol is the largest use. Some of the furfuryl alcohol is further hydrogenated to produce tetrahydrofurfuryl alcohol. The next major product is furan, produced by decarbonylation. Furan is a chemical intermediate, most of it is hydrogenated to tetrahydrofuran, which in turn is polymerized to produce polytetramethylene ether glycol (PTMEG). 

The radical-catalyzed polymerization of furan and maleic anhydride has been reported to yield a 1 1 furan-maleic anhydride copolymer (89,91). The stmcture of the equimolar product, as shown by nmr analyses, is that of an unsaturated alternating copolymer (18) arising through homopolymerization of the intermediate excited donor—acceptor complex (91,92). 

Rubber Modifiers. Derivatives of furan and tetrahydrofurfuryl alcohol are used in the polymerization of synthetic mbber to control stereoregularity and otherproperti.es (149,150). 

Aqueous mineral acids react with BF to yield the hydrates of BF or the hydroxyfluoroboric acids, fluoroboric acid, or boric acid. Solution in aqueous alkali gives the soluble salts of the hydroxyfluoroboric acids, fluoroboric acids, or boric acid. Boron trifluoride, slightly soluble in many organic solvents including saturated hydrocarbons (qv), halogenated hydrocarbons, and aromatic compounds, easily polymerizes unsaturated compounds such as butylenes (qv), styrene (qv), or vinyl esters, as well as easily cleaved cycHc molecules such as tetrahydrofuran (see Furan derivatives). Other molecules containing electron-donating atoms such as O, S, N, P, etc, eg, alcohols, acids, amines, phosphines, and ethers, may dissolve BF to produce soluble adducts. 

Aqueous ring-opening metathesis polymerization (ROMP) was first described in 1989 (90) and it has been appHed to maleic anhydride (91). Furan [110-00-9] reacts in a Diels-Alder reaction with maleic anhydride to give exo-7-oxabicyclo[2.2.1]hept-5-ene-2,3—dicarboxylate anhydride [6118-51 -0] (24). The condensed product is treated with a soluble mthenium(Ill) [7440-18-8] catalyst in water to give upon acidification the polymer (25). Several apphcations for this new copolymer have been suggested (91). 

Alkylation of furan and thiophene has been effected with alkenes and catalysts such as phosphoric acid and boron trifluoride. In general, Friedel-Crafts alkylation of furans or thiophenes is not preparatively useful, partly because of polymerization by the catalyst and partly because of polyalkylation. 

Benzo[Z)]furans and indoles do not take part in Diels-Alder reactions but 2-vinyl-benzo[Z)]furan and 2- and 3-vinylindoles give adducts involving the exocyclic double bond. In contrast, the benzo[c]-fused heterocycles function as highly reactive dienes in [4 + 2] cycloaddition reactions. Thus benzo[c]furan, isoindole (benzo[c]pyrrole) and benzo[c]thiophene all yield Diels-Alder adducts (137) with maleic anhydride. Adducts of this type are used to characterize these unstable molecules and in a similar way benzo[c]selenophene, which polymerizes on attempted isolation, was characterized by formation of an adduct with tetracyanoethylene (76JA867). 

Furfural — see Furan-2-oarbaldehyde, 532 Furfuryl acetate, o -(butoxycarbonyl)-anodic oxidation, 1, 424 Furfuryi acrylate polymerization, 1, 279 Furfuryl alcohol configuration, 4, 544 2-Furfuryl alcohol polyoondensation, 1, 278 reactions, 4, 70-71 Furfuryl alcohol, dihydro-pyran-4-one synthesis from, 3, 815 Furfuryl alcohol, tetrahydro-polymers, 1, 276 rearrangement, 3, 773 Furfuryl chloride reactions... 

Phthalides — see Benzo[c]furan-l (3H)-one Phthalimide, 2-amino-pyridazine synthesis from, 3, 53 Phthalimide, N-cyclohexylthio-as vulcanization accelerator, 1, 404 Phthalimide. methylidine-polymerization, 1, 273 Phthalimide, N-(trichloromethylthio)-biocide, 1, 399 Phthalimide, 1-vinyl-polymerization, 1, 273 Phthalimide, N-vinyl-copolymer... 

Group of plastics composed of resins in which the furane ring is an integral portion of the polymer chain made from polymerization or polyconden-sation of furfural, furfural alcohol and other compounds containing furane rings also formed by reaction of furane compounds with an equal weight or less of other compounds. 

Ryder reported the preparation of an interesting alkyl diaryl furan that was subsequently polymerized and studied as a conducting polymer. The monomer furan 49 was available fron the acid catalyzed cyclization of dione 48. ... 

Scheme 3b). It is instructive at this point to reiterate that the furan nucleus can be used in synthesis as a progenitor for a 1,4-dicarbonyl. Whereas the action of aqueous acid on a furan is known to provide direct access to a 1,4-dicarbonyl compound, exposure of a furan to an alcohol and an acid catalyst should result in the formation of a 1,4-diketal. Indeed, when a solution of intermediate 15 in benzene is treated with excess ethylene glycol, a catalytic amount of / ara-toluenesulfonic acid, and a trace of hydroquinone at reflux, bisethylene ketal 14 is formed in a yield of 71 %. The azeotropic removal of water provides a driving force for the ketalization reaction, and the presence of a trace of hydroquinone suppresses the formation of polymeric material. Through a Finkelstein reaction,14 the action of sodium iodide on primary bromide 14 results in the formation of primary iodide 23, a substance which is then treated, in crude form, with triphenylphosphine to give crystalline phosphonium iodide 24 in a yield of 93 % from 14.

The present review deals with polymerization systems where the furan ring is present in the monomer(s) either as the reactive entity or as a side group to the function responsible for the growth. It covers, therefore, a wide variety of situations, many of them not yet fully understood. In fact, as will become apparent later, there is still a great deal of controversy about the interpretation of experimental results obtained with most of these systems and sometimes even disagreement among authors as to the data obtained. Particular emphasis has therefore been placed in this review on a critical reinterpretation of previous work in view of the recent experience gathered by... 

The furan ring can be made to polymerize through one or both of its double bonds and the polymers obtained will therefore have dihydro- and tetrahydrofuran rings in their backbone. This situation occurs when furan, the alkylfurans, benzofuran and some dihydrofurans are treated with suitable initiators and is discussed in the first section of this chapter. 

If on the other hand the polymerization of a furan derivative takes place through a substituent containing an adequate functionality, such as C=C or C=0, the furan ring should in principle conserve its structure and the polymers obtained will bear it as a side group. It has been found, however, that in some of these systems the normal propagation is accompanied by other reactions which involve participation of the ring and which therefore alter the normal structure of the macromolecule. The second section of this chapter deals with monomers, such as 2-vinylfuran and 2-furaldehyde, which exhibit this general behaviour. 

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