Monomers and polymers containing the trifluoromethyl group

Abstract

The discovery by Ziegler of a heterogeneous catalyst system capable of polymerizing ethylene to a high molecular weight solid under extremely mild conditions, and the subsequent work of Natta2 on the extension of the investigation to other a-olefins is well documented. The unusual properties of the polymers obtained from heterogeneous catalysts led to a search for polymerizable monomers other than the purely hydrocarbon types with which the early investigators were occupied.I n this work a series of polar monomers was prepared in order to find a heterogeneous catalyst system suitable for their polymerization, to correlate the effect of the proximity of the polar substituent to the double bond with the ability of the monomers to polymerize, and to determine the effect of the polar substituent on the properties of the polymer. As an indication of the degree of polar, character of the trifluoromethyl group, 3,3,3trifluoropropene is reported to possess a dipole moment of 2.45 D.3 as opposed to 0.34 D. for propylene4 and 3.15 D. for acryl~nitrile.~ EXPERIMENTAL 3,3,3-Trifluoropropene 3,3,3-Trifluoroproperie was prepared according to the procedure of Syverson and Kroetz6 by conversion of 1 ,l,l-trifluoropropano1-2 to and pyrolysis of the acetate. The monomer was purified as the dibromide, prepared according to Henne17 and was regenerated with zinc in refluxing ethanol. 4,4,4-Trifluorobutene-lPreparation of 4,4,4-Trifluorobutanol. 1,1,1,3-Tetrachloropropane was converted to 1,1,l-trifluoro-3-chloropropane according to Haszeldine8 by reaction with antimony trifluoride dichloride.To sublimed magnesium turnings (23.1 g., 0.95 g.-atom) in 300 ml. of * A portion of a thesis submitted by E.B.11. in partial fulfillment of the requirement for the Degree of Doctor of Philosophy in the graduate school of the Polytechnic Institute of Brooklyn.

Copolymerization of Polar Monomers with Olefins Using Transition-Metal Complexes

“…Although ω-fluoroolefins were not included in the above investigations, Overberger and co-workers studied the polymerization of linear and branched α-olefins containing the trifluoromethyl group with various Ziegler−Natta systems. , 5,5,5-Trifluoro-1-pentene and 4-trifluoromethyl-1-pentene were polymerized in high conversion with VCl 3 / i -Bu 3 Al or TiCl 3 /AlEt 2 Cl (conditions: heptane, 70−100 °C), while 4,4,4-trifluoro-1-butene and 3-trifluoromethyl-1-butene gave low conversions to solid polymer, and 3,3,3-trifluoropropylene produced only an oil. Monomers containing a fluorine atom or a −CF 3 group bound directly to the double bond also failed to polymerize.…”