[1]United States Patent Office 3,311,599 3,311,5-)9 SELECTED N,N-B@S (PERFLUOROAL.XYL) AMINCMERSTH-VREOF ETHYLENES AND POLYI Fr,,ink Shuma-.e Fawcett, WilminFton, Del., gssignor to E. 1. du Pont de Nemours and Company, Wilmingtoll, Del. a corporn'tion of Deloware No 'Draging. Fil@-4- June 17, 1963, Ser. No. 288,461 20 Claims. (C]. 260-87.5) This invention relates to, and has as its principal objects provision of, a new class of ffuoroalkylaminoethylenes having unusual properties and polymers of the same. The novel compolinds of this invention are the N,N@bis(perfluoroalkyl)aminoethylenes havin.- the general formula (Rf) 2NCX'=CXX' wherein each Rf, which can be the same or different, is perfluoroalkyl of up to 6 carbon atoms, X is hydrogen or fluorine, X' is hydro.-en, fluorine, chlorine or (Rf) 2N-, with the provisos that the two Rf substituents and the two X' substituents need not be, respectively, the same, and that not more than one X' is (Rf) 2N-- Amon.- the unusual properties possessed by the N,Nbis(perfli.ioroalkyl)aminoethylenes is their hydrolytic stability. These compounds are not hydrolyzed readily by water as are the known N,N-bis(alkyl)aminoethylenes havin- halogens on the vinyl -roup. The products of this invention can also be polymerized to homopolymers and to copolymers with one or more other polymerizable ethylenic compounds. The polymers, both homopolymers and copolymers, of the N,Nbis(perfluoroalkyl)aminoethylenes are also part of,tms invention. Tle N,N-bis(perfluoroalkyl)aminoethylenes can be prepared by various methods. One method involves the addition of a Nchlorobis(perfluoroalkyl)amine to an acetylene to form the N,Nbis(perfluoroalkylamino)ethylene directly. For example, the addition of N-chloroibis(trifluoromethyl)aniine to acetylene at a temperature of 150-175' C. under auto,@enous pressure gives N(2chlorovinyl) bis (trifluoromethyl) amine. Another me@thod involves a two-step process. In the first step a N-cWorobis(perfluoroalkyl)amine is added to ethylene at a temperature of 150' C., under autogenous pressiire, to form N-(2- chloroethyl)bis(perfltioroalkyl)amine as iilustrated by the followinequation: 150, C. -I, (CF3)2NCI + C,T2==CH2 (CF3)2NCH2Ci -Cl The resultin.- N-(2-chloroethyl)bis(perBuoroalkyl)amine is then dehydrochlorinated. This can -be done by either of two methods, (a) by treatment with aqueous alcoholic potassium hydroxide, or (b) by heating at 650' C. for a few seconds contact time over a nickel surface, to form the N,N@bis(peri'ltioroalkyl)aminoethylene as illustrated by the following equations: (2) A q. Ale. (CH3)2NCH2CH2CI +KOH -------- > (CF3) 2N C !I= C TT2 (3) 650, 0. (CF3) 2'@\CH2CH2CI (CF3) 2'N'CII=CH2 Ni A third method, also a two-step process, for preparin.the products of this invention, involves addition of a Nchlorobis(perffuoroalkyl)amine to ethylene, or a substituted ethylene, in the presenc-- of U.V. li.-ht as the first step. This reaction is illustrated by the equation: (4) U. V. (CF3)21NCI + CIIF=CF2 - (CI"3)2NCHFCF2CI + (CF3)2NCF2--CFHC1 The resulting isomeric mixture of N(haloethyl)bis(per.iluoroalkyl)aniines is then dehydrohalo.@enated by a method similar to (a) described above, i.e., by treatment ivith ponvdered potassiurn hydroxid-, in a hydrocarbon reaction medium, or the mixture is dehalogenated, e.,@., Patented Mar. 28, 1967 2 by heating at 550' C. over a nickel surface. These two methods are illustrated bythe following equations: (5) (C F3) 2NCHFCF2CI (C F3) 2NCr' @C F2 5 +K OH + hy dro(C F3)2N( car bon (CF 3) 2NCF=CFCI (6) (C F3)2iNCHF-CF 'Cil (CF S)2NCH=CF2 10 + + (C F3)2NCF2- CFHCl Ni (C F3)2NCF=CHF The N-chlorobis(perfluoroalkyl)amines used as startina materials for the preparation of the products of this in'vention can be prepared by various methods. Thus, N1,5 eblorobis(trifluoromethyl)amine can be prepared from bis(trifluoromethyl)amine and chlorine -under anhydrous conditions as described in U.S. Patent 3,052,723. Other Nchlorobis(perfluoroalkyl)amines can be prepared by chlorination of N-trifluoromethyl-N-perfluoroethylamine 20 and higher bis(perfluoroalkyl)aniines prepared in turn from the appropriate perfluoroazomethines or imines, havin- a C=N group, by reaction with hydro.-en fl@uoride in accordance with the method ;desciibed in U.S. Patent 2 643 267. An alternative method for preparin@ the N25 ci@or@bis(perfluoroalkyl)amine starting materi'als consists in reaction of mercuric fluoride with a perfluoroazomethine to form a bis-mercury derivative followed by reaction of the latter with chlorine as described by Young, Tsoukalas and Dresdner, J. Am. Chem. Soc., 80, 3604 30 (1958). The N,N-bis(perfluoroalkyl)aminoethylenes can be polymerized to colorless, solid polymers by bulk or solution polymerization, alone or in th-e presence of one or more polymerizable ethylenic compounds, at moderately 35 elevated temperatures in the presence of free radical liberatin- initiators. For example, Nvinylbis(trifluoromethyl)a'mine polvmerizers in the presence of dinitrogen difluoride at 50-6'0' C. under 3,000 atm. pressure to a colorless, solid polymer which is moldable at 100-150' 40 C. into stiff, clear, transparent, tou,-h films. Copolymers ar,- prepared by copolymerizin.- a mixture of the N,N-bis (perfluoroalkvl)aminoethylene with o@ie or mor,- other polymerizable ethylenic comr)oun-,is, e.g., ethylene, under similar conditions. The N@(trifluorovinyl)bis(trifluoro45 metiyl)amine and ethylene form a copolymer whe@i treated with d;nitro,-en diffuoride at 60' C. under 3,000 atm. pressure. The products of this invention are illustrated in greater detail by the following -xampl.--s in which the propo@-tions 50 of in-redients are expressed in parts by wei,aht unless otherwise specified. EXAMPLE I Pi-epai-atioiz of N-viizvlbis(ti-ifluoi-on2ethyl)amitze 55 A. A mixture of 20 @. of Nchlorobis(triffuoromethyl) amine and 6 g. of ethylene is placed in a 240 ml. shake@tube lined with the c4orrosionresistant alloy krown as "Hastelloy" and is heated at 100' C. for 2 he-urs, 125' C. for 2 hours and 150' C. for 4 hours. The volatile re60 action product that is formed is collected in an evacuated cylinder and it amounts to 20 Distillation of this product -ives 11.4 @-. (50% conversion) of colorless 1:1 adduct, N-(2- chloroethyl)bis(trifluoromethyl)-amine, D.P. 28-30' C./143MM-, 71D 24 1.3203. The fluorine nuclear 65 ma,-notic resonance spectrtim shows a single resonance in the CF3N- region and the proton magnetic resonance spectrum shows a peak for CH2- Alialysis.-Calcd. for CF6H@NCI: C, 22.3%; H, 1.87%; F, 53.0%; N, 6.52%; (il, 16.5%. Found: C, 70 22.83%; H, 2.25%; F, 52.49%; N, 6.36%; Cl, 17.09%. B. A pyrolysis tube, consisting of an "Inconel" tlibe 318 in. in inside diaxneter and 6 in. long pack-ed with nickel
[2]3,311,599 3 gauze and with th,- packed section heated by means of an electric beater, is connected directly to a @as chromato.-raphic column (1/4 -in. diameter Fand 12 ft. Ion.-, packed with the ethyl ester of the acid k-nown commercially as Kel-F Acid 8114 on firebrick and ot)erated at 50' C.) Provision is made for collecting samples of tlie gas streain at the times when material is being eltited from the chromato,@raphic column. With the pyrolysis tiibe heated at 650' C., a stream of helium at a rate of 60 ml./min. is passed throu.-h the tube and then into the @as chromato.-raphic column. N-( 2-chloroethyl)bis(triiluoromethY, )amine (20 microliters of liquid) is iiitroduced by means of a hypodermic needle into the gas stream which carries the reactant through the hea.ted zone and th-c pyrolysis products are delivered to the gas chr4Dmato-raphic column. A sample of the material eluted at 4.2 min. after injection time is collected and fotind by mass spectrometric analysis to be N-vinylbis(trifluoromethyl) amine, ( CF3)2N-CH=CH2- EXAMPLE 2 Pi-epa,@-atioji of N-vitiylbis(ti-iflitoi-oiiiethyl)amiiie A. A 5-1. "Pyrex" flask fitted with a test tube-shaued quartz well containin- a c4oiled mercury resonance lam@P and connected to an open-end mercury-in-,-Iass manometer is evacuated and there is introduced 2 g. of ethylene (pressure increment 326 mm.) and 11 .-. of N-chlorobis (trifluoromethyl)-amine (pressure increment 223 mm.). The reactor is shielded a-nd the Ian-ip is turned on for a total of 5 minutes in 30- second intervals with a 1.5 minute dark period between each li.-ht period. Durin.@ this time the pressure in the reactor falls rapidly and a colorless liquid collects in the bottom of the reactor. Further irradiation for 3 minutes @ives only a small reduction in pressure, and no further chan,-e is observed durin- an additional 5-minute irradiation period. Distillation of the liquid reaction product recovered from the reactor -ives 11 g. (85% conversion) 4of N-(2-ebloroethyl)bis(trifluoromethyl)amine, B.P. 71-73' C. This product is identified by infrared and nuclear ma.-netic resonance spectra. B. To,a solution of 15 g. of potassium hydroxide in 15 ml. of water is added 45 ml. of ethanol and the resultin- mixture containin.@ two liquid layers is heated under reflux with stirrin@ while the condenser water is maintained at 32-34- C. The upper end ol' the condenser is connected to a trap cooled by solid carbon dioxidc. Durin,@ a period of 20 minutes there is added 15 -. of N-(2chtoroethyl) bis (trifluoromethyl) amine (CF3) 2NCH2CH2'-'Il The temperature of the refluxin.- mixtiire falls from 80' to 66' C. during this time, and 2 ml. of condensate collects in the trap. Refluxing and stirring are continued and after one hotir the temperature rises to 80' C., sol-ld is present in the reaction vessel, and 7.7 ml. of condensate has collected in the trap. Distillation of the volatile product with a spinnin,@ band column gives a central fraction boiling at 20-22' C. of Nvinylbis(trifluoromethyl)amine amountin-, to 6 g. (50% conversion). Additional product boilin.- at 20-22' C. and amounting to 3 @-. (25% conversion) is isolated fro@m the other fractions. Analytical gas chromato.-raphy shows the larger fraction to contain one major component (96 area p,-rcent) and purification by preparative -as chromato.-raphy yields 5 g. of purified product. The infrared absorption spectrum (gas) shows bands at 3.18 and 3.26 microns (=CH), 6.04 microns (C=C), and stron.- CF absorptio@-i. The fluorine nuclear ma.-netic resonance spectrum shows a sin.-le peak correspondin@ to CF3 and the proton nuclear magnet,@'c resonance specti-um shows the presence of :a - CH==CH2 group. A7zalysis.-Calcd. for C4H3F6N: F, 63.8%. Found: F, 64.04%. 4 EXAMPLE 3 Pi-epai-atio7i of N - (ti-ifliioravitzyl)bis (trifluoi-omethyl) aiiiiizea7idN-(2-chloi-o-1,2-difluoi-ovitiyl)bis (tri]7itorornethyl)atnitie 5 A. A mixture of 53 g. of N-chlorobis(trifluoromethyl) amine and 28 -. of trifluoroethylene is placed in a glass reaction vessel iitted with a reflux condenser cooled by solid carbon dioxide. The reaction mixture is irradiated 10 with an extemal ultraviolet light source for 22 hours. At the end of th-- irradiation period the volatile material is allowed to escape and the colorless Jiquid remaining in the reaction vessel is distilled. There is obtained 38 g. (50% conversion) of the 1: 1 adduct boilin- at 54-59' C. 15 Gas chromatography of this product shows two principal peaks at 10.9 min. (84 area percent) and at 12.45 min. (14 area percent) for the two isomers. (CF,)2NCHF-CF2CI 20 (A) and (CF3)2NCF2--CHFCI (B), respectively. The two-peak mixture is isolated on a 2.3 g. scale by preparative gas chromatography for analysis. The fluorine nuclear magnetic resonance spectrum shows resonances at -655 and at -570 c.p.s. (CF3) :and at +40 c.p.s. 25 (complex multiplet, CF2CI) and at +5,530 c.p.s. (complex multiplet, CFH) from sym. difluorotetrachloroethane as reference. The proton nuclear magnetic resonance spectrum shows a doublet spjit into triplets consistent with -CFHCF2-. The nuclear magnetic resonance spectra 30 indicate that isomer A, (CF3)2NCFHCF2CI, predominates. Analysis. - Calcd. for C41-lFgNCI: F, 63.5%; Cl, 13.15%; mol. wt., 270. Found: F, 64.03%; Cl, 13.55%; mol. wt., 273, 284 (freezing point in benzene). 35 B. A - IaSS Teaction vessel is equipped with a mechanical stirrer, a thermometer and a reflux condenser arranged for control of the cooling water temperature at 32- 34' C. and the upper end of the condenser is attached to a trap cooled by solid carbon dioxide. The reaction vessel is 40 charged with 100 ml. of methylcyclohexane and 27 @. of a mixture of N(chlorotrifluoroethyl) bis (trifluoromethyl) amines (prepared as described above). To the stirred mixture at 25' C. is added cautiously in three portions 32 g. of powdered potassium hydroxide which has previ45 otisly been ground in a mortar under an atmosphere of nitro-en. There is no evidence of reaction during the addition. The resulting slurry is stirred and heated on a steam bath over a one-hour period to 72' C., at which time active refluxin.- occurs and 1.3 ml. of volatile mate50 rial collects in the trap. Stirrin.- and heating are continued at 72-88' C. for a period of 2 hours dtirin- which a total of 10 ml. of volatile material collects in the trap. DistUlation of the volatile product through a spinning band fractionatin.- column gives a central fraction, B.P. 55 17-18' C., of N - (trifluorovinyl)bis(trifluoromethyl) amine, amounting to 9 g. (39% conversion). Additional material in the boien.- i-an.-e 17-26' C. amounts to 4 -,. (21% co@iversion), makin- a total conversion of 60%. Analytical -as chromatography indicates the larger frac60 tion to contain one major component (approximately 99 area percent). The infrared absorption spectrum and the fluorine nuclear magnetic resonance spectrum show the product to be N - (trifluorovinyl )bis(trifluoromethyl) amine. 65 -4tialysis.-Calcd. for C4F9N: F, 73.4%. Found: F, 73.36%. The procedure described in the preceding paragraph repeated two more times with a total of 128 g. of the mixture of N - (chlor otrifluoroethyl) bis (trifluoromethyl) 7o amine isomers gives a total of 59 g. (55% conversion) of N - (triffuorovinyl)bis(trifluorometliyl)amine. There is also obtained a higher boilin--- fraction amounting to 5.3 g., B.P. 25-53' C. (principally 38-40' C.). Preparative gas chromatography of this fraction yields a co-product 75 identified by infrared @and nuclear magnetic resonance
[3]spectroscopy as N - (2 - chloro-1,2-dif[uorovinyl)bis(trifluoromethyl) aniine. Analysis.-Calcd. for C4FgNCI: F, 61.0%. Found: F, 58.2%. This product results from the removal of the elements of HF from the minor component of the starting mixture, i.e., N - (2-chloro-1,2,2- trifluoroethyl)bis(trifluoromethyJ) amine. EXAMPLE 4 Preparation of N-(2,2-diflitoi-ovinyl)bis( ti-ifitioromethyl) anzitie andN-(1,2-difluorovinyl)bis (ti-iflitoromethyl) amine A mixture of N - (chlorotrifluoroethyl)bis(trifluor omethyl)an-iine isomers prepared as described in Example 3 (A) is pyrolyzed over nickel gauze at 550' C. by the _procedure described in Example l(B). Two products are obtained in the gas chromatographic column at 3.4 niin. (3 parts) and at 4.2 min, (I part) retention time. Mass spectrometric analyses of the products indicate them to have the composition (CF3)2NC2HF2, and they are N - (2,2-difluorovinyl)bis(trifluoromethyl)amine and N(1,2- diflLlorovinyl)bis(trifluoromethyl)amine. EXAMPLE 5 P)-eparation of N - (2-chlorovinyl)bis( ii-ifltioramethyl) amine A mixttire of 3 5 of N-chlorobis (trifluoromethyl) amine and 5.0 g. of acetylene is heated in a closed reaction vessel capable of withstanding high pressures at 175' C. for 5 hours, durin.- Nvhich time the auto.@enous pressure drops from 600 to 325 lb./sq. in. Anoth.-r mixture of the same reactants in the same proportion is heated similarly dur'mg which the auto,-Cnous pressure drops from 700 to 490 lb./sq. in. The combined liquid reaction products from both these r-uns amounts to 50 g. of a fluid, yellow liquid. Distillation of this crude product gives 20 g. (27% conversion) of the 1:1 adduct, N - (2-chlorovinyl)bis (trifluoromethyl)amine, boilin.- at 50-62' C. Preparative scale -as chromatographic separation of this distilled product yields the two cis and trans isomers, the inajor one having the shorter retention time. The fluorine nuclear maanetic resonance spectra for both isomers show the presence of C-e-3. The major isomer shows :absorption at 3.24 microns (=CH) and at 6. 1 0 microns (C=:C) ,4nalysis. - Calcd. for C4H2'.'7cCIN: F, 53.5%; C], 16.6%. Found: major isomer, F, 53.71%; Cl, 17.5%, 18.6%; minor isomer, F, 53.0%. EXAMPLE6 Prepat-ation of N-(2-chlot-ovitzyl)bis(ti-iflitoi-ainethyl) a7?zine A. A liauid mixture of 19 g. of vinyl chloride and 55 of Nchlorobis(trifluoromethyl)amine in a qtiartz reactor is stirred under reflux (the condenser cool@ed with solid carbon dioxide) and irradiated for 5 hours by means of an external coiled mercury ultraviolet lamp. Dtiring the early period of irradiation the mixture refluxes actively and after 45 minutes the reiluxing essentially ceases. At the end of the five hours, the liquid product, amountin@ to 72 --a-, is distilled and there is obtained 67 @@- of N - (2,2-dichloroethyl)bis(trifluoromethyl)amine (92% co-@iversion), boiling at 91-96' C. The fluorine nuclear ma,-netic resonance spectr-tim shows a sin.-le fluorine resonance for CF3 and the proton nuclear magn--tic resonance spectrtim shows a small triplet resonance for CH and a larger doublet r@-sonance for CH2, which show the structure to be (CF3) 2NCH2CHC12- Analysis.-Calcd. for C@H3Cl2F6N: F, 45.7%; Cl 28.6%. Found: F, 45.33%; Cl, 28.55%. B. A mixture of 25 a. of N-(2,2-dichloroethyl)bis( trifILiorornethyl)amine and 45 @a. of anhydrous potassium acetate -@'n 75 ml. of N ,N-dimethylforma-inide is stirred and heated under a fractionating column arran.-ed for removal of distillate. Durin-. two hours there is collected a forerun of 2.16 -- boiling at 36-52' C. and then 17.7 of distillate boiling at 52-59' C. The latter is washed with dilute aqueous hydrochloric acid, with water, dried over anhydrous sodium sulfate and redistilled. There is obtained 14.8 -. of colorless distillate (7001o conversion), B.P. 56-65' C., identified by means of infrared and nuclear ma.-net,c resonance spectra and by gas chromato"@ion times as N-(2-chlorovinyl)bis(trifluoro-raphic re ten metbyl)amine (cis and trans isomers). 10 EXAMPLE 7 A. Pi-epai-atioiz of N-ethyizylbis(ti-ifittoi-o7netlzyl)atniiie A mixture of 16 @-- of N-(2-chlorovinyl )bis(trifluoro15 mothyl)amine (mixed isomers), 100 ml. of methylcyclohexane and 60 of micropulverized potassium hydroxide is stirred and heated under reflux with provision for collecting volatile reaction products in a trap cooled with a solid carbon dioxide-acetone mixture. After 6 hours )o of refluxing there is obtained 6.4 ml. of volatile product in the cold trap. A dtiplication of this reaction gives another 5.9 ml. of volatile reaction product. The two products are combined and subjected to fractional distillation. There is obtained a central fraction boiling at 3.5' 25 C. of N-ethynylbis(trifltiorornethyl)amine amountiii.- to 7 @. Aiialysis.--Calcd. for C4HF6N: F, 64.3%. Found: F, 64.96, 64.80%. The str-ucture is conf@@rmed by infrared and nlclear mag30 netic reso-@iance spectroscopy. Iiifrared bands are present at 3.0,a (=-CH), 4.6,u (-C@-C-) and at 7.91i, (CF, strop@). The fiuorine n-m-r spectrum shows a peak for CF3 at -295 c.p.s. from sym.-difluorotetrachloroethane reference, and the proton n-m-r spectrum shows 35 a sin.ale resonance for C--CH at -130 c.p.s. from tetramethylsilane reference. An additional portion obtained in the distillation having a boilinran-e of 0 to 9' C. amounts to 10.5 g. Tle total amount of N-ethynylbis (trifltioromethyl)amine obtained amounts to 17.5 (60% 40 conversion). B. Pi-epaiatioii of N,N,N',Nl-teti-ck-is(ti-iflito i-ainetliyl)-lchloro-1,2-(and 2,2)ethetiedia7,nines A test tube-shaped quartz reactor of 250 ml. cai)acity conn@cted to arl open end manometer and provided with 45 arl external coiled mercury resonance lamp is evacuated and charged with I g. of N-ethynylbis(trifluoromethylamine) (press,,ire i-iicreinent 300 mm.) and then I g. of N-chlorobis(trifluoromethyl)amine (pressure increment 303 mm.). The reactor is shielded and the mercury reso50 nance lamp turned on for one minutes. This results in a decrease of pressure in the reactor and the formation of colorless liquid in the bottom of the vessel. The irridiation is conti-@iued for two 1-miniate periods and then for two 2-minute periods with 1-minute dark periods between 55 each irradiation. The above reaction is repeated usin.- a 500 rnl. capacity reactor to which is char.-ed 1.5 g. of N-ethynylbis (trifluoroniethyl)amine and 2 .-. of Nchlorobis(trifluoromethylamine. After irradiation i.1 a manner similar to 60 that described above there is a pressure decrease in the reactor and a liquid product forms. The liqtiid products from both experiments (amounting to 3.1 rnl., or 4.9 g., combined) are distilled and there is obtained 1.8 ml. of colorless liquid boiling at 92-95' C. The following data 65 show this product to be a mixture o'L isomers formed by combination of one molecule of each reactant, narnely, N,N,N',N'-tetra kis(triflLoromethyl) - 1-chloro1,2-ethenediamine (cis and trans) and N,N,N',N'-tet rakis(trifluoromethyl) - I - chloro-2,2-othenediamine. The infrared ab70 sorption spectrum shows bands at 3.25 microns (=CH), at 6.01 microns (C=C) and strong absorption at 7-9 microns (CF). The fluorine nuclear magnetic resonance specti-um shows CF3 resonances and the proton nuclear ma.anetic resonance spectrum sho,@vs a resonance at -380 75 to -400 c.p.s. (from tetrametby@lsilar@e reference, 60 mc.)
[4]7 with complex splittin,-. Aralvtical scale -as chromatography shows the presence of two major componerts. A ttal3,sis.-Calcd. for C6Fl2N2CIH: F, 62.5%; N, 7.7%. Found: F, 63.42 %; N, 7.83 %. EXAMPLE8 Pi-epai-at,'Oiz of N-ethyizylbis(ti-ifluoroi7zetliyl)aiiiiiie A mixture of 39 g. of N-(2,2-dichloroethyl)bis(trif luoromethyl)amine and 100 of micropulverized potassium hydroxide in 150 ml. of iuethylcyclohexane is heated under the conditions described in Example 7-A above. After 21 hours reaction there is obtained 13.5 ml. of volatile product. Distillation of this product _--ives 10.5 g. of Nethynylbis(trifluoromethyl)amine (477o conversion), B.P. 3-4' C. EXAMPLE 9 Po@vinei-izatioil of N-i,iizylbis(ti-iflitoi-oiiiethyl)aniltie A mixttirc of 2 g. of N-vinylbis(trifluoromethyl)amine and 5.8 milligrams of dinitrogen di'@luoride in a sealed platinum tlibe is heated for 6 hours at 50-60' C. under 3,000 atm. pressure. There is obtained 1.83 g. of colorless, solid polymer. This polymer is insoluble in hot N, N-dimetbylformamide or hot toluer@e and is not affected by cold concentrated sulfuric or nitric acid, or by n-butylamine at its boilin,- point. Tfie polymer is mol@ded at 100-150' C. to a stiff, clear, trar@sparent, touL-,h, self-supporting film. EXAMPLE 10 Pi-eparatioit of a copolyii7ei- of N-(ti-iflitoy-ov itzyl)bis-(ti-ift'uoi-oiiiethyl)a77iiiie aizd ethyleize A mixture of approximateiv 2.8 of N-(trifluorovinyl )bis(tri.,quoromethyl)amine, 0.3 g. (>f ethylene and 6 m-. of dinitrogen difluoride (all measured as gases at 1 Itm., 300 cc., 300 cc., and 2 cc. volumes, respectively) is placed in a platinum tube at liquid nitro.-en temperature. The tube is sealed and the mixture is then heated with shakin.- at 60' C. for i'Our hours under 3000 atm. pressure. On opening the tube a volatile liquid is evolved and there remains 0.4 @@. of white, solid copo'@ymer of ethylene and N(trlfluorovinyl) bis (trifluoromethyl) amine. This polymer is pressed at 50-90' C. into films that are transparent and elastic. The film shows infrared absorption bands at 3.4g (CH) and strong absorption at 7-9g (CF). The polynier is insoltible in hot xylene. The copolymer contains 53.57% F and 4.74% N. EXAMPLE I I Pi-epai-atio!z of a copolynzei- of N-vitiylbis(ti-iflito,,-oiizcth),I)aiiiiiie aiid teti'aflitoi-oethyleiie By t@'ie proc,-du.@e of Example 10, a mixture of 2.0 ml. of liquid perfluorodiniethylcyclobutane and 2 of Nvinylbis(tr ifluoromethyl)amine, 1.3 g. of tetrafluoroethylene, and 6 m-. of dinitro.-en difluoride is heated at 60' C. and 3000 atm. pressure for 4 hours. There is obtained a white, tacky polymer which on dryin.- in vacuum, cuttin.- into small pieces and further dryin-, at 100' C. in vacuum to constant wei.-ht gives 3.23 g. of white, toti--h, horny solid copo.@ymer of Nvinylbis(trifluoromethyl) amine and tetrafluoroethylene. The copolymer contains 5.1 1 % N. The copolvmer is pressed into clear, colorless, flexible, transparent films at 140- 180' C. The copolymer film shows infrared absorption at 3.31i, (CH) and strong absorption at 7-10A (CF). Films are manually drawn cold, or when warm, to the extent of several times the ori,-inal len---th. EXAMPLE 12 Pi-epai-atio;z of a copolytizei- of N-viiiylbis(ti-iflitoi-ornethyl)ainitic ajid tetraflitoroethyleize An 80 ml. stainless steel shaker tube is flushed with nitro@,en ar@d there are added 15 ml. of perfluorodimethylcyclobutane as solvent and 0.1 -. of a,a-azobis(rt-cyclo3,311,599 8 propylpropionitrile) and the reactor is closed and cooled promptly in a bath of acetone and solid carbon dioxide. The vessel is evacuated and char@ed in a barricaded area with 6 g. of N-vinylbis(trifluorometbyl)amine and 50 g. of tetrafluoroethylene. The closed reactor is then heated with shakin- at 35-40' C. for 15 hours. At the end of this time the volatile material in the reactor is bled throu,,@h a trap cooled with solid carbon dioxide, and on opening the rez-,ctor there is obtained 10 g. of a colorless, syrupy, 10 slurry of poly.-ner. Additional perfluorodimethylcyclobutane is added and the resulting polymer solution is filtered through a fluted filter paper. The faintly turbid fi'@trate is concentrated to dryness under reduced pressure in a glass flask. The polymer daposits as a film on the 15 walls of the flask and, after dryin@ to constant weight in a vacuu@.-n on a steam bath, it amounts to 1.65 g. This tou-b, faintiy tan-colored copolymer is extracted with boilin- benzene under reflux for 15 Tninutes and then vacuum dried. The tou@h polymer mass is cut up into 20 small pieces and further@ dried in vacuum on a steam bath. There is obtained 1.51 g. of polymer. This copolymer contains 4.32% nitrogen and 69.66% fluorine. The copolymer is pressed at 130-160' C. into clear, colorless, transparent, flexible films of 0.5 to 1.8 mil thickness. 25 These films can be cold drawn with necking down. Infrared absorption spectra of the films show absorption at 3.3 microns (CH) and strong absorption in the 7-9 micron region (CF). Tlle proton nuclear magnetic resonance spectrum of the polymer in @perfluorodimethylcyclo3o butane solution shows two broad resonances centered at -2.5 p.p.m. (relative size about 2) and at -4.6 p.p.m. (relative size about 1) (tetramethylsilane reference). EXAMPLE 13 35 Pi-epai-atioti of a copolyinet- of N-(ti-iflitor oviliyl)bis(ti-lflitoi,oi7iethyl)aniiiie atid vitzylideize fliiot-ide By the procedure of Example 10 a mixture of 2 ml. of perfluorodimethylcyclobutane, 0.8 -. of vinylidene fluoride, 3.3 -. of N(trifluorovirlyl)bis(trifluoromethyl) 40 arnine and ab'out 6 m-. of dinitrogen difluoride is heated at 60' C. and 3000 atm. pressure for 2 hours. There is obtained 0.36 g. of white, solid copolymer of N-(trifluoro, vinyl)bis(trifluoroinethyl)amine and vinylidene fluoride. The polymer is pressed to form clear, colorless, transpar45 ent, flexible films at 105-175' C. The filmof copolymer can be manually cold drawn. The copolymer contair@s 1.48% nitrogen and 61.00% fluorine. EXAMPLE 14 5 0 Polyt2zei-izatioiz ol N-etlzynylbis(ti-iflitoi -oniethyl)ainiiie A mixture of 3.0 g. of N-ethynylbis(trifluoromethyl) amine, 0.021 g. of triphenylphosphine-nickel tricarbonyl catalyst and 1.0 ml. of benzene is sealed in a "Pyrex" class tube iand kept at room temperature (25'-30' C.) 55 urder auto.-enouspressure with occasional a.-itation. The initially clear homogeneous solution gradually turns light yellow in color (5 minutes), then turns to a darker -reenish-yellow color (25 minutes). After aboi-it 35 minutes a sli,-ht evolution of heat is noted and after 55 min60 utes the mixture evolves -additional heat and deposits a mass of solid polymer. Aftercoolin-, the tube is opened and the solid po'@yi-ner is extracted @repeatedly with hot benzene and dried in vacuum. There is obtained 1.2 g. of brown, solid polymer. This polymer is insoluble iri 65 concentrated sulfuric acid at 100' C., and in the following solvents heated to the boiling point: pyridine, NNdimethylformamide, methyl ethyl ketone, glacial acetic acid, dimethyl sulfoxide, and aqueous sodium hydroxide. The polymer is pressed at 170-180' C. under a pressure 70 of 500 lb./sq. in. to form self-supporting, flexible, transparent films of 0.5 to 2 mils thickness that are orange-red in color. Remoldin- gives films of increased clarity. Infi@ared examination of the polymer as a film or as a potassium bromide mull shows absorption at 3.0 microns 75 (@=CH), at 6-6.5 n-iicrons (C--C), and strong absorl)tioil
[5]:3 311,599 9 at 7-9 microns (CF). The visible spectrum shows strongabsorption near 450-500 millimicrons with increasing strenoth of absoill)tion at shorter wave lengths. ,4,zalysis.--Calcd. for C4HF6N: C, 27.2%; H, 0.6%; F, 64.3%; N, 7.9%. Found: C, 28.83%; H, 0.93%; F, 6 63.12%; N, 7.99%. The examples have illustrated the products of this inven'Lion by reference to the preparation of specific compounds covered by the -eneral formula given hereinbefore. Other srecific N,N-bis(perfltioroalkyl)arninoethylenes that 1( are in@luded by this invention and which can be made by the procedures illustrated by the examples include the compounds listed in the right-hand column of the following Table 1. The startin.- materials from which they are prepared are listed in the first column of the table. TABLE I.-PREPARATION OF N,N-BIS(PERFLUOROALKYL) AillINOETHYLENES St,,irting Materials Products 10 a similar solution of I part of the polytetraffuoroethylene in 8 parts of warin N,N,N',N'- tetrakis(trifluoromethyl)1-chloro-1,2-(or 2,2-)ethenediamine (prepared as described in Example 7-B). After drying in air to remove solvent, the treated paper samples are highly resistant to wettin.- by water, which remains as droplets on the treated zone, whereas portions of the same paper that are not treated or are treated with the pure solvents are readily wetted by water to become limp. Since obvious modifications and equivalents in the invention will be evident to those skilled in the chemical arts, I propose to be bound solely by the appended claims. The embodiments of the invention in which an exclusive property or privilege is
