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Home , Bismuth pentafluoride, Hafnium tetrafluoride, Organozinc compound, Tellurium tetrafluoride

3,446,788 United States Patent Office Patented May 27, 1969 2 3,446,788 polybutadiene segment has a high content of cis 1,4 struc POLYMERIZATION OF BUTADENE BY A ture. Other objects will become apparent as the descrip CATALYST CONTAINING ALUMNUM tion proceeds. ALKYLS, COMPOUNDS AND METAL FLUORDES According to the invention, butadiene or butadiene in Morford C. Throckmorton and William M. Saltman, combination with other diolefins is polymerized by con Akron, Ohio, assignors to The Goodyear Tire & Rub tact under solution polymerization conditions with a cat ber Company, Akron, Ohio, a corporation of Ohio alyst comprising (1) at least one organometallic com No Drawing. Filed Mar. 20, 1967, Ser. No. 624,219 pound in which the metal is selected from Groups I, II int. C. C08d 1/14, 3/08; B01j 1 1/84 and III of the periodic system, (2) at least one organo U.S. C. 260-94.3 10 Claims 0. nickel compound and (3) a metal fluoride selected from the group consisting of , ABSTRACT OF THE DISCLOSURE vanadium pentafluoride, A method and a catalyst system for the solution uranium hexafluoride, polymerization of butadiene or butadiene in mixture with 5 osmium hexafluoride, other diolefins to form polymers containing a high con rhenium hexafluoride, tent of cis 14 addition is described. The solution iodine pentafluoride, polymerization is carried out under conventional , polymerization conditions. The catalyst employed is a tin tetrafluoride, mixture of (1) organometallic compounds of metals of 20 antimony trifluoride, Groups I, II and III; (2) organonickel compounds and induim trifluoride, (3) a metal fluoride selected from the group consisting , of pentafluoride, phosphorus pentafluoride, 25 niobium pentafluoride, vanadium pentafluoride, tantalum pentafluoride, uranium hexafluoride, , osmium hexafluoride, , rhenium hexafluoride, difluoride, iodine pentafluoride, 30 hexafluoride, antimony pentafluoride, tetrafluoride, tin tetrafluoride, tetrafluoride, antimony trifluoride, lead tetrafluoride, indium trifluoride, cadmium difluoride, arsenic pentafluoride, titanium trifluoride, bismuth pentafluoride, iron trifluoride, niobium pentafluoride, cobalt trifluoride, tantalum pentafluoride, vanadium trifluoride, titanium tetrafluoride, trifluoride, zirconium tetrafluoride, 40 germanium tetrafluoride, zinc difluoride, tetrafluoride, platinum hexafluoride, difluoride and difluoride. hafnium tetrafluoride, The organometallic compounds useful in this inven thorium tetrafluoride, tion are organocompounds of such metals as , lead tetrafluoride, , potassium, rubidium, cesium, magnesium, cadmium difluoride, calcium, strontium, beryllium, barium, zinc, cadmium, titanium trifluoride, aluminum, gallium and indium. By the term, "organo iron trifluoride, metallic' is meant alkyl, cycloalkyl, aryl, arylalkyl, cobalt trifluoride, alkaryl radicals are attached to the metal to form the vanadium trifluoride, organo compound of the particular metal. palladium trifluoride, Of the organometallic compounds useful in this inven germanium tetrafluoride, tion, it is preferred to use organoaluminum compounds, tellurium tetrafluoride, organomagnesium compounds, organozinc compounds copper difluoride and silver difluoride. and organolithium compounds. 5 5 By the term "organoaluminum compound' is meant any organoaluminum compound responding to the for This invention is directed to methods of polymerizing imula butadiene and butadiene in mixture with other diolefins R1 to form polymers having a high content of cis 1,4 addi / tion. It is also directed to catalyst systems useful for this 60 purpose. A R3R. Polymers of butadiene or butadiene in mixture with in which R1 is selected from the group consisting of other diolefins containing a high proportion of the buta alkyl (including cycloalkyl), aryl, alkaryl, arylalkyl, hy diene units in the cis 1,4 configuration possess prop drogen and , Ra and Ra being selected from the erties which make then useful as synthetic rubbers. 65 group of alkyl (including cycloalkyl), aryl, alkaryl, It is an object of this invention to provide a method alkoxy and arylalkyl. Representative of the compounds whereby butadiene can be polymerized to a high con responding to the formula set forth above are: tent of cis 1.4 polybutadiene. Another object is to provide diethylaluminum fluoride, a catalyst system by which these polymerizations may be di-n-propylaluminum fluoride, accomplished. Another object is to form copolymers of 70 di-n-butylaluminum fluoride, isoprene or other diolefins and butadiene in which the diisobutylaluminum fluoride, 3,446,788 3 4. dihexylaluminum fluoride, n-, sec- or t-butyllithium, hexyllithium, styryllithium or dioctylaluminum fluoride, and phenylithium. Also, the organolithiumaluminum com diphenylaluminum fluoride. pounds may be used. These compounds respond to the formula R'R''LiAl where R' and R' may be alkyl, Also included are alkaryl or arylalkyl groups and R' and RR' may or may diethylaluminum hydride, not be the same group. Representative of these com di-n-propylaluminum hydride, pounds are n-butyltriisobutyllithium aluminum, tetra di-n-butylaluminum hydride, butyllithium aluminum, butyltriethyllithium aluminum, diisobutylaluminum hydride, tetraisobutyllithium aluminum and styryltrinormalpropyl diphenylaluminum hydride, lithium aluminum. di-p-tolylaluminum hydride, 0 Representative of other organometallic compounds dibenzylaluminum hydride, which may be employed in this invention are sodium, phenylethylaluminum hydride, potassium, calcium, beryllium, cadmium and phenyl-n-propylaluminum hydride, alkyls, arkaryls, arylalkyls and aryls. p-tolylethylaluminum hydride, The component of the catalyst of this invention which p-tolyl-n-propylaluminum hydride, contains nickel may be any organonickel compound. It is p-tolylisopropylaluminum hydride, preferred to employ a soluble compound of nickel. These benzylethylalumium hydride, soluble nickel compounds are usually compounds of nickel benzyl-n-propylaluminum hydride, and with a mono or bi-dentate organic containing up benzylisopropylaluminum hydride and 20 to 20 atoms. "Ligand' is defined as an or other organoaluminum hydrides. Also included are molecule bound to and considered bonded to a metal diethylethoxyaluminum and dipropylethoxyaluminum. atom or ion. Mono-dentate means having one position through which covalent or coordinate bonds with the Also included are metal may be formed; bi-dentate means having two posi trimethylaluminum, 25 tions through which covalent or coordinate bonds with triethylaluminum, the metal may be formed. By the term "soluble' is meant tri-n-propylaluminum, soluble in inert solvents. Thus, any nickel salt of an triisopropylaluminum, organic acid containing from about 1 to 20 carbon atoms tri-n-butylaluminum, may be employed. Representative of such organonickel triisobutylaluminum, 30 compounds are nickel benzoate, nickel , nickel tripentylaluminum, naphthenate, bis (alpha furyl dioxime) nickel, nickel oc trihexylaluminum, tanoate, nickel palmitate, nickel stearate, nickel acetyl tricyclohexylaluminum, acetonate, bis(salicylaldehyde) ethylene diimine nickel trioctylaluminum, and nickel salicaldehyde. Nickel tetracarbonyl also may triphenylaluminum, be employed as the nickel containing catalyst in this in tri-p-tolylaluminum, vention. The preferred component containing nickel is tribenzylaluminum, a nickel salt of carboxylic acid or an organic complex ethyldiphenylaluminum, compound of nickel. ethyl-di-p-tolylaluminum, The third components of the catalyst which are the ethyldibenzylaluminum, 40 metal fluorides listed above should be, of course, an diethylphenylaluminum, hydrous and as pure as possible. Since some of these diethyl-p-tolylaluminum, metal fluorides are gases, it may be more desirable to diethylbenzylaluminum and other triorganoaluminum dissolve them in a solvent and charge them to the polym compounds. erization system as liquid solutions. Such solvents may By the term "organomagnesium compounds' is meant be any alkyl, aryl, alkaryl or arylalkyl hydrocarbons, ben first any organomagnesium complex responding to the 45 Zene or heptane being usually preferred. formula RaMgxi where R may be alkyl, aryl, arylalkyl The three catalyst components may be charged sepa or alkaryl; X is a , and a and b are mole fractions rately in either stepwise or simultaneous addition to the whose sum equals 2 while the ratio of a/b is greater than polymerization system or they may be mixed with one 2 but is not infinite. Representative among the com 50 another in an inert solvent and this "preformed' catalyst pounds responding to the formula set forth above are can then be added to the monomer-solvent polymeriza ethylmagnesium chloride complex, cyclohexylmagnesium tion system. bromide complex and phenylmagnesium chloride com The three component catalyst system of this invention plex. Such compounds are usually prepared in the ab has shown polymerization activity over a wide range of sence of . 55 catalyst concentrations and catalyst ratios. The three Also "organomagnesium compounds" means any or catalyst components inter-react to form the active cata ganomagnesium compound or any organomagnesium lyst. As a result, the optimum concentration for any one of the Grignard type corresponding to the formulas catalyst is dependent upon the concentration of each of R2Mg or RMgY where R may be alkyl, aryl, arylalkyl the other catalyst components. While polymerizations will or alkaryl and M is fluorine, or R'R''Mg where R' may 60 occur over a wide range of catalyst concentrations and be alkyl, aryl or alkaryl and R' may be either alkyl, ratios, polymers having the most desirable properties are aryl, arylalkyl or alkaryl. Representative among the com obtained over a narrower range. pounds responding to these formulae are diethylmag When the metal fluoride is PF6, VFs, UF, OsF, ReF, nesium, dipropylmagnesium, ethylmagnesium fluoride and IF5 or SbF5, the mole ratio of the organometallic com phenylmagnesium fluoride. pound (Me) to the organonickel compound (Ni) should By the term "organozinc compound' is meant any or 65 range from about 2/1 to about 60/1, the mole ratio of ganozinc compound responding to the formula R22n the metal fluoride (MeF) to the organometallic com where R may be alkyl, aryl, alkaryl or arylalkyl. Repre pound (Me) should range from about 1.2/1 to about sentative among such compounds are , dibutyl 3/1 and the mole ratio of the metal fluoride to the or zinc or diphenylzinc. 70 ganonickel compound should range from about 2/1 to By the term "organolithium compounds' is any or about 35/1. When the metal fluoride is SnR, SbF, InF, ganolithium compound responding to the formula R-Li AsF5, BiFs, NbF5 or TaF5, the Me/Ni mole ratio should where R is an alkyl, alkaryl, arylalkyl or aryl group. range from about 2/1 to about 60/1, the mole ratio of Representative among the compounds responding to the the MeF/Me should range from about 1.2/1 to about formula set forth above are ethyllithium, propyllithium, 10/1 and the MeF/Ni mole ratio should range from 3,446,788 5 6 about 2/1 to about 125/1. When the metal fluoride em indicated in the table below, were injected. These mix ployed is TiF, TiF, ZrF4, Znf2, PtF6. HfF4, ThEA, PbF, tures were allowed to polymerize at a temperature of CdF. FeF, CoF, VF, PdE3, GeF, TeFA, CuF2 or 50° C. while being agitated for a period of 18 hours. The AgF2, the Me/Ni mole ratio should range from about resulting polymers were stopped by the injection of 0.1 2/1 to about 60/1, the MeF/Me mole ratio should range gram of 1,1,1'-nitrilotri - 2 - propanol and 2,4-di-t-butyl from about 2.5/1 to about 20/1 and the MeF/Ni mole 5 para-cresol, and dried at 45 C. at a vacuum. The yields ratio should range from about 5/1 to about 250/1. were calculated and are reported in the table below. The The concentration of the catalyst employed depends DSV was determined and it is reported in the table. The on factors such as purity, rate desired, temperature and cis 1,4 content of each of the polymers was determined other factors, therefore, specific concentrations cannot by infrared analysis and is reported in the table. TABLE I Millimoles/100 gms. Bd Exp. Metal Yieldwt. Percent No. fluoride TEAL NiOct Me. percent cis DSW

i------Sn 1.0 .05 3.0 84 96 2.8 0.6 .05 ... O 57 94 2.0 1.0 .10 3.0 52 94% 1.5 .0 .0 6.0 99 97 2.7 1.0 .05 6.0 84 97 2.9 1.0 10 12.0 83 96 3.6 1.0 ... 10 6.0 34 96 4.1 1.0 10 12.0 39 9 3.8 i.0 05 12.0 34 96 3.6 ... O .0 12.0 20 96 3.6 1.0 05 3.0 15 '96 ------1 IR film analysis. be set forth except to say that catalytic amounts are used. 25 Example II Some specific concentrations and ratios which produce elastomers having desirable properties will be illustrated Polymerizations were prepared in the manner of that in the examples given herein to explain the teachings of of Example I using various metal fluorides except that this invention. the infrared analysis was not run. The results and amounts In general, the polymerizations of this invention are of catalyst and the metal fluoride employed are set forth carried out in any inert solvent, and thus, are solution 30 in the table below. polymerizations. By the term "inert solvent" is meant that TABLE II the solvent or diluent does not enter into the structure of Millimoles/100gms. Bd Yield, the resulting polymer nor does it adversely affect the prop Ex Metal weight erties of the resulting polymer nor does it have any ad No. fluoride TEAL. NiOct MeF. percent DSV verse effect on the activity of the catalyst employed. Such 0, 6 0.05 0.75 17 ------1. 0 6 66 3.8 solvents are usually aliphatic, aromatic, or cycloaliphatic 1. ... 10 12 83 3.. 6 hydrocarbons, examples of which are pentane, hexane, .05 6 65 2.9 heptane, toluene, benzene, cyclohexane and the like. Pre ferred solvents are hexane and benzene. The solvent/ 40 While certain representative embodiments and details monomer volume ratio may be varied over a wide range. have been shown for the purpose of illustrating the in Up to 20 or more to 1 volume ratio of solvent to mono vention, it will be apparent to those skilled in this art mer can be employed. It is usually preferred or more that various changes and modifications may be made there convenient to use a solvent/monomer volume ratio of in without departing from the spirit or scope of the in about 3/1 to about 6/1. Suspension polymerization may 45 vention. be carried out by using a solvent, e.g., butane or pentane, What is claimed is: in which the polymer formed is insoluble. It should be 1. The process for the polymerization of butadiene and understood, however, that it is not intended to exclude butadiene in mixture with other diolefins to form poly bulk polymerizations from the scope of this application. mers containing a high proportion of the butadiene units It is usually desirable to conduct the polymerizations 50 in the cis configuration comprising contacting butadiene of this invention employing air-free and moisture-free and butadiene in mixture with other diolefins under po techniques. lymerization conditions with a catalyst comprising (1) at The temperatures employed in the practice of this in least one organometallic compound in which the metal is vention have not been found to be critical and may vary selected from Groups I, II and III of the Periodic Sys from a low temperature such as -10° C. or below up 55 tem, (2) at least one organonickel compound selected to high temperatures of 100° C. or higher. However, a from the group consisting of nickel salts of carboxylic more desirable temperature range is between about 30 acids, organic complex-compounds of nickel and nickel C. and about 90° C. Ambient pressures are usually used tetracarbonyl and (3) a metal fluoride selected from the but higher or lower pressure may be employed. group consisting of phosphorous pentafluoride, vanadium The practice of this invention is further illustrated by 60 pentafluoride, uranium hexafluoride, osmium hexaflu reference to the following examples which are intended oride, rhenium hexafluoride, iodine pentafluoride, anti to be representative rather than restrictive of the scope of mony pentafluoride, tin tetrafluoride, antimony trifluoride, this invention. Unless otherwise noted, all parts and per indium trifluoride, arsenic pentafluoride, bismuth penta centages are by weight. Dilute solution viscosities (DSV) fluoride, niobium pentafluoride, tantalum pentafluoride, have been determined in toluene at 30° C. 65 titanium tetrafluoride, zirconium tetrafluoride, zinc di Example I fluoride, platinum hexafluoride, hafnium tetrafluoride, thorium tetrafluoride, lead tetrafluoride, cadmium diflu A butadiene-benzene solution was purified by passing oride, titanium trifluoride, iron trifluoride, cobalt triflu through a silica gel column and by Sparging with puri oride, vanadium trifiuroide, palladium trifluoride, ger fied nitrogen. One hundred milliliters of this solution 70 manium tetrafluoride, tellurium tetrafluoride, copper di which contained 10 grams of butadiene was placed in a fluoride and silver difluoride. series of polymerization vessels. Triethylaluminum 2. The process according to claim 1 in which butadiene (TEAL) and nickel octanoate (Ni oct) in amounts as in 1,3 alone is employed. dicated in the following table were added. The vessel was 3. The process according to claim 1 in which the or closed and the amounts of the various metal fluorides, as 75 ganonickel compound is selected from the group consist 3,446,788 7 8 ing of nickel salts of carboxylic acids and organic com about 2/1 to about 60/1, the mole ratio of the metal flu plex compounds of nickel. oride to the organometallic compound ranges from about 4. The process according to claim it in which the or 2.5/1 to about 20/1 and the mole ratio of the metal ganometallic compound is selected from the group con fluoride to the organonickel compound ranges from about sisting of organoaluminum compounds, organomagnesi 5/1 to about 250/1. um compounds, organozinc compounds and organolithium 8. The process according to claim 4 in which the or compounds. ganometallic compound is an organoaluminum com 5. The process according to claim 1 in which the metal pound, fluoride is selected from the group consisting of phos 9. The process according to claim 8 in which the or phorous pentafluoride, vanadium pentafluoride, uranium 10 ganoaluminum compound is an aluminum trialkyl. hexafluoride, osmium hexafluoride, rhenium hexafluoride, 10. A catalyst composition comprising (1) at least one iodine pentafluoride, and antimony pentafluoride and in organometallic compound in which the metal is selected which the mole ratio of the organometallic compound from Groups I, II and III of the Periodic System, (2) to the organonickel compound ranges from about 2/1 to at least one organonickel compound selected from the about 60/1, the mole ratio of the metal fluoride to the group consisting of nickel salts of carboxylic acids, or organometallic compound ranges from about 1.2/1 to ganic complex-compounds of nickeis and nickel tetracar bout 3/1 and the mole ratio of the metal fluoride to bonyl and (3) a metal fluoride selected from the group the organonickel compound ranges from about 2/1 to consisting of phosphorous pentafluoride, vandium penta about 35/1. fluoride, uranium hexafluoride, osmium hexafluoride, 6. The process according to claim in which the metal 20 rhenium hexafluoride, iodine pentafluoride, antimony fluoride is selected from the group consisting of tin tetra pentafluoride, tin tetrafluoride, antimony trifluoride, in fluoride, antimony trifluoride, indium trifluoride, arsenic dium trifluoride, arsenic pentafluoride, bismuth pentaflu pentafluoride, bismuth pentafluoride, niobium pentaflu oride, niobium pentafluoride, tantalum pentafluoride, oride and tantalum pentafluoride, and in which the mole titanium tetrafluoride, zirconium tetrafluoride, zinc defiu ratio of the organometallic compound to the organonickel 25 oride, platinum hexafluoride, hafnium tetrafluoride, thori compound ranges from about 2/1 to about 60/1, the um tetrafluoride, lead tetrafluoride, cadmium difluoride, mole, ratio of the metal fluoride to the organometallic titanium trifluoride, iron trifluoride, cobalt trifluoride, compound ranges from about 1.2/1 to about 10/1 and vanadium trifluoride, palladium trifluoride, germanium the mole ratio of the metal fluoride to the organonickel tetrafluoride, tellurium tetrafluoride, copper difluoride compound ranges from about 2/1 to about 125/1. 30 and silver difluoride. 7. The process according to claim 1 in which the metal fluoride is selected from the group consisting of titanium References Cited tetrafluoride, titanium trifluoride, zirconium tetrafluoride, UNITED STATES PATENTS zinc difluoride, platinum hexafluoride, hafnium tetraflu 3,143,537 8/1964 Hagemeyer et al. ---- 260-93.7 oride, thorium tetrafluoride, lead tetrafluoride, cadmium difluoride, iron trifluoride, cobalt trifluoride, vanadium JAMESA. SEIDLECK, Primary Examiner. trifluoride, palladium trifluoride, germanium tetrafluoride, R. A. GAITHER, Assistant Examiner. tellurium tetrafluoride, copper difluoride and silver deflu oride, and in which the mole ratio of the organometallic U.S. C. X.R. compound to the organonickel compound ranges from 40 252-429; 260-82.1 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3, 446, 788 May 27, 1969 Morford C. Throckmorton et al. It is certified that error appears in the above identified patent and that said Letters Patent are hereby corrected as shown below: Column 2, line 22, 'induim' should read -- indium -- . Column 4, 1ine 5, "RR'" should read -- R^ - - ; 1ine 14, "arkaryls' should read - - alkaryls -- . Column 5, line 73, ' (Ni oct) ' should read - - (Ni Oct) -- . Column 7, line 17, 'bout' should read -- about - - ; line 38, 'deflu-' should read -- diflu - - -. Column 8, line 24, 'de flu-' should read -- diflu - - - . Signed and sealed this 2nd day of June 1970.

(SEAL) Attest: Edward M. Fletcher, Jr. WILLIAM E. SCHUYLER, JR. Attesting Officer Commissioner of Patents