3,528,957 United States Patent Office Patented Sept. 15, 1970

2 ing and forming machinery. In spite of its relatively high 3,528,957 cis-1,4 content, the polybutadiene produced by this proc METHOD OF PRODUCING POLYBUTADENE ess is, on the average, no better or no worse in processing MorfordAkron, C.Ohio, Throckmorton, assignors to Theand GoodyearWilliam M.Tire Saltman, & Rub. properties than polybutadiene made with the alkyl-lithium ber Company, Akron, Ohio, a corporation of Ohio catalyst System which produces a polybutadiene with No Drawing. Filed July 10, 1967, Ser. No. 651,991 about a 40% cis-1,4 structure. Polybutadiene made with Int, C. C08d, 3/06 the two component catalyst system comprising alkyl U.S. CI. 260-94.3 10 Cains aluminum halides and cobalt salts results in molecular Structures very high in cis-1,4 configuration (in the neigh borhood of 98%), yet these polymers do not show ap ABSTRACT OF THE DESCLOSURE 10 preciable processing advantage over the polybutadiene A method and a catalyst system for the solution po type polymers made by either of the other two processes lymerization of butadiene or butadiene in mixture with previously mentioned. other diolefins to form polymers containing a high con Based on the most practical test of what indicates good tent of cis-1,4 addition is described. The solution polym 5 polymer processability, that is, manifestations during ac erization is carried out under conventional polymeriza tual factory processing, polybutadiene produced by a tion conditions. The catalyst employed is a mixture of ternary catalyst System comprising (1) triethylaluminum, (1) organometallic compounds of metals of Groups I, (2) an organonickel salt, and (3) boron trifluoride di II and III; (2) at least one compound selected from the ethyl ether complex, which possesses a very high cis-14 class consisting of organonickel and organocobalt com 20 molecular structure of about 98%, shows an appreciable pounds, and (3) at least one boron trifluoride complex gain in processability over the polybutadienes prepared prepared by complexing boron trifluoride with a member in the aforementioned process. of the class consisting of monohydric alcohols, phenols, The present invention also employs a ternary catalyst Water and mineral acids containing oxygen. System similar to the just mentioned except that one 25 catalyst component comprises borontrifluoride complexed with at least one member from the group comprising This invention is directed to methods of polymerizing a monohydric alcohol, a phenol, water and an oxygen butadiene and butadiene in mixture with other diolefins containing mineral acid, the result of which, produces to form polymers having a high content of cis-14 ad an unexpected increase in the polymerization reaction dition. It is also directed to catalyst systems useful for 30 rate of 2 to 3 times greater than that achieved by the this purpose. just-mentioned catalyst system. The processability of the Polymers of butadiene or butadiene in mixture with polymer produced by the system of the present invention other diolefins containing a high proportion of the is equivalent to that produced by the system using boron butadiene units in the cis-1,4 configuration possess proper trifluoride diethyl ether complex. ties which make them useful as synthetic rubbers. 35 In addition to promoting unexpected reaction rates, It is an object of this invention to provide a method the catalyst system of the present invention has also shown whereby butadiene can be polymerized to a high content an unexpected versatility in performance. of cis-1,4 polybutadiene. Another object is to provide a For example, the catalyst System just mentioned using catalyst System by which these polymerizations may be the boron trifluoride" diethyl ether complex appears to be accomplished. Another object is to form copolymers of 40 quite limited with respect to the selection of the trialkyl isoprene or other diolefins and butadiene in which the aluminum component if optimum reaction rates for this polybutadiene segment has a high content of cis-1,4 struc system are to be attained. To maintain the optimum re ture. Another object is to produce high cis-1,4 poly action rate with this catalyst system, the choice of trialkyl butadiene with excellent processing properties. Other ob aluminum compound appears o be limited to triethyl jects will become apparent as the description proceeds. aluminum. When the ethyl group in the trialkylaluminum The term "good processability” describes a polymer compounds is replaced with longer chain alkyl groups, which before and after compounding manifests properties for example, n-propyl or isobutyl, not only is the polym ideal for use on rubber processing equipment. These de erization reaction rate of this system appreciably reduced, sirable porperties lead to ready banding on mix mills, but the molecular weight of the resulting polymer de good tack, and ease of extrudability. 50 creases below desirable values. The decline in reaction It is still obscure which chemical and physical param rate and polymer properties is particularly sharp when the eters of a polymer contribute to the properties associated triethylaluminum is replaced with diisobutyl aluminum with good processability. It is hypothesized that a given hydride, triisobutylaluminum and/or organoaluminum molecular weight distribution of the polymer influences compounds containing even longer chain alkyl group than the processing properties of the polymer to a greater 55 the butyl group. degree than a high cis-1,4 molecular orientation. In contrast, the catalyst system of the present inven For example, polybutadiene made by a process, using tion, using as one catalyst component, boron trifluoride a two component catalyst system consisting of trialkyl complexed with at least one member from the group aluminum and titanium tetraiodide, has a cis-1,4 molec comprising a monohydric alcohol, a phenol, water and ular configuration in the neighborhood of 90 to 94% of 60 an oxygen-containing mineral acid, is much more versa the polymer structure formed. However, as a general rule, tile than the aforementioned system with respect to the the polybutadiene produced by this process does not pos selection of the trialkylaluminum compound. Various tri sess the ultimate in processability properties, and often alkylaluminum or dialkylaluminum hydrides (as indi requires blending with other elastomers to attain the cated by the specific embodiments herein) can be used in desired degree of processability with standard rubber mix 65 the catalyst system of this invention without affecting the 3,528,957 3. 4. rapid polymerization, the high yield, or the desirable poly Also “organomagnesium compounds' means any or mer viscosities characteristic of the system. ganomagnesium compound or any organomagnesium Thus, according to the invention, butadiene or buta halide of the Grignard type corresponding to the for diene in combination with other diolefins is polymerized mulas RMg or RMgY where R may be alkyl, aryl, by contact under solution polymerization conditions with arylalkyl or alkaryl and Y is fluorine, or R'R''Mg where a catalyst comprising (1) at least one organometallic R’ may be alkyl, aryl, or alkaryl and R' may be either compound in which the metal is selected from Groups I, alkyl, aryl, arylalkyl or alkaryl. Representative among the II and III of the Periodic System, (2) at least one organo compounds responding to these formulea are diethylmag metallic compound selected from the class consisting of nesium, dipropylmagnesium, ethylmagnesium fluoride and organonickel and organocobalt compounds, and (3) at phenylmagnesium fluoride. least one boron trifluoride complex prepared by complex O By the term “organozinc compound is meant any or ing boron trifluoride with a member of the class consist ganozinc compound responding to the formula R27n ing of monohydric alcohols, phenols, water and mineral where R may be alkyl, aryl, alkary or arylalkyl. Repre acids containing oxygen. sentative among such compounds are diethylzinc, dibu The organometallic compounds wherein the metals are tylzinc or diphenylzinc. selected from Groups I, II and III of the Periodic System By the term “organolithium compounds' is any organo are organocompounds of such metals as lithium, Sodium, lithium compound responding to the formula R-Li where potassium, rubidium, cesium, magnesium, calcium, stron R is an alkyl, alkaryl, arylalkyl or aryl group. Represent tium, beryllium, barium, zinc, cadmium, aluminum, gal ative among the compounds responding to the formula lium, and indium. The term “organometallic,' as used 20 set forth above are ehtyllithium, propyllithium, n-, sec here to refer to compounds, indicates that metals of or t-butyllithium, hexyllithium, styryllithium or phenyl Groups I, II and III of the Periodic System are attached lithium. Also, the organolithiumaluminum compounds directly to a carbon atom of alkyl, cycloalkyl, aryl, aryl may be used. These compounds respond to the formula alkyl and alkaryl radicals. All of the above compounds R'R''LiAl where R and R' may be alkyl, alkaryl or may be used in the practice of this invention. arylalkyl groups and R and R' may or may not be the When considering the organometallic compounds con same group. Representative of these compounds are taining metals from Groups I, II and III, it is preferred n-butyltriisobutyllithium aluminum, tetrabutyllithium for this invention to use organoaluminum compounds, aluminum, butyltriethyllithium aluminum and tetraiso oragnomagnesium compounds, organozinc compounds butyllithium aluminum. and organolithium compounds. 30 Representative of other organometallic compounds By the term “organoaluminum compound' is meant any with metals selected from Groups I, II and III of the organoaluminum compound responding to the formula Periodic System are compounds containing at least one of the metals, sodium, potassium, calcium, beryllium, / cadmium and mercury combined with at least one organic A-R radical selected from the group consisting of alkyls, alkaryls, arylalkyls, and aryls. in which R1 is selected from the group consisting of alkyl The second component of the catalyst system of this (including cycloalkyl), aryl, alkaryl, arylalkyl, hydrogen invention is an organometallic compound which contains and fluorine, R2 and R3 being selected from the group of nickel and/or cobalt. The compound may be any organo alkyl (including cycloalkyl), aryl, alkaryl, alkoxy and 40 nickel compound or any organocobalt compound. It is arylalkyl. Representative of the compounds responding preferred to employ soluble compounds of nickel and/or to the formula set forth above are: diethylaluminum fluo cobalt. These soluble compounds of nickel and/or cobalt ride, di-n-propylaluminum fluoride, di-n-butylaluminum are usually compounds of the said metals with a mono fluoride, diisobutylaluminum fluoride, dihexylaluminum or bi-dentate organic ligand containing up to 20 carbon fluoride, dioctylaluminum fluoride, and diphenylalumi atoms. "Ligand” is defined as an ion or molecule bound num fluoride. Also included are diethylaluminum hydride, to and considered bonded to a metal atom or ion. Mono di-n-propylaluminum hydride, di-n-butylaluminum hy dentate means having one position through which cova dride, diisobutylaluminum hydride, diphenylaluminum hy lent or coordinate bonds with the metal may be formed; dride, di-p-tolylaluminum hydride, dibenzylaluminum hy bi-dentate means having two positions through which dride, phenylethylaluminum hydride, phenyl-n-propylalu covalent or coordinate bonds with the metal may be minum hydride, p-tolylethylaluminum hydride, p-tolyl-n- formed. By the term "soluble' is meant soluble in inert propylaluminum hydride, p-tolylisopropylaluminum hy solvents. Thus, any nickel salt and/or cobalt salt of an dride, benzylethylaluminum hydride, and other organoalu organic acid, containing from about 1 to 20 carbon atoms minum hydrides. Also included are diethylethoxyalumi may be employed. num and dipropylethoxyaluminum. Also included are tri Representative of such organonickel compounds are methylaluminum, triethylaluminum, tri-n-propylalumi nickel benzoate, nickel acetate, nickel naphthenate, bis num, triisopropylaluminum, tri-n-butylaluminum, triisobu (alpha furyl dioxime) nickel, nickel octanoate, nickel pal tylaluminum, tripentylaluminum, trihexylaluminum, tricy mitate, nickel stearate, nickel acetylacetonate, bis(salicyl clohexylaluminum, trioctylaluminum, triphenylaluminum, aldehyde) ethylene dimine nickel and nickel salicylalde tri-p-tolylaluminum, tribenzylaluminum, ethyldiphenyl 60 hyde. Nickel tetracarbonyl also may be employed as the aluminum, ethyl-di-p-tolylaluminum, ethyldibenzylalu nickel containing catalyst in this invention. The preferred minum, diethylphenylaluminum, diethyl-p-tolylaluminum, component containing nickel is a nickel salt of a carbox diethylbenzylaluminum and other triorganoaluminum ylic acid or an organic complex compound of nickel. compounds. Representative of such organocobalt compounds are By the term "organomagnesium compounds' is meant cobalt benzoate, cobalt acetate, cobalt naphthenate, bis first any organomagnesium complex responding to the (alpha furyl dioxime) cobalt, cobalt actonoate, cobalt formula RaMgxt where R may be alkyl, aryl, arylalkyl palmitate, cobalt stearate, cobalt acetylacetonate, bis(sali or alkaryl; X is a halogen, and a and b are mole frac cylaldehyde ethylene dimine) cobalt and cobalt salicyl tions whose sum equals 2 while the ratio of a/b is greater aldehyde. Dicobalt octacarbonyl also may be employed than 2 but is not infinite. Representative among the com as the cobalt containing catalyst in this invention. The pounds responding to the formula set forth above are preferred component containing cobalt is a cobalt salt of ethylmagnesium chloride complex, cyclohexylmagnesium a carboxylic acid or an organic complex compound of bromide complex and phenylmagnesium chloride com cobalt. plex. Such compounds are usually prepared in the absence The third component of the catalyst system is a boron of ether. trifluoride complex prepared by complexing boron trifluo 3,528,957 5 6 ride with a member of the class of monohydric alcohols, catalyst. As a result, the optimum concentration for any phenols, water and mineral acids containing oxygen. The one catalyst component is dependent upon the concen BF molecule has a strong tendency to accept electrons tration of each of the other catalyst components. Although from donor molecules. Hence boron trifluoride complexes polymerization will occur over a wide range of catalyst can be formed from a large number of electron donating concentrations and ratios, polymers having the most desir compounds among which is the class consisting of mono able properties are obtained over a narrower range. It hydric alcohols, phenols, water and mineral acids contain has been found that polymerization will occur when the ing oxygen. All members of the above class contain mole ratio of the organometallic compound in which the active hydrogen. metal is selected from Groups I, II and III of the Periodic The monohydric alcohol sub-group of the above class System (Me) to the organonickel compound (Ni) ranges of compounds can be symbolically portrayed as R-OH O from about 0.3/1 to about 500/1, and when the mole where R represents an alkyl, cycloalkyl, and an arylalkyl ratio of the boron trifluoride complex prepared by com radical containing from 1 to 30 carbon atoms. Representa plexing boron trifluoride with a member of the class tive but not exhaustive of the alcohol group are methanol, consisting of monohydric alcohols, phenols, water and ethanol, n-propanol, isopropanol, n-butanol, benzyl alco mineral acids containing oxygen (BF complex) to the hol, and the like. The preferred complexes formed from organonickel compound (Ni) ranges from about 0.33/1 the above group are as follows: to about 300/1, and where the mole ratio of the organo metallic compound of Groups I, II, III metals (Me) to BF'methanol the BFs' complex ranges from about 0.1/1 to about 4/1. BF' ethanol The preferred Me/Ni mole ratio ranges from about BF-butanol 20 1/1 to about 150/1; the preferred BF complex/Ni mole The phenol sub-group of the above class of compounds ratio ranges from about 1/1 to about 150/1; and the pre can be symbolically portrayed as d-OH where p repre ferred Me/BFa' complex mole ratio ranges from about sents a benzenoid group. Representative but not exhaustive 0.3/1 to about 1.4/1. of the phenol group are phenol, p-cresol, resorcinol, naph 25 When organocobalt compounds replace organonickel thol, hydroquinone and the like. compounds or mixtures of organonickel and organocobalt The preferred complexes formed from the above phenol are used as the Second catalyst component in the ternary Sub-group are as follows: System of this invention, the mole ratio of cobalt (Co) and/or nickel (Ni) to the other catalyst components are BF-2 phenol 30 similar to those of nickel (Ni) shown above. BFap-cresol The three catalyst components may be charged to the polymerization system as separate catalyst components in BF-2 phenol is the most preferred complex formed from either a stepwise or a simultaneous manner, sometimes the phenol Sub-group. called "in situ.” The catalyst may also be “preformed” A number of the members in the sub-group of mineral outside the polymerization system whereby all the cat acids containing oxygen will complex with BF. Repre alyst components are mixed in the absence of the buta sentative but not exhaustive of the mineral acid sub diene, either with or without an inert diluent and the group are phosphoric acid, sulfuric acid, nitric acid and complete blend then added to the polymerization system. the like. The preferred complexes formed from the mineral An improved preformed catalyst system can be pre acid sub-group are BF-100% phosphoric acid and 40 pared by having a small amount of a diolefin, for example BF-85% phosphoric acid with the first mentioned com butadiene or isoprene, present when the catalyst compo plex being preferred. nents, Me, Ni and BF3 are mixed together. The diolefin Water, although in a sub-group by itself, forms at apparently reacts with the catalyst components to form a least two hydrate complexes with BF3. These are Catalyst complex which is more active, particularly when BFH2O and BF2HO. the polymerization system contains impurities, than either The various boron trifluoride complexes vary greatly the in situ catalyst (which is prepared in the presence in their shelf-life stability. Some, for example, BF iso of a very large amount of monomer) or the simple pre propanol are quite unstable in daylight at room temper formed catalyst prepared in the absence of the diolefin. ature. Others, for example, BF32 phenol are quite stable The improved preformed catalyst may be prepared by and possess a relatively long shelf-life at room temper dissolving a small amount of diolefinin a hydrocarbon ature. Solvent such as benzene or hexane, and then adding the When not available commercially, many of the boron Me component, the Nicomponent and then the BF3 com trifluoride complexes can be readily formed by directly plex component to the solvent. contacting boron trifluoride gas (a colorless gas at ordi The particular order of addition may be varied some nary temperatures and pressures, its boiling point being What but it is advantageous to have (1) the diolefin pres -101° C.), with the compound used as the complexing ent before the addition of both Me and Ni component agent, that is, the electron donor compound. This contact and (2) the Ni component present before the addition is accomplished with a reacting apparatus combined with of both Me and BF3 complex catalyst components. The a sensitive weighing mechanism in order to achieve the amount of the diolefin which can be present to form desired mole ratios between the BF and the electron the improved preformed catalyst can be varied over a donor compound. The reaction is carried out under an 60 inert atmosphere. The reaction environment may consist Wide range, and of course, is somewhat dependent on only of the reacting components, BF gas and the electron the other catalyst concentrations. However, the amount donor compound, or when convenient, the reaction may of diolefin, preferably butadiene, used to prepare the be carried out in the medium of an inert organic diluent. preformed catalyst should be between about 0.001 and This last condition is usually necessary when the electron 65 3.% of the total amount of monomer to be polymerized. donor compound exists as a solid and must be put into Based upon catalyst mole ratios, the diolefin to the Ni Solution or Suspension to insure adequate contact with mole ratio should be between about 0.5/1 and 1000/1, the BF3 gas. Where the particular BF complex, specified and preferably between about 2/1 and 100/1. as a catalyst component, possesses an unstable shelf-life, The concentration of the total catalyst system em it should be prepared as near to the time of polymerization O ployed depends on factors such as purity of the system, as feasible. polymerization rate desired, temperature and other fac The three component catalyst system of this invention tors therefore, specific concentrations cannot be set has shown polymerization activity over a wide range of forth except to say that catalytic amounts are used. Some catalyst concentrations and catalyst ratios. Apparently, Specific concentrations and ratios which produce elasto the three catalyst components interact to form the active merS having desirable properties will be illustrated in the 3,528,957 7 8 examples given herein to explain the teachings of this cosity is shown as DSV. DSV is a measure of molecular invention. weight of the polymer. In general, the polymerizations of this invention are carried out in any inert solvent, and thus, are solution TABLE I polymerizations. By the term “inert solvent' is meant Benzene solvent, 50° C.; Polymerization time, 1 hour Millinole O.0 gm. BD that the solvent or diluent does not enter into the struc Yield, ture of the resulting polymer nor does it adversely affect BF3.2 Wit. the properties of the resulting polymer nor does it have TEAL Nisalt phenol percent DSV any adverse effect on the activity of the catalyst em 0.06 0.00 0.079 49 2.96 ployed. Such solvents are usually aliphatic, aromatic, 0.06 0.0025 0.0775 70 2.88 cycloaliphatic hydrocarbons and ethers, representative 0.06 0.005 0.075 82 2.79 of which are pentane, hexane, heptane, toluene, benzene, 0.06 0.0075 0.0725 76 2.49 cyclohexane, diisopropyl ether and the like. Preferred 0.06 0.010 0.070 68 2.37 solvents are hexane and benzene. The solvent/monomer The data in the above table indicate that a variation in volume ratio may be varied over a wide range. Up to the concentration of the Ni salt (nickel octanoate) cata 20 or more to 1 volume ratio of solvent to monomer can lyst component has only little effect on the dilute solu be employed. It is usually preferred or more convenient tion viscosity of the formed polybutadiene. The total to use a solvent/monomer volume ratio of about 3/1 to about 6/1. Suspension polymerization may be carried catalyst concentration remained constant. out by using a solvent, such as butane or pentane, in EXAMPLE II which the polymer formed is insoluble. It should be Butadiene was polymerized in a manner similar to understood, however, that it is not intended to exclude that of Example I using the same catalyst components bulk polymerizations from the Scope of this application. and procedures, except that heptane rather than benzene The polymerization may be continuous or batch type. was used as the inert organic diluent. The results are It is usually desirable to conduct the polymerizations 25 shown in Table II below. of this invention employing air-free and moisture-free techniques. TABLE I The temperatures employed in the practice of this in Heptane solvent, 50° C.; Polymerization time, 1 hour vention have not been found to be critical and may vary MillimolefiO.0 gm. BO Yield, from a low temperature such as -10° C. or below up to 30 BF3.2 Wit. high temperatures of 100° C. or higher. However, a more TEAL. Nisalt phenol percent DSV desirable temperature range is between about 30° C. and 0.06 0.00 0.075 35 3.52. about 90° C. Ambient pressures are usually used but 0.06 0.0025 0.0775 78 3.54 higher or lower pressures may be employed. 0.06 0.005 0.075 85 3.62 0.06 0.010 0.070 79 3.53 The practice of this invention is further illustrated by 0.06 0.020 0, O60 70 3.9 reference to the following examples which are intended 0.06 0.030 0.050 42 3.02 to be representative rather than restrictive of the scope of this invention. EXAMPLE III EXAMPLE I 40 Butadiene was polymerized in a manner similar to A purified butadiene in benzene solution containing that of Example II using the same catalyst components 10 grams of butadiene per hundred milliliters of solution and procedures except that the amounts of the catalyst was charged to a number of 4-ounce bottles. Nitrogen components were varied. In Experiments 4, 5 and 6 below, was flushed over the surface of this premix while the cata the total catalyst quantities were approximately double lyst was charged in the amounts shown in the table below. the quantities used in Experiments 1, 2 and 3 below, as The catalyst employed was a mixture of triethylaluminum well as in all of the experiments in Examples I and II (TEAL), nickel octanoate (Nisalt or Ni oct) and boron above. Table III below indicates that all of the varia trifluoride 2phenol complex, and was charged by the in tions in the catalyst ratios have not affected significantly situ method. The bottles were tumbled end over end for the micro-structure of the polybutadiene formed. In all one hour in a water bath maintained at 50° C. The po experiments in Table III, the cis-1,4 addition content is lymerizations were deactivated by the addition to the above 96%.

TABLE II Heptane solvent, 50° C.; Polymerization time, as shown Millimoles/10gm. BD Polyn erization Yield IR, BF3.2 time, Wit. percent TEAL Nisalt phenol hrs. percent DSV cisi

0.02 0.0025 0.17 8 28 ------96.5 0.06 0.005 0.075 0.5 73 3.61 97.6 0.095 0.005 0.40 18 45 6.46 97.8 0.15 O.00 0.129 29 ------97. 0.06 0.005 0.215 84 2.43 96. 20.0 0.005 0.10 91 3.84 99. i. When the cis-14 content is 96% or greater, the balance of the microstructure is comprised of approximately equal parts of trans-1,4-polybutadiene and 12-polybutadiene. However, the percent 1,2-addition is seldon greater than 2%. 2 The organometallic compound in Experiment 6 was triisobutyl-aluminum rather than TEA (tricthylaluminum). system of an amine-type stopping agent and an antioxi EXAMPLE IV dant, both components being added as one part per Butadiene was polymerized in a manner similar to that hundred parts of original monomer charged. used in Example I using the same catalyst components, The results are shown in Table I. Dilute solution vis- 75 except that the catalyst components were charged at a 3,528,957 9 10 constant ratio with respect to each component and also Table VI indicates that the order of charging the catalyst at constant total level in all the experiments in Table IV components has an effect on the early reaction rate of below. Table IV below indicates that the DSV (dilute Solution viscosity) of the polybutadiene polymer remains the polymerization system. Table VI indicates that in relatively independent of the degree of conversion. situ addition Order “A” promotes both an earlier re TABLE IW Benzene Solvent, 50° C.; Polymerization time, as shown (Five Identically Charged. Bottles) MillimolesfiOgms. Bid Polym ------mm----- erization. Yield, BF3-2 Total time, wt., TEAL. Nisalt Phenol catalyst hrs. percent DSW Ex. No. 0.06 0.005 0.075 0.40 0.5 58 2.65 2 0.06 0, 005 0.075 0,140 O 82 2 3 0, 06 0, 005 0.075 0.40 2.. O 9. 4 0.6 0.005 0.075 O. 140 4. O 96.5 5 0.06 0.005 0.075 0.40 18.0 98 EXAMPLE V action (a very short induction period), and a faster re Butadiene was polymerized in a method similar to that 20 " ": EXAMPLE VII used in Example I except that a different ratio and total quantity of catalyst components were employed, Butadiene was polymerized using a procedure simi Also, the catalysts were added in both preformed and lar to the procedure used in Example I except that various in situ addition. In both the preformed and in situ addi BFalcohol complexes were used in addition to BF-2 tions, the catalyst component ratios and total 9tantities 25 phenol. Catalyst components and catalyst concentrations charged were the same. By “in situ' addition is meant are shown in Table VIIa below. Results are given in that the catalyst components are added separately to the Table VIIb. main polymerization reaction vessel. Preformed addition means adding all the catalyst components together and TABLE WIIa, then charging the separate active catalyst system to the 30 (Solvent, benzene; Polymerization temperature, 50° C. main polymerization system. MillimolesliOgm. BD TABLE W Ni Oc- BF3. R8 BFscom Solvent, benzene; Temperature, 50°C. R3Al tanoate complex charged charged Catalyst charge, millimoles/10gm. BD; TEALNi salti|BF3. 2 phenol .i.00.005/0.11. Exp. No.: X 35 " "... 0.06 0, 005 0.075 TEAL 2 MeOH Yield, wt. percent at time in hours 2 0.06 0.005 0.075 TEAL MeOH - DSW 3 - 0, 06 0.005 0.075 TEAL EtOH Catlayst 0.25 0.50 at 2 percent 4 - 0.06 0.005 0.075 TEAL BOE charged hrs. hrs. 1 hr. 2hrs. 4 hrs. hrs. cis-1,4 5 0.06 0.005 0.075 TEAL 2 phenol 6 0.06 0.005 0.075 TEAL 2 phenol In situ addition.------66 77 87 91 2.71. 96.8 7 0.06 0, 005 0.075 TEAL p-cresol Performed.------57 72 83 90 9. 2.96 96.8 40 8 0.04 0.005 0.040 TNPA. .EtOE ------a-mammarmamrm 9 ------0.0 0, 0075 0.40 TNPA MeOH Table V indicates that a preformed catalyst system pro motes an earlier and a faster reaction rate. TABLE WIb EXAMPLE VI Yield, wt. percent at 45 time in hours Butadiene was polymerized using a procedure similar Percent to the procedure used in Example I except for the foll 1 2 4 19 DSW cis-1,4 lowing: (1) All catalyst ratios and quantities were held constant. s 7. s (2) Tri-normal-propyl aluminum (TNPA) replaced tri- S. S. ethyl aluminum (TEAL) in one series of experiments. 34 00---- (3) The order of catalyst component addition was varied. s g S; (4) BF-EtOH was used as the boron trifluoride com- 58 82 89 plex rather than BF-2 phenol. Two different orders 83 85 92 of addition were tried with two different R3A com- 5 pounds as follows: (A) Charging order: EXAMPLE VIII RaAl--Ni octanoate--BFEtOH Butadiene was polymerized using a procedure similar to the procedure used in Example I except that various (B) Charging order: 60 BF3 complexes of hydrates and mineral acids were em Ni octanoate--BF EtOH--RAl ployed as one catalyst component. TNPA (tri-normal propyl aluminum) was used as the organoaluminum com Table VI below shows the effects of the two different ponent. Table VIIIa below shows the catalysts used and orders of catalyst component additions. the catalyst concentrations. Table VIIIb gives the polym ABLE VI 65 erization results. Solvent, benzene; Temperature, 50° C.; In situ system. Catalyst ratios and quantities, RaAl/Ni salt/BFalEtOHe TABLE WII, 0.06/0.005/0.075 millimole/10 gms. BD. Solvent, benzene; Temperature, 50° C.) Yield, wt. pereent at time in hrs. Millinolesfl0gms. BD orderCharging - 0.5 - - 2 - 4. - 8 70 - NiOc-- BF3- complexBF3. R3, Al tanoate complex used

R3A1 component: ------53 77 87 88 - - - 7 42 67 77 0.060 0,005 0.075 PO 27 48 87 83 87 0.10 O. O. 0, 10 .2EO w - - - - - 5 26 51 82 0.06 0.005 0.075 .H2O 3,528,957 12 umn headed “Nickel salt' indicates the particular nickel TABLE WIb Salt employed. Yield, wt. percent at time in hours percent TABLE XI 4 CS Benzene solvent, 50° C.; Polymerization time, as show.a. Catalyst concentration : TEALANi sat/BEa-2 phenol - 0.06/0.005/0.075 millimole/10 gm. BD. Yield: Wt. percent at time in hours In Table VIII above the mineral acid and hydrate Com Nickel Salt 4 20 SW O plexes are immiscible with the polymerization Solvents. Exp. No.: 1------Octanoate------78 90 ------2.30 It is believed that these BF complexes will operate more 2------Naphthenate------76 ------2.73 efficiently and consistently if excellent dispersion of the 3------Acetylacetonate.------65 ------2.5 4------Salicylaldehyde------30 76 ------2.66 catalyst complex can be effected by either use of Sur 5. - Stearate------5 43 3.21. factants or mechanical techniques. 6- - Acetate. 4H2O.-- - 10 18------EXAMPLE IX 7--- -- Acetate, 4H2O --- 33 53 3.44. 1 TEAL (triethylaluminum) concentration was 0.075 millinoles;10 Butadiene was polymerized in a manner similar to the gns. of BD in Experiment 7. manner used in Example I except that a number of BF3 complex types were used, and the polymerization time was The nickel acetate used in Experiments 6 and 7 con 18 hours. The types of BF complexes used and the quan- 20 tained water of hydration and was much less active than tities are shown in Table IX below. the other nickel salts at equivalent concentrations. An TABLE X Solvent, benzene; Temperature, 50° C...... ------w-ear-o-Hi Yield, wt. per cent in Exp. No. TEAL. NiOct Complex BF3 complex used 18 hrs. DSW 0.06 0.005 0.075 .2-acetic acid Nil 0.06 0.005 0.075 -Acetic acid 10 Solid. 0.06 0,005 0.075 Butyric acid 6 0.06 0.005 0.075 .2-propylene glycol 0.06 0.005 0.075 2-ethoxy-etnaonl 20 0.06 0.005 0.15 .2 propylene glycol 8 - - - - 0.10 0.01 0.30 -Butyric acid 22 Semi-liquid.

Table IX above indicates that many BFa complexes. 2. increase in the TEAL catalyst component in Experiment 7 not suitable and will not form a high cis-1,4-polybutadiene increased the overall catalyst activity to some extent but at ordinary polymerization conditions. the activity was still much less than that when nickel octanoate was used. EXAMPLE X 40 While certain representative embodiments and details Butadiene was polymerized using a procedure similar have been shown for the purpose of illustrating the inven to the procedure used in Example I except that various tion, it will be apparent to those skilled in this art that alkyl aluminum and alkyl aluminum hydride compounds various changes and modifications may be made therein were used as one catalyst component, and the catalyst com without departing from the spirit or scope of the inven ponents were charged at a constant ratio with respect to tion. each component and at a constant total catalyst level. 45 What is claimed is: Table X, below, indicates that would the exception of 1. The process for the polymerization of butadiene and where EtAIOEt (diethylethoxyaluminum) was used as butadiene in mixture with other diolefins to form polymers the organoaluminum catalyst component, the use of vari containing a high proportion of the butadiene units in the ous alkyl aluminum compounds results in similar polym cis-1,4 configuration comprising contacting at least one erization rates and polymer viscosities. 50 monomer from the group of butadiene and butadiene in TABLE X mixture with other diolefins, under polymerization condi Benzene solvent, 50° C.; Polymerization time, as shown. tions, with a catalyst comprising (1) at least one organo Catalyst concentration: Al/NiOctanoate/BFs-2 phenol metallic compound in which the metal is selected from s: 0.06/0.005/0.075 millimoles/10 g. BD. Groups I, II and III of the Periodic System, (2) at least Yield: wit. percent 55 one organometallic compound selected from the class con at time in hours Reducing Percent sisting of nickel salts of carboxylic acids, organic com agent 0.5 1 2 4 22 DSW cis-1,4- plex compounds of nickel, nickel tetracarbonyl, cobalt Exp. No Salts of carboxylic acids, organic complex compounds of

1------TEAL 63 78 84 90 ---- 2.30 ------cobalt and dicobalt octacarbonyl and (3) at least one 2------TIBA 59 76 84 ------2.62 ------60 8------DIBAL-H 62 77 84 89 - 2.47 97.1 boron trifluoride complex prepared by complexing boron a Et2AlOEt ------3.45 97. trifluoride with a member of the class consisting of mono NOTE: hydric alcohols, phenols, water and mineral acids contain TEAL = triethylaluminum. ing oxygen. TIBAL =triisobutylaluminum. DIBAL-FIs diisobutylaluminum hydride. 65 2. The process according to claim in which butadiene Et3AOEt= diethylethoxyaluminum. 1,3 alone is employed. 3. A process according to claim in which the organo EXAMPLE X metallic compound of metals from Groups I, II and III Butadiene was polymerized using a procedure similar to of the Periodic System is selected from the group con the procedure used in Example I except that various or sisting of organoaluminum compounds, organomagnesium ganic salts of nickel were used. 70 compounds, organozinc compounds and organolithium Table XI, below, indicates that the specific organo compounds; and in which the organonickel compound is metallic compound of nickel used has an effect on the Selected from the group consisting of nickel salts of carbox polymerization reaction rate as determined by the yield ylic acids and organic complex compounds of nickel; and calculated at given time increments after the start of the in which the boron trifluoride complex is selected from polymerization, and the molecular Weight also. The col- 75 the group consising of BF-2 phenol, BF 100% phos 3,528,957 13 14 phoric acid, BF butanol, BFethanol and BF hydrates. sisting of an aluminum trialkyl and a dialkylaluminum hy 4. The process according to claim 1 in which the mole dride. ratio of organometallic compound with metals selected 9. A catalyst composition comprising (1) at least one from Groups I, II and III of the Periodic System/organo organometallic compound in which the metal is selected nickel and/or organocobalt compound ranges from about from Groups I, II and III of the Periodic System, (2) at 0.3/1 to about 500/1, the mole ratio of the BF-complex/ least one organometallic compound selected from the class organonickel and/or organocobalt compound ranges from consisting of nickel salts of carboxylic acids, organic com about 0.33/1 to about 300/1 and the mole ratio of the or plex compounds of nickel, nickel tetracarbonyl, cobalt ganometallic compound with metals selected from Groups Salts of carboxylic acids, organic complex compounds of I, II and III of the Periodic System/BF complex ranges cobalt and dicobalt octacarbonyl and (3) at least one from about 0.1/1 to about 4/1. O boron trifluoride complex prepared by complexing boron 5. The process according to claim 4 in which the mole trifluoride with a member of the class consisting of mono ratio of the organometallic compounds with metals se hydric alcohols, mineral acids containing oxygen, phenols lected from Groups I, II and III of the Periodic System/or and water. ganonickel and/or organocobalt compound ranges from 5 10. The composition according to claim 9 in which the about 1/1 to about 150/1; the preferred mole ratio of the mole ratio of the organometallic compound with metals BF8" complex/organonickel and/or organocobalt com Selected from Groups I, II and III of the Periodic System/ pound ranges from about 1/1 to about 150/1; and the organonickel and/or organocobalt compound ranges from preferred mole ratio of the organometallic compound with about 0.3/1 to about 500/1, the mole ratio of the BF. metals selected from Groups I, II and III of the Periodic 20 complex/organonickel and/or organocobalt compound System/BF complex ranges from about 0.3/1 to about ranges from about 0.33/1 to about 300/1 and the mole 1.4/. ratio of the organometallic compound with metals selected 6. The process according to claim 4 in which the cata from Groups I, II and III of the Periodic System/BF. lyst is preformed in the presence of a small amount of the complex ranges from about 0.1/1 to about 4/1. diolefin to be polymerized by adding to the diolefin (1) at least one organometallic compound in which the metal is References Cited selected from Groups I, II and III of the Periodic Sys UNITED STATES PATENTS tem and (2) at least one organometallic compound selected from the class consisting of organonickel and organoco 2,977,349 3/1961 Brockway et al. ----- 260-94.3 balt compounds and subsequently adding (3) at least one 30 3,170,905 2/1965 Ueda et al. ------260-94.3 boron trifluoride complex prepared by complexing boron 3,170,907 2/1965 Ueda et al. ------260-94.3 trifluoride with a member of the class consisting of mono 3,219,650 1 1/1965 Hill ------260-94.3 hydric alcohols, phenols, water and mineral acids con 3,458,488 7/1969 Duck et al. ------260-82.1 taining oxygen, the mole ratio of the diolefin to the organo 3,471,462 10/1969 Matsumoto et al. --- 260-94.3 nickel and/or organocobalt compound being between FOREIGN PATENTS about 0.5/1 and 1000/1. 7. The process according to claim 3 in which the or 662,850 5/1963 Canada. ganometallic compounds with metals selected from Groups JOSEPH L. SCHOFER, Primary Examiner I, II and III of the Periodic System is an organoaluminum compound. 40 R. A. GAITHER, Assistant Examiner 8. The process according to claim 7 in which the or U.S. C. X.R. ganoaluminum compound is selected from the group con 252-431; 260-82.1 73' UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,528,957 September 15, 1970 Inventor(s) Morford C. Throckmorton and Willian M. Saltman It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below: - - Column l, line 9, "properties" is misspelled. Column 2, line ll, between "appears" and "be" insert -- to . Column 8, Table II, Exil, under heading "BF32 phenol", 'O. O75" should read -- O. O79 --. Column 8, Table IIT, Ex. 3, under heading "BF2 phenol", "O.O" should read -- 0.00 -- . Column lo, Table VIIa, the heading "R3 charged" should read -- R3All charged --. Column l0, Table VIIa, the heading "BF oom- charged" should read - a BF3 complex charged --. Column ill, Table IX, under heading entitled "BF complex used", Ex. 5, "ethanol" is misspelled. Column ill, line 46, "would" should read -- with --. Column ill, Table X, under heading "22" of Ex. 2, -- 57 -- has been omitted and should be inserted. SIGNED AND SEAED FE231971 r l- SEAL) - A. WAM E. SCBUYIER, JR. Edward M. Fletcher, Jr. Commissioner of PaPatent S