Патент USA US3095416код для вставки
United States Patent 0 3,095,406 Patented June 25, 1963 1 2 polymerization catalyst so as to thereby obtain rubbery 3,095,406 polymer products having desirable physical properties. PREPARATION OF POLYMERS 0F CONJUGATED DIENES James N. Short and James E. Puckett, Bartlesville, Okla, assignors to Phillips Petroleum Company, a corporation Other and further objects and advantages of the in vention will become apparent to those skilled in the art No Drawing. Filed July 28, 1958, Ser. No. 751,187 15 Claims. (Cl. 260-943) whereby conjugated dienes can be consistently polym upon consideration of the ‘accompanying disclosure. of Delaware The instant invention is concerned with .a process erized to rubbery polymers of a desired inherent vis cosity. Broadly speaking, in a process in which a con ' This invention relates to the preparation of polymers 10 juga-ted diene is contacted with a polymerization cata of conjugated dienes. In one ‘aspect, the invention re lyst, the instant invention resides in the improvement lates to a method for polymerizing conjugated dienes in which comprises treating the conjugated diene with a the presence iof a catalyst comprising an organomet-al v polyhydric alcohol prior to its being contacted with the or metal hydride. In another aspect, the invention relates catalyst. It has been discovered that the polymerization to ‘a polymerization process in which the conjugated 15 can be effected at relatively low catalyst levels to give diene to be polymerized is pretreated prior to contact ?rm, non-sticky, rubbery polymers if the conjugated diene with the polymerization catalyst. is ?rst treated with a polyhydric alcohol. The poly It has been previously disclosed that conjugated dienes hydric alcohol treatment can be effected by ‘any suitable can be polymerized in the presence of a catalyst com method known in the art, for example, by liquid-liquid However, 20 extraction with subsequent separation of the monomer it has been found that when the polymerization is car phase or by vapor-liquid extraction in a column. . ' ried out at low catalyst levels, for example, in the case The monomeric material polymerized to produce rub of butyllithinm at below 4 millimols per 100 grams of bery polymers by the process of this invention comprises monomer charged to the process, rather erratic results conjugated dienes‘ containing from 4 to 10, inclusive, ‘are often obtained. In other words, the polymerization 25 carbon ‘atoms. Examples of conjugated dienes which prising an organometal or a metal hydride. reaction may or may not occur. In many cases where can be used include 1,3—butadiene, 2-methyl-l,3~buta polymerization does take place, the product has a low inherent viscosity (low molecular weight), and a poly diene (isoprene), 2,3-dimethyl-l,3-butadiene, 1,3-penta mer is often obtained which is soft and sticky or it may in some instances resemble a wax instead of 1a rubber. 30 Although .the conjugated dienes are ordinarily used in a high state of purity, it appears that they-still contain diene, 2—methyl—1,3-pentadiene, 2,3-dimethyl-1,3-penta diene, 3-methyl-1,3-pentadiene, 2-phenylbutadiene, vand the like. . This invention is applicable to the polymerization of the above-de?ned conjugated dienes either alone or in small amounts of materials which have a deleterious admixture with each other and/or with one or more effect on the polymerization catalyst and which are be ‘other compounds containing an active CH2=C< group 35 lieved to be in some way responsible for the erratic which are copolymerizable therewith. Included vamong results obtained. Treatment of conjugated dienes, such these latter compounds are aliphatic l-ole?ns having up as butadiene or isoprene, with a drying agent, .e.g., cal to and including 8 carbon atoms per molecule, such ‘as cium sulfate, prior to polymerization has been tried in ethylene, propylene, l-butene, l-hex-ene, and l-octen‘e. order to remove traces of moisture which might account 40 Branched chain ole?ns, such as isobutylene, can be used as well as 1,1-dialkyl-substituted and 1,2-di-alkyl-substi~ for the ‘unsatisfactory results. However, even when fol lowing this procedure, polymerization may not occur tuted ethylenes such as butene-Z, pentene-Z, hexene-Z, heptene-Z, 2~rnethylbutene-1, 2-‘methylhexene-1, Z-ethyl with any regularity unless comparatively large ‘amounts heptene-l, and the like. Other ole?ns which can be of catalyst ‘are utilized. Furthermore, in instances where polymerization does occur, the conversion is frequently 45 used include di- ‘and polyole?ns, such as 1,5-hexadiene, 1,4-pentadiene and 1,4,7-octatriene, and cyclic ole?ns, low and the polymer product may have ‘a low inherent such as cyclohexene. Other examples of compounds viscosity. While the use of higher catalyst levels might containing an active CH2=C< group which ‘are co polymerizable with one or more of .the conjugated dienes appear to be feasible, increasing the amount of the cata lyst often results in the production of polymers with de are ‘styrene, acrylonitrile, methacrylonitrile, methyl acry creasing inherent viscosity, and low molecular weight, late, methyl methacrylate, vinyl acetate, vinyl chloride, sticky ‘and non-rubbery products are often obtained. It is an object of this invention, therefore, to provide ‘an improved process for polymerizing conjugated dienes in the presence of a catalyst comprising an organometal or a metal hydride. Another object of the invention is to provide a process for polymerizing conjugated dienes in which the polym erization is carried out at catalyst levels lower than those vinyl-idene bromide, Z-methyl-S-vinylpyridine, 2-vinylpy ridine, 3-vinylpyridine, 3-viny-1tol-uene, l-vinylnap-htha lene, Z-Vinylnaphthalene, 4-v-inyltoluene. 55 As previously mentioned prior to contact with the polymerization catalyst, the conjugated dienes to be polymerized are treated with a po'lyhydric alcohol. The polyhydric alcohol is liquid under the treating condi tions and preferably contains not more than 10, more usually employed while obtaining a product having good 60 desirably not more than .5, carbon atoms per molecule. physical properties. The term “polyhydric alcohol” as used herein is intended A further object of the invention is to provide a proc to designate an alcohol containing two or three hydroxy 1 ess for polymerizing conjugated dienes in which the con groups. As the treating agent, it is preferred to use the j jugated dienes are pretreated prior to contact with the glycols', particularly ethylene glycol. Examples of poly 3,095,406 3 hydric alcohols which can be employed include glycols, such as ethylene glycol, propylene glycol, ‘diethylene glycol, trimethylene glycol, triethylene glycol, tetrameth ylene glycol, diethylene glycol, triethylene glycol, butyl ene glycol, amylene glycol, 1,6-hexamethylene glycol (1,6-hexanediol), 2,4-hexanediol, 1,8-octanediol, 4,5 octanediol, 1,10-decanedio-l, and 1,2-decanediol, glycerol, 1,2,3-butanetriol, 1,3,5-pent-anetriol, and 2,3,4-hexane tr-iol. With the lower viscosity treating agents, such as ethylene glycol, the treatment can be effected at room temperature, e.g., at about 25° C. However, with ma terials which are very viscous or solid at room tempera— 4 cyclohexane, 1,2,3,5-tetralithio-4-hexylanthracene, and the like. When employing a two component catalyst system to polymerize conjugated dienes according to this invention, one component is an organometal or a metal hydride and the second component is 1a Group IV to V1 and VIII (Mendeleef’s Periodic System) metal compound, e.g., a salt or alcoholate. The organometal compounds referred to include, without limitation, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, alkylcycloaryl, or cycloalkylaryl com pounds of di-, tri-, or tetravalent metals, particularly Group I, II, III or IVB metals such as sodium, potassium, lithium, rubidium, cesium, magnesium, cadmium, mer ture, such as glycerol or 1,8-octanediol, higher tempera cury, zinc, barium, lead, tin, aluminum, boron, gallium, tures, e.g., up to about 80° C., are advantageously uti lized in order to facilitate contact of the conjugated diene 15 indium and beryllium, or such organometal compounds in which one or more of the organo groups is replaced with the treating agent in liquid form. by a hydrogen atom and/ or a halogen atom. The organo After treatment of the conjugated dienes with the poly groups can be quite large, compounds being applicable hydric alcohol treating agent, the polymerization is which have 15 or more carbon atoms in each group and effected by contacting the conjugated dienes with the polymerization catalyst. Because of this treatment of 20 40 or more carbon atoms in the molecule. Speci?c ex amples of such organometal compounds include triethyl the monomeric materials, it has been found that the polymerization can be carried out at much lower catalyst levels than those ordinarily employed. Thus, it has been found that polymerization can be e?ected using catalyst levels as low as 1.5 millimoles per 100 grams of mono mers. On the other hand, when untreated monomers are used, about 3 millimoles are required. Furthermore, when operating at a catalyst level of 1.5 to 3 millimoles, high conversions are consistently obtained while produc aluminum, triisobutylaluminum, a mixture of diethyl aluminum chloride and ethylaluminum dichloride, some times referred to as ethylaluminum sesquichloride, di ethylaluminum hydride, ethylaluminum dichloride or di ethylaluminum chloride, taken alone, trioctylaluminum, tridodecylaluminum, triphenylaluminum, triphenylgal lium, ‘diphenylberyllium, dicyclohexylberyllium, diethyl zinc, cyclohexylzinc chloride, tetraphenyllead, tetracthyl adversely affect the polymerization catalyst. Since treat til'l, land CHgAlClz, (C4H9)2AIBI‘, CQHHAIIQ, (031402631: (C6H11)2GaCl (cyclohexane derivative), C5H5GaBrZ, Cz0H4iGaBr2, (c14H29)2GaF, (ceHshlncl, caHnlnFz, CGHHInBrZ (cyclohexane derivative), C17H35BGI, and the corresponding to the general formula R(Li)x, ‘wherein halogen, and R is an organic radical, usually having 20 ing rubbery polymers having desirable physical character istics. The reason for such improvement in the polymer ization is not completely understood. However, it ap pears that the treatment with the polyhydric alcohols results in the removal of materials which when present like. ment with a conventional drying agent does not result in The metal hydrides which can be employed include the unexpected improvement, it appears that the poly hydrides of Groups I, II and III metals. Speci?c ex hydric alcohol treatment of the conjugated dienes has an effect other than the mere removal of moisture from the 40 amples of suitable hydrides are aluminum hydride, lithium aluminum hydride, barium hydride, gallium hydride, in monomeric materials. dium hydride, sodium aluminum hydride, and potassium The catalysts used in the practice of the process of this beryllium hydride, and the like. invention are, in general, those which are effective for The compounds of a metal of Groups IV to VI and polymerizing conjugated ‘dienes to solid polymers. It is VIII of the Periodic System include the oxides, hydrides, usually preferred to employ a catalyst comprising a member selected from the group consisting of organo 45 halides, oxyhalides, and salts of organic acids, usually having 20 or less carbon atoms, such as formic acid. Ex metals and metal hydrides. The organometals and the amples of these metals are titanium, zirconium, thorium, metal hydrides are often used in admixture with certain hafnium, vanadium, chromium, molybdenum and iridium. metal compounds as will become apparent hereinafter The 'alcoholates of a metal of Group IV of the Periodic from the description of catalyst systems containing two System which can be employed with an organometal or components. metal hydride conform to the formula XnM(OR)m, One particularly effective catalyst for use in the process where m-l-n equals the valence of the metal M, X is a of this invention comprises an organolithium compound R is a hydrocarbon radical selected from the group con or less carbon atoms and preferably being an alkyl, cyclo sisting of aliphatic, cycloaliphatic and aromatic radicals 55 alkyl or aryl group. Speci?c examples of such alcohol ates rare titanium butoxide (tetra-n-butyl titanate), tetra sec-butyl titanate, tetraisopropyl titanate, tetra-Z-ethyl from 1 to 4, inclusive. The R group has a valence equal butyl titanate, tetrastearyl titanate, tetracthyl titanate, to the integer x and preferably contains from 1 to 20, tetra(choroethyl)titanate, tetra-m-tolyl titanate, tetraallyl inclusive, carbon atoms, although it is within the scope of the invention to use higher molecular weight compounds. 60 titanate, tetracyclohexenyl titanate, tetracyclopentyl titanate, tetracthyl zirconate, tetramethyl zirconate, tetra Examples of org-anolithium compounds which can be and combinations of these radicals and x is an integer used include methyllithium, isopropyllithium, n-butyl lithium, tert-octyllithium, n-‘decyllithium, phenyllithium, naphthyllithium, 4-butylphenyllithium, p-tolyllithium, 4 phenylbutyllithium, cyclohexyllithium, 4-butylcyclohexyl lithium, 4-cyclohexylbutyllithium, dilithiomethane, 1,4 dilithiobutane, 1,10-dilithiodecane, 1,20-di1ithioeicosane, 1,4-dilithiocyclohexane, 1,4-dilithiobutene-2, 1,8-dilithio 3-decene, 1,4-dilithiobenzene, 1,5-dilithionaphthalene, 1,2 dilithio-1,2-diphenylethane, 1,5-dilithioanthracene, 1,2-‘di lithio-1,8-diphenyloctane, 1,3,5-trilithiopentane, 1,5,15 trilithioeicosane, 1,3,S-trilithiocyclohexane, 1,2,5-tri1ithio naphthalene, 1,3,S-trilithioanthracene, 1,3,5,8-tetralithio decane, 1,5,l0,20-tetralithioeicosane, 1,2,4,6-tetralithio isopropyl zirconate, tetraamyl zirconate, dichlorodiethyl titanate (Cl2Ti(OC2H5)2), monochlorotriethyl titanate (ClTi(OC2H5)3), and ‘dichlorodiethyl zirconate (C12ZT(OC2H5)2) Also included are such compounds as Hf(OCH3)4, Tl(OC3H7)4, Th(OC6H5)4, Cl3Ti(OC6H4OH3), ZF(OC4H7)4, C12Hf(OC10H21)2, Th(OCsHia)4, and ZT(OC12H25)4 -A particularly useful catalyst system for employment in the process of this invention comprises (1) a compound corresponding to the formula M'R’X, where M’ is one of the metals aluminum, gallium, indium, thallium, beryl 3,095,406 5 6 lium, mercury, lead, zinc or mercury, R’ is hydrogen, an lithium compound as the catalyst, it has been found that the use of polar compounds in admixture with the hydro carbon diluent increases the reaction rate of the polym erization process of this invention. Examples of polar compounds which do not inactivate the organolithium alkyl, cycloalkyl, aryl, alkaryl, :aralkyl, alkylcycloalkyl, or cycloalkylalkyl radical and x is equal to the valence of the metal M, and (2) a halide of a Group IV, V or VI metal, such as titanium, vanadium or molybdenum. Ex amples of the M’R'x compounds have been given herein catalyst and which may, therefore, be utilized with the before. The M'R'x compounds can also be used in the hydrocarbon diluents are ethers, thioethers (sul?des), form of their known and stable organic complexes, such and tertiary amines. Speci?c examples of such polar as complexes with ethers, thioethers, amines, alkali metal materials include dimethyl ether, diethyl ether, ethyl hydrides, alkali metal alkyls or alkali metal ,aryls. Ex 10 methyl ether, ethyl propyl ether, di-nspropyl ether, di-n amples or such complex compounds which can be em octyl ether, tetramethylene oxide (tetrahydrofuran), di ployed include LiAlH4, NaAl(CH3)4, NaBe(C6H5)3, NaBe(C2H5)3, and the like. ‘Examples of suitable catalyst systems in accordance with the foregoing disclosure are as iollows: (a) Aluminum trialkyls, e.g., triethylaluminum or tri isobutylaluminum, and the tetravalent metal halides of the type represented ‘by titanium tetrachloride or titanium 15 oxane, paraldehyde, anisole, 1,2-dimethoxyethane, di benzyl ether, diphenyl ether, dimethyl sul?de, diethyl sul?de, di-n-propyl sul?de, di-n-butyl sul?de, methyl ethyl sul?de, dimethylethylamine, tri-n-propylamine, tri-n-tbut ylamine, trimethylamine, triethylamine, N,N-dimethyl amine, pyridine, quinoline, N-ethylpiperidine, 'N-methyl N-ethyl aniline, N-methylmorpholine, ‘and the like. It is tetraiodide; to be understood also that mixtures of these polar com (b) Molybdenum pentachloride and an organometal 20 pounds can be employed in the practice of the instant compound exempli?ed by diethylzinc or diisobutylmer invention. When a polar compound is used in admixture CUTS’; with the hydrocarbon diluent, the polar compound is (c) A complex metal hydride, such as lithium alumi num hydride, and a Group IV metal halide, such as titani _ um tetraiodide or titanium tetrachloride; usually present in an amount in the range of 0.005 to 50 percent by weight of the total solvent mixture. 25 '(d) A complex metal halide, exempli?ed by potassium iluotitanate, and an organometal compound, exempli?ed by triethylaluminum; I (e) A derivative of a Group VIII metal selected from the group consisting of halides, oxides and complex com The polymerization process of this invention can be carried out at any temperature within the range of about —80 to 150° C., but it is preferred to operate in the range of —Z0 to 80° C. The polymerizatoin reaction can be carried out under autogen-ous pressures. It is usually desirable to operate at pressures suf?cient to pounds of iridium, platinum and osmium, said complex compounds corresponding to the formula M",,M"’Xb, maintain the monomeric material substantially in the liquid phase. The pressure will thus depend upon the where M” is an alkali metal or an ammonium radical, particular material :being polymerized, the diluent being M'” is irridium, platinum or osmium, X is a halogen, employed, and the temperature at which polymerization is and b is at least 1 and the sum of a and b is equal 35 conducted. However, higher pressures can be employed to the valence of M'” and an organometal compound exempli?ed by triethylaluminum, for example, iridium chloride and triethylaluminum or ethylaluminum sesqui if desired, these pressures being obtained ‘by some such suitable method as the pressurization of a reactor with a gas which is inert with respect to the polymerization reaction. The polymerization according to this invention (f) At least one derivative selected from the group 40 is generally carried out in the liquid phase. However, consisting of oxides, halides, and oxyhalides of vanadium depending upon the diluent and polymerization tempera and complex salts of said halides with a member selected ture selected, the polymerization can be conducted in the from the group consisting of ammonium halide and an solid phase. 7 alkali metal halide and an organometal compound, for As previously indicated, the process of this invention is example, vanadium oxide and triethylaluminum; 45 concerned with the production of rubbery polymers of (g) A derivative of a Group VI metal selected from conjugated dienes. The term “rubbery polymer” in— chloride; the group consisting of halides, oxyhalides, hydroxy halides, oxyhydroxyhalides of a metal selected from the cludes elastomeric, vulcanizable, polymeric material which after vulcanization, i.e., crosslinking, possesses the group consisting of molybdenum, tungsten, uranium, properties normally associated with vulcanized rubber selenium, tellurium- and polonium, and complex salts of 50 including materials which when compounded and cured said halides and said oxyhalides with a member selected from the group consisting of halides of sodium, potassium, lithium, rubidium, cesium and ammonia and an organo metal compound, for example, molybdenum pentachlo ride and ethylaluminum dichloride; (h) A chromyl halide and an org-anometal compound, exhibit reversible extensibility at 801° F. of over 100 per cent of a specimen’s original length with a retraction of at least ‘90 percent within one minute a?ter release of the stress necessary to- elongate to 100 percent. The rub bery polymers produced in accordance with this inven tion are linear polymers. With regard to the solubility such as chromyl chloride and triisobutylaluminum; and (i) At least one halide of titanium, zirconium or hafni um and at least one hydride of lithium, sodium, potassium, of the rubbery polymers of this invention, it is preferred derstood that mixtures of these materials can also be used. is not intended to limit the invention to a speci?c charging that they contain less than 50% gel as determined by the standard gel determination test. Actually, it has been rubidium, cesium, magnesium, calcium, strontium, bari 60 found that the polymers produced in accordance with the um, lanthanium or thorium, for example, zirconium tetra instant process generally contain not gel or substantially chloride and calcium hydride. no ‘gel. The polymerization process of this invention is usually The process of this invention can be carried out as a carried out in the presence of a hydrocarbon diluent batch process by charging the monomeric material after which is liquid and inert under the conditions of the 65 treatment with the polyhydric alcohol treating agent into process. Examples of suitable diluents include aromatic, a reactor containing the polymerization catalyst and para?inic and cycloparaf?nic hydrocarbons, it being un the hydrocarbon diluent. It is to be understood that it Speci?c examples of suitable hydrocarbon diluents include procedure since the catalyst diluent and monomer can be propane, isobutane, n-pentane, iso-octane, n-dodecane, 70 added in any desired order. The process can also be cyclopentane, cyclohexane, methylcyclohex-ane, benzene, carried out continuously by maintaining the above-men toluene, xylene, and the like. It is also within the scope of the invention to employ in admixture with the hydro carbon diluent polar compounds which do not inactivate the organolithium catalyst. When employing an organo 75 tioned concentration of reactants in the reactor for a suit able residence time. The residence time in a continuous process will, of course, vary within rather wide limits de pending on such variables as the reaction'temperature 3,095,406 7 and pressure, the amount of catalyst used, and the mono meric material which is being polymerized. In a con 8 A. Butadiene was passed upward through a 2" x 24" column packed with calcium hydride, through a 3” X 30" tinuous process, the residence time generally falls within column packed with Drierite (calcium sulfate), through a and moisture from the reaction vessel in which the polym The bottle was swept with prepuri?ed nitrogen prior to transfer of the butadiene. Vigreux column with Dry Ice re?ux to remove any the range of 1 second to 1 hour when conditions within dimer that was present, and then into a receiver pro the speci?ed ranges are employed. When a batch process tected with a calcium sulfate drying tube. The liquid is being utilized, the time for the reaction can be as butadiene was allowed to stand for approximately 45 high as 24 hours or more, although it is generally less minutes at ~80° C. in a Dry Ice-acetone bath to freeze than 24 hours. out any water which might still be present. It was then It is preferred that the diluent used in the process be substantially free of impurities such as water, oxygen and 10 transferred to a bottle containing calcium sulfate, using 100 grams of calcium sulfate per 300 grams of butadiene. the like. In this connection, it is desirable to remove air erization is carried out. B. Butadiene was passed through a knock out column At the conclusion of the polymerization reaction, when a batch process is used, the total reaction mixture is then 15 (Vigreux column with Dry Ice re?ux) to remove any treated by any suitable method to inactivate the catalyst and recover the polymer. In one suitable method, a catalyst inactivating material, such as water or an alco dimer that was present, through ethylene glycol which had been dried by heating it to 200° C. and cooling it in an atmosphere of nitrogen, then through a 1" x 13” tube packed with glass helices to remove ethylene glycol, hol, e.g. isopropyl alcohol, is added in amount which is su?icient to deactivate the catalyst without causing pre 20 and then into a receiver protected with a calcium sul fate drying tube. It was transferred immediately from cipitation of the desired polymer. It has also been found to be advantageous to add an antioxidant, such as phenyl beta-naphthylamine, to the polymer solution prior to precipitation of the polymer. After addition of the cata the receiver to a 24-ounce beverage bottle which had been swept with prepuri?ed nitrogen. present in ‘the solution can then be precipitated by the C. But-adiene was passed through a knock out column as in 13 above, and then over the surface of water. The bu-tadiene was thereafter passed as in B above through addition of an excess of a material such as water, ethyl alcohol or isopropyl alcohol. It is to be understood that to remove ethylene glycol, and ?nally into a receiver. It lyst inactivating agent and the anti-oxidant, the polymer ethylene glycol, through a tube packed with glass helices was transferred immediately from the receiver to a 24 mer can be accomplished in a single step. The precipi 30 ounce beverage bottle which has been swept with pre deactivation of the catalyst and precipitation of the poly puri?ed nitrogen. tated polymer can then be recovered by ?ltration, decan D. Butadiene was passed through a knock out column tation, or the like. as in B and then through water. Treatment of the buta The rubbery polymers which result when a monomeric diene was then continued by passing same through ethyl~ material comprising a conjugated ‘diene is polymerized ene glycol, etc., as described in B and C hereinabove. by the method of this invention can be compounded by E. Butadiene was distilled, shaken with ethylene glycol any of the known methods such as have been used in the using 10 parts by weight of the glycol per 100 parts past for compounding natural rubber. Vulcanization ac butadiene, passed through a l” x 18” tube packed with celerators, reenforcing agent, and ?llers such as have glass helices to remove the ethylene glycol, and then been employed in natural rubber can likewise be used in 40 passed into a receiver protected with a calcium sulfate the compounds of this invention. drying tube. It was transferred immediately from the A more comprehensive understanding of the invention receiver to a 24-ounce beverage bottle which had been can ‘be obtained by referring to the following illustrated swept with prepuri?ed nitrogen. examples which are not intended, however, to be unduly Butadiene, treated according to the above-described limitative of the invention. methods, was polymerized in accordance with the fol EXAMPLE I lowing recipe: Grams Butadiene, treated in various Ways with ethylene rglycol Butadiene _________________________________ __ 100 and also without the glycol treatment, was polymerized in a series of runs using n-butyllithium as the catalyst. Cyclohexane _______________________________ __ 390 The n-butyllithium catalyst was prepared and used in 50 Butyllithium (0.244 M solution) ____________ __ Variable Temperature, ‘’ C ___________________________ __ 50 n-pentane solution. A 1000 milliliter three-necked ?ask, ?tted with a re?ux condenser, a dropping funnel with a Time, hours _________________________________ _. 17 gas outlet sidearm, and a high speed stirrer, was swept The polymerization runs were conducted in 7-ounce with prepuri?ed nitrogen and charged With 300 milliliters of dry, ole?n-free n-pentane and 5.9 grams of lithium 55 beverage bottles which were ?rst charged with dry cyclo hexane. Prior to charging, prepuri?ed nitrogen was wire which was cut into lengths of about 0.5 centimeter. bubbled through the cyclohexane for 30 minutes at the The dropping funnel was then attached, and a solution of 38.9‘ grams of l-chlorobutane in 100 milliliters of n pentane was charged to it. The stirrer was started and brought to high speed, and the chlorobutane solution was added without cooling at a rate so as to maintain gentle re?ux. After the addition was completed, stirring was continued for three hours. The mixture was allowed to stand overnight in a nitrogen atmosphere and was then transferred to a 7-ounce beverage bottle and centrifuged. The supernatant n-butyllithium solution was pressured into a dry, nitrogen-?lled bottle. Analysis showed the solution to be 0.610 M n-butyllithium. This solution was diluted with n-pentane to a concentration of 0.244 rate of 3 liters per minute. After the diluent was charged, prepuri?ed nitrogen was dispersed through a fritted glass tube and bubbled through it at the rate of 3 liters per minute for 5 minutes. The bottles were capped with rubber gaskets and perforated metal caps, and the mono mer and n-butyllithium were introduced in that order by syringe. The bottles were then agitated in a constant temperature bath (50° C.) for 17 hours. The polymer in each run was precipitated by the addi~ tion of isopropanol, separated, and then dried in a vacuum oven. Five series of runs were made in which the butadiene M when used in the polymerization runs hereinafter de 70 was treated in each series by one of the treating pro scribed. cedures described above. The catalyst levels and results There is set forth hereinbelow a description of the are set forth below in Table I, and the letters A, B, C, procedures (designated as A, B, C, D and E) used in D and E are used in the table to designate the particular treating the butadiene prior to its being contacted with n 75 procedure used in treating the butadiene. butyllithium. 3,095,406 10 Table I Millimols Run N0. Bntadiene Treatment Catalyst/- 100 Grams 70° C. Toluene which had been dried ‘by a nitrogen purge was added to the bottles. After addition to the bottles, the toluene was purged with nitrogen for an addi tional minute at 3 liters per minute for each 50 m1. of ‘ Conversion, percent Inherent viscosity Monomer toluene. The catalyst was prepared by adding triiso butyl aluminum and titanium tetrachloride to toluene. A (control)_. Aliquots of this toluene suspension were then added to the bottles by means of a syringe. Thereafter, the buta A (control).. A (control __ A (control)_. A (c0ntrol)__ diene was added to the bottles. In run 31, as shown in Table II, the butadiene prior to use was passed Ifrom a % (e0ntrol)__ storage cylinder through a column to knock out dimer and then collected in a Dry Ice-cooled container. In run 32, as shown in Table II, the butadiene was passed through a tower which was ?lled to a depth of 8 inches with ethylene glycol and then collected in a Dry Ice— cooled container. Both samples of butadiene until used were then stored in quart bottles over Drierite (calcium sulfate) at —20° C. The polymerization recipe used in these runs was as follows: Parts by weight Butadiene Toluene 100 ._____ 440 Triisobutylaluminum '(TBA) _____________ __ Variable Titanium tetrachloride (TIC) ____________ __ Variable Temperature, ° C ______ __‘_________________ __ 30 Time, hours 16-17 Polymerization was obtained in control run 3 but the The results of these runs are shown hereinbelow in product had a much higher inherent viscosity than that in runs 9, 15, 21, and 27. The catalyst level was the 30 Table II. Table 11 same in all runs. The data show that with the glycol treated butadiene, polymerization can be effected‘ at rela tively low catalyst levels to give consistently good con versions whereas with the untreated butadiene, erratic results were obtained with only one run of the ?rst four 35 Run No. TBA, MHM 1 T'I‘C, Conver MHM 1 sion, percent - yielding any polymer. 1. 0 1. 0 EXAMPLE RII Polymerization grade isoprene was distilled, and the 40 center cut was used in :a series of polymerization runs O, 83 0. 83 10 18 1 Millimoles per 100 parts of monomer. 9 Not treated with ethylene glycol. 3 Treated with ethylene glycol. in which n-lbutyllithium was employed as the catalyst. A portion of the center cut from the distillation of iso From a consideration of the data in Table II, it is seen that a higher conversion of the 1,3-butadiene to polymer prene was contacted in vapor phase with ethylene gly col which had ‘been dried by heating to 200° C. and 4:5 is obtained when the monomer is treated with ethylene glycol prior to use in the polymerization. It is noted then cooling in an atmosphere of nitrogen. The iso that these runs were carried out ‘at very low catalyst prene vapor was dispersed into the ‘glycol through a levels, indicating that the treatment of the monomer fritted glass v‘disk. It was then passed through a tube with a polyhydric alcohol makes it feasible to employ packed with glass helices to remove the ethylene glycol, lower catalyst levels in the polymerization than is pos 50 through a Vigreux column, and then into a receiver pro sible with the untreated monomer. vided with a calcium sulfate drying tube. Nitrogen was passed slowly through the system to maintain a EXAMPLE IV positive nitrogen pressure during this operation. A solution of n-butyllithium in n-pentane was pre pared in the manner ‘described in Example I. The con 55 centration of the solution employed in the polymeriza tion of isoprene was 0.330 M. Samples of the distilled isoprene and samples of dis tilled isoprene which had been treated with ethylene gly A series of runs was carried out in which 1,3-butadi one was polymerized in the presence of a catalyst con sisting of diethylzinc and molybdenum pentachloride. In runs 33 and 35, as shown in Table III, the butadiene was not treated with ethylene glycol while in runs 34 and 36 the butadiene was treated with ethylene glycol col were employed in two series of polymerization runs 60 as described in Example III. Essentially the same pro using 2.5, 3.0, and 3.5 millimols of n-butyllithium per cedure as described in Example III was followed in con 100 grams of monomer. Cyclohexane (390 grams) was ducting these runs. ‘ employed as the diluent. Polymerization was effected The polymerization recipe used in these runs was as in the manner described in Example I using a tempera 65 follows: ture of 50° C. and a reaction time of four hours. Po Parts by weight Butadiene 100 lymerization occurred in all cases. Toluene EXAMPLE 1r But-adiene, treated with ethylene glycol and also with 70 out the glycol treatment, was polymerized in runs using a catalyst consisting of triisobutyla-luminum and titani um tetrachloride. The runs were carried out in 7-ounce beverage bottles which had been ‘dried in an air oven at 75 _ _.__._.. 880 Diethylzinc _ Variable Molybdenum pentachloride ______________ __ Variable Temperature, Time, ° C ___________________________ .. 50 hours _______________________________ .... 72 The results of these runs are shown hereinbelow in Table III. ‘ 3,095,406 Table V Table III Run No. TBA Diethylzinc, M0015 Con MHM 1 MHM 1 version, 3. 6 3. 6 3.0 3. 0 percent 3. O 3.0 2. 5 2. 5 T'I‘I Run No. Conversion, percent Parts MHM1 Parts MHM1 15 35 0 15 411 ____________________ __ 423 ____________________ __ 10 1 Millimoles per 100 parts of monomer. 2 Not treated with ethylene glycol. B Treated with ethylene glycol. 0.397 0.397 2.00 2.00 0.222 0.222 0.400 0.400 0 05 1 Millimoles per 100 parts of monomer. 1 Not treated with ethylene glycol. 3 Treated with ethylene glycol. From an examination of the data in Tables IV and V, it is seen that higher conversions are obtained when the a polyhydric alcohol prior to use in the polymerization. 15 monomer is treated with a polyhydric alcohol prior to the It is apparent from the data in Table III that a higher conversion is obtained when the monomer is treated with polymerization. The rubbery polymers produced in accordance with this invention have utility in applications where natural and EXAMPLE V A series of runs were carried out in which 1,3-buta diene was polymerized in the presence of a catalyst con synthetic rubbers are used. sisting of lithium aluminum hydride and titanium tetra other rubber articles. As will be evident to those skilled in the art, many variations and modi?cations can be practiced upon con iodide. In runs 37 and 39, as shown in Table IV, the butadiene was not treated with ethylene glycol while in runs 38 and 40 the butadiene Was treated with ethylene glycol as described in Example III. Essentially the same procedure as described in Example 111 was followed in conducting these runs. sideration of the foregoing disclosure. Such variations and modi?cations are believed to be within the spirit and scope of the invention. We claim: 1. In a process for preparing rubbery polymers com The following polymerization recipe was employed in these runs: For example, they can be 20 used in the manufacture of automobile tires, gaskets, and prising contacting a conjugated diene suitable for polym erization and containing from 4 to 10, inclusive, carbon Parts by weight _____________________________ __ 100 atoms per molecule with a catalyst selected from the Cyclohexane ___________________________ __ 780 group consisting of (1) a compound corresponding to the Bu-tadiene Lithium aluminum hydride (LAH) _______ __ Variable formula RLiX, wherein R is a hydrocarbon radical se Titanium tetraiodide (TTI) _______________ __ Variable M01 ratio, LAH/TTI ____________________ __ 1.20/1 lected from the group consisting of aliphatic, cycloali Temperature, ° C _______________________ __ 50 Time, hours _________________________ _t____ 17.5 The results of these runs are shown hereinbelow in Table IV. Table IV LAH 35 phatic and aromatic radicals and x is an integer from 1 to 4, inclusive, and (2) mixtures obtained by mixing at least two essential components, one of said components eing selected from the group consisting of hydrides of metals of Groups I, II and III and organo compounds of 40 Groups I, II, III and IV-B metals and the other of said components being a metal compound selected from the group consisting of Group IV—A, Group V, Group VI TTI Run No. and Group VIII metal compounds, said contacting occur ring in the presence of a hydrocarbon diluent, the im Conversion, percent Parts MHM! Parts MHMl 45 1.50 l. 50 1.25 1. 25 0. 695 0. 695 0.578 0. 578 1. 25 1.25 1.04 1. 04 85 95 0 95 50 1 Millimoles per 100 parts of monomer. 1 Not treated with ethylene glycol. 3 Treated with ethylene glycol. provement which comprises mixing said conjugated diene with a polyhydric alcohol, thereby forming a conjugated diene phase and an alcohol phase, said polyhydric alcohol being liquid under the mixing conditions and being sc leoted from the group consisting of dihydric and tri hydric alcohols having from 2 to 10 carbon atoms per molecule; separating said conjugated diene phase from said alcohol phase; and contacting said catalyst with said conjugated diene phase. EXAMPLE VI as described in Example III was followed in conducting 2. The process according to claim 1 in which said poly hydric alcohol is a glycol. 3. The process according to claim 2 in which said gly col is ethylene glycol. 4. The process according to claim 1 in which said poly hydric alcohol is glycerol. 5. A process for preparing rubbery polymers of con jugated dienes which comprises passing a conjugated diene suitable for polymerization and containing from 4 to 10, [these runs. inclusive, carbon atoms per molecule into a treating zone; Butadiene, treated with ethylene glycol and also with out glycol treatment, was polymerized in runs using a catalyst consisting of triisobutylaluminum and titanium tetraiodide. In run 41, as shown in Table V, the buta diene was not treated with ethylene glycol while in run 42 the butadiene was treated with ethylene glycol as de scribed in Example III. Essentially the same procedure The polymerization recipe used in these runs Was as follows: Butadiene Parts by weight _____________________________ __ 100 Toluene _______________________________ __ 866 Triisobutylaluminum (TBA) ______________ __ Variable Titanium tetraiodide (TTI) _______________ __ Variable Mol ratio, TBA/TTI _____________________ __ 5.00/1 Temperature, ° C _______________________ __ 50 Time, hours ____________________________ __ 3 The results of these runs are shown hereinbelow in Table V. mixing said conjugated diene with a substantially anhy drous polyhydric alcohol having from 2 to 10 carbon atoms per molecule in said treating zone, thereby form ing a conjugated diene phase and an alcohol phase, said polyhydric alcohol being liquid under the mixing condi tions and being selected from the group consisting of dihydric and trihydric alcohols; recovering said conju gated diene phase from said treating zone; contacting said conjugated diene phase with a catalyst selected from the group consisting of (l) a compound corresponding to the formula RLix, wherein R is a hydrocarbon radical selected from the group consisting of aliphatic, cyclo 3,095,406 13 1.4 aliphatic and aromatic radicals and x is an integer from 12. The process according to claim 5 in which said 1 t0 4, inclusive, and (2) mixtures obtained by mixing catalyst consists essentially of triisobutylaluminum and at least two essential components, one of said compo— titanium tetrachloride. 13. The process according to claim 5 in which said nents being selected from the group consisting of hy drides of Groups I, l1 and Ill metals and organo com catalyst consists essentially of diethylzinc and molyb denum pentachlori-de. pounds of Groups I, II, III and IV~B metals and the other of said components being Ia metal compound se 14. The process according to claim 5 in which said catalyst consists essentially of lithium aluminum hydride lected from the group consisting of Group ‘IV-A, Group V, Group VI and Group VIII metal compounds, said con ‘and titanium tetraiodide. 15. The process according to claim 5 in which said tasting occurring at a temperature in the range of —20 to 150° C. and in the presence of a hydrocarbon diluent, inert and liquid under conditions of the process; and catalyst consists essentially of triisobutylaluminum and titanium tetraiodide. recovering a rubbery polymer of said conjugated diene. 6. The process according to claim 5 in which said con jugated diene is 1,3-butadiene. 7. The process according to claim 5 in which said con 15 jugated diene is isoprene. jugated diene is 1,3-pentadiene. 9. The process according to claim 5 in which said poly 20 hydric alcohol is a glycol. 10. The process according to claim 9 in which said glycol is ethylene glycol. ’ 11. The process according to claim 5 in which said catalyst consists essentially of n-butyllithium. References Cited in the ?le of this patent UNITED STATES PATENTS 2,552,198 2,832,759 8. The process according to claim 5 in which said con 25 ' 2,913,444 2,925,452 2,953,556 2,979,488 Mayland et a1 __________ __ May 8, Nowlin et al. _________ __ Apr. 29, Diem _______________ __ Nov. 17, Broughton ___________ __ Feb. 16, Wolfe _______________ __ Sept. 20, Carpenter ___________ __ Apr. 11, 1951 1958 1959 1960 1960 1961 OTHER REFERENCES Moor et al.: Chem. Abstracts, vol. 29, 6034 (1935).