Патент USA US3046278код для вставки
aired rates Pater O?lice 1 3,ii46,268 Patented July 24, 1962 2 3,046,268 CATALYTIC PRQCESS FOR POLYMERIZING ETHYLENHCALLY UNSATURATED HYDRO CARBONS Howard J. Cohen, Cincinnati, Ohio, assignor to National Distillers and Chemical Corporation, New York, N.Y., a corporation of Virginia strong reducing agents such as alkali metals (e.g., sodium), alkaline earth metals (e.g., magnesium, calcium), organo alkali compounds (e.g., alkylsodium), organometallic compounds (e.g., trialkylaluminum), and the like with further speci?c examples including tripropylaluminum, triisobutylaluminum, tri-n-decylaluminum, butyl magne sium chloride, dibutyl magnesium, metal hydrides such No Drawing. Filed Sept. 22, 1959, Ser. No. 841,448 9 Claims. (Cl. 260-943) as lithium hydride, magnesium hydride, etc. Reaction conditions at which the polymerization may be carried out with the novel catalyst system include the The present invention relates to an improved polymer 10 following: ization process and, particularly, to such a process utilizing Temperature _______________ __ From —120° C. to 300° 0., a novel catalyst system for polymerizing ole?ns to high preferably 50 to 250° C. molecular weight polymers. Still more particularly, the Pressure ___________________ __ Subatmospheric to 3000 at invention relates to such a process using a catalyst system that is advantageously soluble in conventional reaction media employed for polymerizing ole?ns and is highly stable against objectionable hydrolysis and thermal de composition. Ratio of catalyst components (mol ratio of reducing agent: mospheres, preferably at mospheric to 200 atmos~ pheres. M-contarning compound)_____ 0.1260 £50 : 1, preferably 1 to Total catalyst concentration (based on weight of monomer In the process embodied herein, the catalyst system to be polymerized) ________ __ 0.005 to 10%. comprises (1) a suitable reducing agent and (2) a com 20 The compounds which may be polymerized according pound of the formula to the present invention consist generally of hydrocarbons, such as the ole?ns containing 2 to 16 carbon atoms. Spe ci?c examples of such hydrocarbons include ethylene, wherein M’ is a metal from groups IVb, Vb and VII: of the periodic table, such as Tit2 to +4, Zr+2 to +4, Hft2 to 25 propylene, butene-l, pentene~1, hexene-l, 4-methyl-pen tene-l, butadiene, isoprene, styrene, methylstyrene, etc. +4, V+2 to +5, Nb+2 to +5, and Ta+2 to +5, M is selected Mixtures thereof, as for example mixtures of ethylene and from the group consisting of Si, Ge, Sn and Pb, y is the butene-l, may be used for copolymerization with the valence of the metal M’, and R1, R2 and R3 is a hydro catalyst system embodied herein. carbon radical, e.g., alkyl, aralkyl, aryl, cycloalkyl, etc., The polymerization reaction is carried out in batch, and preferably an alkyl radical such as one containing semi-continuous or continuous operation. Most conveni from one to eight carbon atoms and speci?cally, methyl, ently, and in preferred embodiments, the process at lower ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, temperature operations is carried out in a diluent or liquid t-butyl, n-amyl, isoamyl, n-hexyl, n-octyl, Z-ethylhexyl, etc., and aryl radicals such as phenyl, p-tolyl, and the like. Speci?c compounds falling within the scope of the afore~ “ said structural formula include tetrakis(trimethylsiloxy) titanium, Ti[OSi(CH3)3]4, tetrakis(trimethylsiloxy)-zir conium, tetrakis(triphenylsiloxy) vanadium, pentakis(tri methylsiloxy) tantalum, tetrakis(triphenylstannoxy) tita nium, Ti[OSn(C6I-I5)3]4, and others. Compounds, other than the reducing agent, embodied for use as a catalyst component may, for example, be pre pared by the method of English and Sommer, J.A.C.S. 77, 170 (1955), and illustrated by preparation of tetrakis (trimethylsiloxy)titanium by reacting trimethylsilanol with titanium tetrachloride; by the method of Zeitler and Brown, J.A.C.S. 79, 4616 (1957) showing preparation of tetrakis (triphenylsiloxy) titanium by reacting triphenyl reaction medium, the amount not being unduly critical but it should be at least su?icient to permit eifective agita tion and preferably to hold the major portion of the poly mer in solution. Suitable organic media include aliphatic alkanes or cycloalkanes such as pentane, hexane, heptane, cyclohex 40 anes; hydrogenated aromatics such as tetrahydronaphtha lene, high molecular weight liquid para?ins which are liquid at‘ the reaction temperature; aromatics such as ben zene, toluene, xylene, halogenated aromatics such as chlorobenzene, chloronaphthalene, etc. Other reaction media include ethylbenzene, isopropylbenzene, ethyltolu ene, n-propyl benzene, diethylbenzenes, mono- and di alkyl naphthalene, n-pentane, n-octane, isooctane, methyl cyclohexane, tetralin, decalin, and other inert liquid hydro— carbons. In carrying out the polymerization reaction at silanol with tetrabutoxytitanium; and still other com 50 relatively high pressures, such as at one thousand atmos pounds, such as those in which M’ is vanadium may be pheres and above, it may be carried out in the absence prepared by reacting an appropriate alkali metal triorgano or substantial absence of such reaction media and, in such silanolate or stannolate with, for example, vanadium tetra instance, the need for solvent recovery systems, etc., may halide in accordance with the procedure of Tatlock and be obviated. Rochow, J. Am. Chem. Soc. 77, 170 (1955), and, forex 55 It is preferred that the reaction medium that is used ample, the reaction of sodium triphenylsilanol or sodium be essentially free of impurities which may react to de trimethylsilanol with vanadium tetrachloride to prepare, stroy catalyst activity or which copolymerize with the respectively, tetrakis-(triphenylsiloxy) vanadium and tet rakis~(trimethylsiloxy) vanadium. ole?nic hydrocarbon; that is, appreciable quantities of material such as carbon dioxide, oxygen and acetylenic In reference to the ‘reducing agent that is one compo‘~ compounds should preferably be absent. nent of the catalyst system embodied herein, particularly For this process, the polymerizable hydrocarbons may suitable and preferred are the alkylaluminum halides, be used in substantially pure form or there may be used such as dialkylaluminum halides, alkylaluminum dihalides, a mixture containing major quantities thereof, provided and mixtures thereof generally called “alkylaluminum sesj ' no impurities are present in substantial amounts to de quihalides.” Thus, embodied for use herein are ethyl 65 stroy the catalyst and/or contaminate ‘the polymer aluminum sesquibromide, ethylaluminum sesquichloride, methylaluminum dibromide, dimethylaluminum bromide, . methylaluminum vdichloride, dimethylaluminum chloride, butylaluminum dibromide, dibutyl aluminum chloride, hexylaluminum dibromide, dihexylaluminum bromide, and similar alkylaluminum halides and mixtures thereof. Still other reducing agents embodied for use herein are product. For instance, ethylene obtained by the cracking of hydrocarbon streams is satisfactory if acetylenic and oxygenated materials are not present in more than trace amounts. In carrying out the herein described polymerization process, it is preferable and highly desirable to maintain the polymerization zone free of extraneous gases. This 3,046,268 4% Example 2 can be done by keeping the reaction blanketed at all times with an inert gas, for example, operating with an inert gas such as nitrogen, argon or helium. Preferably, the reactor and its contents are blanketed with the polymeriza-ble sub In another run, the polymerization of ethylene was carried out using V[OSi(C6H5)3]4 and diethylaluminum chloride as the combination catalyst. In such a run, Stance’ e'g" ethYRM‘gaF’ to avc?d unnecessary dilution of 5 500 ml. of preheated decalin was charged to the reac th? reactor contents with .the melt gasfs' . tor and the temperature adjusted to 125° C. The re In order to further ‘describe the invention, the following actor Contents, 2.1 m1. of a 0.133 M- decaun Solution of examples set forth speci?c embodiments of catalyst sys(C H ) Alcl was added ‘followed b O 085 millimole of terns embodied herein for polymerizing ethylene to high molecular weight polymers. 5, 2C H di For the examples set forth, 1O V[OS,1( 6 5)3]4 1 d . 90 3'1 ‘f d F80 W m “ m' o 1. Aft eca m‘, ' _ er the reducing agent component of the catalyst System was ethyl aluminum sesquichloride (a 1:1 mixture of 30 minutes of reaction at an ethylene pressure mamtained at 60 mm- Hg gang?’ 2-57 grams of elhylene was ab_sorbefl A1(C5H2)C12 and (A1(C2H5)2C1) o1- diethyl aluminum The product was isolated and puri?ed as ‘described in chloride and the other component was Ti[OSi(CH3)3] 4, EXample 1 t0_Y1e1d Z61 _g1‘ ams of a tough: Yvnlte Polymer V[OSi(C6H5)3]4 or Ti[OSi>(C6H5)3]4. 15 ‘The following tabulation sets forth additional data per In each of the examples, the polymerization was carried taming to the run of Example 2. AW tide? 11 if use“ £3?‘ “ltii‘i?i? Agggggcilbigiiig. egglggglagle ggllggggr poiylii?i’tca’???é’?d grams (CgHQzAlCl-i- grams’ V[OSi(CsH5)3]4 7 ____ __ 0.28 3.3 2.57 260 2.61 tough, white solid. out in a three-necked glass reaction ?ask equipped with Example 3 a high speed stirrer7 thermometer, mercury manometer \for 30 In another run, ethylene was polymerized using a cam reading reactor pressure, and feed lines supplying puri?ed lyst combination of Ti[OSi(C6H5)3]4 and triethylalumi ethylene and decahydronaphthalene. The ethylene was Supplied through a Pressure reducmg valve on a demand basis during the polymerization to maintain a constant mum. In Such a mm, 300 ml_ of daca?n was introduced into a one liter stirred pressure autoclave previously ?ushed with pure nitrogen The contents of the ?ask ethylene Pressure in the reactor (60 mm Hg gauge)’ 35 were then heated to 180° C. under nitrogen and, after The amount 0i ethylene absorbed was determmed fFOm releasing the pressure in the autoclave, 5.72 grams (0.005 the pressure drop observed at constant temperature 111 a mole) of THOSKCGHshh dispersed in 20 m1‘ of decalin SUP-Ply tank of ‘known volume . was added, ‘followed by addition of 13 ml. of d 0.5 M Example 1 . 4 sroklution 01f triethylaluminurg t(0.57610 gram, 0.0035 trlrliolle). 0 with 1.60 _m1' of decahydronaphthalene. (hell/[ed to 125. C‘) m a 250 m1‘ Team", a 0'1 solution (In ‘19”- e au oc ave was r ressure r o .s.r1.g. w1 e y ene and the polymerizatrion carried out fit one hour and ten minutes, the autoclave being repressured to 500 p.s.i.g. hydronaphthalene) of the ethylaluminum sesqurchlo-ride each time ‘it fell to 400 P Sig‘ The tsmperature of the was added in amount su?icient to provide the concentraPolymerization reaction [ganged from 146434.. C At tion shown for each run in the ‘following tabulation and, 45 the end of ‘the o1‘ merization reaction the viscol‘ls re_ after an elapse of 11/2 minutes, a 0.1 M solution of tetrakis(trimethylsiloxy) titanium was added to provide the a t. d t p 1 d1. h d f h’ ‘ 1 . cum pm 110 was Sc arge. mm t e autoc ave mm amount thereof shown for each run. After such addition an excess of Water‘ The_s°hd Product: when cool’ was of catalyst components, the polymerization was conducted wnected ‘and treated Yvl‘th :hPptane 1“ ‘a mechamfial at an ethylene pressure of 60 mm. Hg gauge, at 1250 Q 50 blender to remove decalin, agaln collected, treated twice for 20 minutes, whereupon tha viscous Solution of the with acetone in the blender, and ?nally collected‘ and dried polymeric product was withdrawn from the reactor and at 95° 0' “Pdar Vacuum- The dried Polym?nc Product diluted with an equal volume of acetone. The solid polymer was collected by ?ltration, boiled 10 minutes in each Obtalned Wglghad 8'2 grams, Corresponding to 3- yiald of 25 moles of Polyethylene P61‘ mole of iotal Catalyst of three successive portions of a solution of one part by 55 While there are ‘above disclosed but a limited number of embodiments of the process of the invention herein volume of concentrated HCl and two parts by volume or‘ isopropyl alcohol, then boiled 10 minutes in each of three portions of isopropyl alcohol, washed with acetone, and dried in a vacuum oven at 120° C. to constant weight. IEU‘JYL Run N0. (mm? (millimoles) Al/Ti a .er 20 Ratio per gram Viscosity 1 grams/cc.2 Atomic grggnn?gies Relative Density, Softening moles) 0. 193 0. 158 O. 123 0. 101 0. 16 O. 208 ments without departing from the inventive concept here in disclosed, and it is desired therefore that only such 5135355541011 Properties of Isolated Polymer a “111mm Tl.[OSl(CH3)3]l cs?lsgilgg presented, it is possible to produce still other embodi mol of total catalyst O. 035 0. 017 0. 017 O. 017 0. 035 O. 035 110612;, ' 11. 0 18. 0 14.0 11'. 8 9. l 11. 9 1 Relative viscosity of a 0.1 weight percent solution in decahydronaphthalene at 130° 0. B ASTM D-1238. 3 Under compression at 66 p.s.i. 3,046,268 limitations be imposed on the appended claims as are stated therein. What is claimed is: reducing agent from the group consisting of tn'alkylalumi num and alkylaluminum halides and (2) a compound of the formula ' 1. A polymerization process which comprises contact ing a lower molecular weight ethylenically unsaturated hydrocarbon with a combination catalyst comprising (1) a reducing agent from the group consisting of trialkyl aluminum and alkylaluminum halides and (2) a com pound of the formula wherein M’ is a metal from groups IVb and Vb of the periodic table, M is a member from the group consisting of Si, Sn, y is the valence of M’ ‘and R1, R2 and R3 is 10 a hydrocarbon radical in which the mole ratio of .the reducing agent to said compound is 0.1 to 50:1 to produce wherein M’ is a metal from groups IVb and Vb of the a normally solid polymer of said monoole?nic hydro carbon. periodic table, M is a member from the group consisting of Si and Sn, y is the valence of M’, and R1, R2 and R3 ole?nic hydrocarbon is ethylene. is a hydrocarbon radical to produce a normally solid polymer of said unsaturated hydrocarbon. 2. A process, as de?ned in claim 1, wherein M’ is a member from the group consisting of tetravalent vanadi um and tetravalent titanium and M is silicon. 3. A process, as de?ned in claim 1, wherein the reduc 7. A process, as de?ned in claim 6, wherein the mono 15 8. A process, ‘as de?ned in claim 6, wherein the poly merization reaction is canied out in presence of an inert liquid reaction medium. 9. A process, as de?ned in claim 6, wherein the com— pound is from the group consisting of Ti[OSi(CH3)3]4, V[OSi(C6H5)3]4aI1d Ti(0Si(C6H5)3]4 ing agent is an alkyl aluminum halide. References Cited in the ?le of this patent 4. A process, as de?ned in claim 1, wherein R1, R2 and R3 is methyl. UNITED STATES PATENTS 5. A process, as de?ned in claim 1, wherein R1, R2 2,938,000 Wanless ______________._ May 24, 1960 and R3 is phenyl. FOREIGN PATENTS 6. A polymerization process which comprises contact 25 ing a lower molecular weight monoole?nic hydrocarbon 534,792 Belgium ______________ __ Jan. 31, 1955 at from ~120° to 300° C. with from about 0.005 to OTHER REFERENCES? about 10%, based on the weight of the monoole?nic et al.: J. Am. Chem. Soc. 77, January 5, 1955, hydrocarbon, of a combination catalyst comprising (1) a 30 p. English 170.