Патент USA US2403779код для вставки
July 9, 1946. 2; ,35779 G. C. BAILEY ì PROCESS FOR TREATMENT 0F'OLEFIN--CONTAINING~MIXTURES. 1 Filed octfso, 1941 ` *A S mm m9251 l wm/ 'aoivavdas -aézl On. ì.ov f2 Y mm mv Patented July '9, 1946 y l, 2,403,779 UNITED STATES Afiißxl‘fENi‘ OFFICE PROCESS FOR TREATMENT 0F OLEFIN ` CONTAIîN‘ING IVIIXTURES ' Grant C. Bailey, Bartlesville, Okla., assignor to Phillips Petroleum Company, V,a corporation .jof » Delaware Application october so, 1941, serial No. 41");,30’1l 4 Claims. (Cl. ZBO-683.15) l yl-l-pentene, Z-methyl-2-pentene, 3-.methyl-2A This invention relates to the catalytic polymer- l» pentene and the like. y l ization of oleñns, and more particularly it re-Y lates to the polymerization of selected Aoleiins The rate at >which mono-ole?ins are polymer contained in a 'hydrocarbon mixture. It further V ized is also to some extent a function of the mo leculary weight of >said oleñns. In general," the relates to the production of an optimum yield of f superior lubricating oil low-boiling olefins. stock from a. mixture of * ' The catalytic polymerization of olefins to com pounds of higher molecular Weight is well known. higher molecular Y»Weight oleñns polymerize `less yrapidly than the lower molecular weight oleñns. There‘are, however, exceptions to this general ization, one of the most outstanding being ethyl ene whichr is polymerized with diiliculty even> by Charge stocks for such processes are preferably mono-olefins, and include normally gaseus or liq uid oleñns prepared by dehydrogenation of par aluminum chloride catalyst. , , ’ .I In’some polymerization proCSSSes'it has been found that when a mixture of oleñns is to _be pol afüns, dehydration of'alcohols, cracking or dehy ymerized to form >lubricating oil stocks, high drogenation of waxes or gas oils, etc. The ole ñns may be used either singly or mixed with 15 yields of desirable products are rapidly obtained by first removing substantially all of the tertiary other oleñns or inert diluents. ' The reactions base olei'ins and then polymerizing‘nontertiary may be effected over a wide range of tempera base cleñns in the presence of a suitable catalyst ture, but usually in the range `of from "-30°1F. to produce polymers suitable Afor use as lubricat to 200° F. The active metal halides are preferred as catalysts such as aluminum chloride, zirconi 20 ing «oil stock. The most desirable polymers suit able for use as a lubricating cil stock are `pro um chloride,`boron fluoride, and the like, used duced from the polymerization of individual non either alone or in combinationv with'various mod vtertiary-base l-oleñns. f iñers such as are well known, including inorganic . I have now found a satisfactory method of materials such as sodium chloride and. organic materials suchas ketones, etc. 25 , Inpolymerization reactions, as briefly outlined above, oils may be obtainedhaving widely vary ing characteristics, depending markedly on both the olefin charge and the properties and condi tions of the polymerization system, In practice, the charges used for the preparation of oils fre' quently contain a wide variety of oleñn react ants, even though one type may be 'in predomi nance. e ' , ' ' ' ‘ Metal halides of the Friedel-Crafts type such as boron ñuoride and aluminum chloride, gener ally polymerizeoleñns at a rapid rate. For ex .selectively 'polymerizing tertiary-base olefins which are present in a hydrocarbon mixture com 'prising also nontertiary-base mono-olefins. More specifically I have found a catalyst mate rial that will polymerize tertiary-base oleñns, -such 'as isobutene, without'promoting apprecia ble polymerization of,> other types, of mono-olefins ‘such as >nontertiary-base mono-oleñns, that `may bepresent in a hydrocarbon mixture. Such cat alyst material comprises a tin tetrahalide, pref erably in conjunction with a stabilizer, such as will be discussed hereinafter. As a tin tetrahal ide catalyst I include mixtures of tin4 tetrahal ides, vsuch as a mixture of tin tetrachloride and ample, when aluminum chloride is added to liq uid isobutene at temperatures above about 0° F., ' tin"tetrabromide, and "also mixed tin tetrahal the reaction proceeds with such rapidity that it ¿140 . ides, such astin tribromochloride, tin dibromodi ' vrchloride, tin bromotrichloride, and the like. is difficult to maintain the temperature of the One object» ofY this invention is >to selectively reaction mixture at a constant value. Polymer polymerize ole?lns. . ization reactions using phosphoric acid type cat Another object of this invention is to polymer > alysts usually proceed much more slowly. Still ize only tertiary-base olefins »in awhydrocarbon other catalysts such as those comprisingsilica gel may require specific Yconditions of somewhat higher temperature and pressures to ïpolymerize ~ oleñns atan appreciable rate.> mixture containing tertiary-base oleflns and nontertiary-baseV mono-oleñns. _ Another object of this invention is to produce a lubricating oil base stock having superior qual. In general, mono-oleiins having the tertiary 5.0 ities from low-boiling oleiins. ` ' ' base structure polymerize more rapidly than Still another object of this invention is to pro _other types of mono-olefins. By tertiary-base vide a superior catalytic conversion system-for oleñns I intend to include, in general, such'ole' 'the production ofV desired oils fromoleñns. , ñns which correspond to the formula `R2C=CRK2 A- further object of this invention is to purify where each R is an alkyl group and each R’ is 55 an' olefin-containing mixture in such a manner `hydrogen or any alkyl group. Such oleñns, up that undesirable materials, such as tertiary-base on hydrolysis in an acidic> medium, will general ly yield a tertiary alcohol. Typical' low-boiling tertiary-base ole?ins are Z-methyl-propene», oleñns and/orv compounds >containing reactive oxygen, sulfur, nitrogen, and the like, are re moved. ` ‘ ' l >Z-methyl-ll-loutene, Z-methyl-Z-butene, 2:-meth- L 60. f' Other objects and advantages of my invention 2,403,779 4 3 will be apparent from the accompanying disclo of heat. sure and discussion. decreases with a concomitant separation of a light ` amorphous precipitate, apparently a complex Tin tetrahalides such as tin tetrachloride and tin tetrabromide have been classed by other workers in the art as active metal halide cat alysts and as Friedel-Crafts type catalysts, along with aluminum chloride, aluminum bromide, boron iiuoride and the like. I have found, how ever, that the tin tetrahalicles di’îer fundamental However, the reaction rate gradually stannous compound. The activity of the cat alyst for such reactions can be increased and maintained for a prolonged length of time by the use of selected organic stabilizers. Such sta bilizers include nitro hydrocarbons, such as nitro methane and nitrobenzene, and ketones having ly from such catalysts in their polymerization 10 an alpha carbon atom to which is attached a single hydrogen atom, such as methyl-isopropyl characteristics; Aluminum chloride, aluminum ketone, diisopropyl ketone, and isopropyl-phenyl bromide, boron fluoride and the like readily poly ketone. Other types of ketones, such as acetone, merize nontertiary-base mono-oleñns such . as acetophenone, benzophenone, and cyclohexanone, propene, butene-l, butene-2, pentene-l, and the like. Hereinafter, such catalysts will be termed 15 do not act as stabilizers for the reaction. Relatively large proportions of such organic metal halide catalysts which are active for the stabilizers are necessary to influence the poly polymerization of nontertiary-base oleñns. How merization rate in a positive manner for a suit ever, tin tetrahalides, such as tin tetrachloride able period of time. For example, in the poly and tin tetrabromide, do not polymerize such compounds to any detectable extent under the 20 merization of isobutene ,at room temperature, and atmospheric pressure using'tin tetrachloride reaction conditions which form a part of my in catalyst, it was >necessary to add 0.1 mole per vention, but only polymerize tertiary-base ole cent of nitrobenzene, based on the number of iins, such as isobutene, as will be clearly shown moles of tin tetrachloride in the systenrto ob hereinafter. For example, I have found that Y neither n-pentene-l, n-pentene-2, n-hexene-l, 25 tain appreciable stabilizing action; this was ef Íective for only a short time. In contrast, the nor n-octene-l can be polymerized in the pres addition of 65 mole per cent of nitrobenzene on ence of a tin tetrahalide at a temperature equal the same basis not only accelerated ’the poly to or below the boiling points of said compounds merization but maintained the catalyst activity at atmospheric pressure, although at the higher temperatures halogenation reactions appeared to 30 at a constant value for a prolonged period oi time. ' take place. My invention is based, therefore, Although it may be that the factors which result in eventual decrease in activity when a small amount of stabilizer is present will eventu ally cause deactivation of catalyst even when a upon the discovery that tin tetrahalides, per se, are completely selective in their catalyzing action for the polymerization of only tertiary-base ole ñns under the reaction conditions which form a larger amount of stabilizer is present, it is to be appreciated that the actualfactors which affect the system containing catalyst and stabilizer are alyst will promote the polymerization of tertiary not yet'completely known. base olefins sufficiently faster than the polymeri When producing products within the conven zation of other oleflns that a selective polymeriza 40 tional lubricating oil range it is desirable that tion vmay be accomplished. Furthermore, I have such products have‘viscosities ranging from about found that tin tetrahalide catalysts do not appear 100 seconds at 160° F. to about 2Go seconds Say to promote copolymerization reactions between bolt viscosity at 210° F. although oils above tertiary-base oleñns and other mono-oleíins, so and/or below this range may be useful for spe that tin tetrahalide catalysts may be used to de part of my invention, and not upon determining conditions at which a known polymerization cat cial purposes. crease the content of tertiary-base olefins in a The molecular weights of these desired products are normally greater than about 300 and less than 800, and generally they are less than 500, although products somewhat either side Vmixture without concomitantly decreasing the content of other mono-oleñns. It is a character istic of catalysts such as aluminum chloride, of these-limits may at times be found desirable. boron fluoride, zirconium tetrachloride and >the The primary product of my process is a simple like, that in the polymerization of oleiins the olefin polymer, having one double bond pe'r‘mole reaction is promoted by the presence of the cor cule, and for use as a> component of lubricating responding hydrogen halide or a compound that oil it is generally desirable to increase its sta produces hydrogen halide under the conditions of the reaction, such as water or tertiary butyl 55 bility toward oxidation, as by nondestructive hy drogenation. The hydrogenated or unhydrogen chloride. Other types of modifiers, such as or ganic nitro compounds, ketones, ethers, and the like, have little or no apparent effect and in some cases may even have a tendency to lower the reaction rate. I have found that tin tetrahalides, particularly tin tetrachloride and' tinl tetrabro mide, when used as catalysts in olefin polymeriza tion reactions show unique response to added so ated produ-ct _may be used as a lubricating oil as such, or may be blended with various other stocks to produce a composite lubricating oil. In some instances my process may be operated to produce oleñnic products from the tertiary-base olefin polymerization and/or the nontertiary-base mono-olefin polymerization of somewhat lower molecular weight than that suitable for direct modiñers. As an illustration, when a tin tetra halide comprises the catalytic material for facili 65 use as lubricating oil, and such olefinic products may be employed to alkylate aromatic hydrocar tating the polymerization of olefins, the presence of hydrogen halide actually inhibits said reaction. bons, such as benzene, or toluene, or their deriv atives,~to form hydrocarbons of suitable molecu This is in direct contrast to the action exhibited lar weight and viscosity characteristics having by the presence of a hydrogen halide in the pres ence of an aluminum chloride type of catalyst 70 also enhanced solvent characteristics and the like. Oleñnic products suitable for such addi for a similar charge stock. Also, when passing isobutene for example, in intimate contact with tional treatment are included, along with prod a tin tetrahalide, such as tin tetrachloride at ucts suitable for direct use as lubricants, in the atmospheric pressure and room temperature, said broader consideration of my invention, and are isobutene is rapidly polymerized with @Volutlon 75 to be included in the term lubricating oil stocks. 2,403,179 According to» thisinvention. a mixture con fins.. . îI'he catalystand stabilizer,v are-so» chosen tainingtertiary-base-and nontertiary-base mono-êy that: theyV canbe satisfactorilyïremoyecl from vthe reactionjmixture `Without interfering Awithisub oleñnssis treated with a tin. tetrahalide, such' as tin tetrachloride or 'tin tetrabromide, preferably in admixture with, a stabilizer, as is described herein, at a temperature in a' >range of about 30 sequent usage of any other desirable compu nentzof the reactionmixture. Usually Y,both cata lyst and` stabilizer'.> are removed kby extraction to v212° F. and at a'pressure at which said olefin mixture is'v inthe> liquid state. Tin tetrachloride methods. >based 4on their own physicaland/ox: chemical, properties,l as will -he readily" appre and tin> tetrabromide are» very soluble in hydro ciated by one’skilled in theV art.. . carbons and-_under the conditions oftreatment 1.0 the system is homogeneous and thevr reaction' takes place inv a single liquid phase.V Thereac tion is exothermicr and suitablemeans ofagi'ta ` , . ' Whena mixtureto be' treated. according to my invention containsr hydrocarbons having ai com paratively wide range of molecular weightsizfor example from' 3 »tof16 carbon. atom'sxper‘molecule, it is evident-that after a treatment .withïa tin tetrahalide there may be van appreciable ramount tion and’cooling shouldbe >provided- for optimum results. By this treatment substantially only vtertiary-base> joleñns. are selectively converted to polymers, Vthe lowest. boiling ofrwhich'isr :diiso butene having a boiling point of about- 215A to 2210" F. ¿ By conducting the.` polymerization' at of tertiary-base `‘oleiin- polymers> withinl >this means known to the art.. Before a separation tially olefin and'some-parañ‘i-n hydrocarbpnsïhav; step, ‘such as distillation, it may bey desirable to remove tin halide catalyst,> such as` by extracting with cold water followed by filtration *using- an jected to polymerization conditions „to form molecular weight. range., Such a situation-may be undesirable and' .often should? be gavoided‘. This can be accomplished in mostl instancesfby about room temperature, only a small. propor 20 separating such a mixture into >fractions` >of tion of isobuteneY polymer will consist of dimer..l narrower boiling range and treating‘feachffrac The remaining nontertiary-base mono-oleñns tion separately.Y However, in'k specific- . »casess maybe- separated fromjthe reaction mixture by special techniques may produce thenesiredî re- l distillation, absorption methods, or any Aother sul't. For example, a mixture contai-ningessen ing 6 to `16 carbon> atoms per moleculefwas sub products Yin the viscosity range oi'VV lubricating oils. The mixture comprisedfprimarily straight chain mono-ol‘eñns but contained> su-,mci'ent ter tiary-base Yolefins, di'olefms, bXygenw-containing compounds, and Vthe/like that polymerization usingy zirconium tetrachloride: plus "hydrogen chloride promoter produced an oil having- van adsorptive clay filter aid,i especially when the catalyst is tin tetrachloride. In some cases tin tetrahalide may be separated and' purified in such a manner that-itA may be recycled Vto treat additional mixtures ‘containing oleñn hydro carbons. » ' ' ' ' ' ` f ` f' Besides promoting the removal of tertiary unsatisfactorily low viscosity index. ` 1_ ~~ ` base mono-oleñns from mixtures containing such oleñns, I have.' alsov found that tin tetrahalides tetrachloride together withf'd-iisopropylketone at can be used to separate di'olefins,` reactive or a temperature of- about 175 to 210°'Fiy and sufñ‘ ’ When the? mixture-was first Vtreated'y with tin ganic oxygen-containing compounds, reactive cient pressure to Yallow liquid phase'y operation, organic sulfur compounds, and the like from 40 the- polymers produced were almost’enïtirely'be mixtures containing such ycompounds and non low `thel molecular weight' range of lubricating tertiary-base `mono-ole?lns without appreciably aiîecting the nontertiary-base` mono-oleñns. Such a separation isaccomplished by converting dioleñns, reactive- organic oxygen-containing oils. Also, the ¿tin tetrachloride reacted with undesirable compounds to form a precipitate. The reaction mixture was cooled, filtered and- the catalyst removed by the extraction with cold water. The purified eñluent which stillu «con compounds and reactive organic` sulfurV com pounds intol higher molecular 4weight compounds in the presence of a tained a small amount of diisopropyffketone was tetrahali'cle catalyst, subjected to polymerization condi-tionsusi-ng zir these compounds oftenv being insoluble. in the conium tetrachloride in the presence of hy" unreacted hydrocarbon material'. ' y 50 drogen chloride. The product in the lubricating When the material that is being- treated' by a oil range from» this polymerization possessed a tin tetrahal-ide isv essentially a hydrocarbon high viscosity index. The tertiary-base, oleñn mixture containing tertiary-base olefins and non polymers in the charge to the zirconium tetra tertiary-base mono-olefinsv and no appreciable chloride polymerization step had only'l a slight amount of dioleñn's andwhen the-tertiary-base 55 tendency to polymerize further to luìn'i‘cat'i'ngJ oil olefin content of said mixture is- substantially range product. Such polymer" was Í therefore pure isobutene, polymerization at room tempera easily separated from higher boiling" material by ture and sum-cient pressurev to result in a liquid fractional distillation. » ` Y phase will produce an appreciable proportion of Ideally, all tertiary-base Aoleflns> in av mixture polymer in the viscosity range of lubricating oil'. 60 treated with a, tinV tetrahalide are polymerized On separation of this oil from the remainder of and Äall nontertiary-base mono-ol'efirisy are- un the mixture, such as by fractionation, an oil frac changed. Actually', such complete conversion -of tion is- obtained having> a relatively high viscosity tertiary-base oleñns is often impracticable and index, higher than the viscosity index of a frac unnecessary. The deleterious effect of the tionk of similar Viscosity obtained by polymerizing 65 presence of tertiary-base olefins inthe subse‘-, substantially pure isobutene using aluminum chloride catalyst. Y - Removal of tertiary-base, Aoleñns from .a mix ture containing them is readily accomplished ‘ whenftheboiling range ofthe mixtureis so narrow that the boiling rangev of the .polymers produced by treatment- with a tin tetrahalide is above the boiling range of said mixture. . In such cases fractional distillation serves; to separate polymeric material from vunreacted ,mono-ole-î quent polymerization of nontertiary-'b‘ase mono oleiins is Aroughly proportional tothe concentra tion of the tertiary-base oleñns-softhat in some cases essentially complete frenio'valj lis necessary, while in others economic considerationsfmay'per mit as much as» several! per cent of theremain-Í ing olelinicf material toïbe tertiary-base oleñns; VWhen it is- stated that vol'eiinic material is freed o_f its content of- tertiary-base 'oleñnsg 'such‘fac tors should be taken into consideration. " ‘ ‘ 2,403,779 7 . It -is preferred that the conversion of tertiary base oleiins- according to my invention be carried out inthe liquid phase, and while higherv pres 8 . be added to the polymerization zone with the tin halide through conduit 49, or separately through sures may-be used where an additional advan tageous effect resu1ts,» generally a pressure suñì conduit 39 controlled by a valve 40. vThe poly merization is preferably carried out under condi tions suitable to produce low-boiling polymers, cient to maintain an initial liquid phase will be found sufficient. With low-boiling oleñns it may such as aresuitable for use as motor fuel or as motor fuel stocks, or such as to produce polymers be desirable to include a high-boiling inert dil uent to aid in forming and maintaining a liquid suitable for use as lubricating oil stocks, as pre phase under relatively low pressures. Generally paraiiins and cycloparafiins are best suited for such-use. The reaction time for polymerizing tertiary zone I2 vwill consist of suitable polymerization viously discussed herein. The polymerization units together with heaters, coolers, catalyst chambers, and the like known to the art. When the hydrocarbonmixture to be treated according to my invention contains tertiary-base base oleñns in the presence of a tin tetrahalide varies over a wide range depending to a great 15 and nontertiary-base mono-oleiins within a wide range of molecular weights it may be desirable to extent upon the amount of'tin tetrahalide cata pass such a mixture through. conduit I3 con lyst employed in the polymerization step and on trolled by valve I4 to a separating meansV I5 from the temperature. For example, when the cata which a selected fractionof narrow boiling range lyst comprises 10 to 20 weight per cent of the re actant material, a reaction time within the range 20 or narrow molecular weight range is removed through conduit I6 controlled by a valve I1 and of thirty to fifty minutes at room temperature passed tothe polymerization zone I2. Material and under sufficient pressure to result in liquid removed through conduit 20 controlled by Valve 2I may be further separated into other narrow the vamount - of catalyst is only about 2 to 5| 25 boiling range fraction and each fraction sub jected to individual polymerization conditions weight per cent of the reactant material, a re which are optimum for polymerization of sub action time as high as six hours is not uncom stantially only tertiary-base oleiins in the pres mon for producing desirable results. The reac ence of a tin tetrahalide. Often, however, it will tion time is lowered by an increase in the tem perature employed for the polymerization step. 30 be unnecessary to separate such a mixture into several fractions when desirable results can be A tin tetrahalide employed as a catalyst in my obtained by treatment of such a mixture in a process is preferably soluble under the reaction single zone under conditions suitable for the conditions and when a tin tetrahalide catalyst polymerization of tertiary-base oleñns contained isV employed which is normally solid within the temperature range disclosed herein for operat therein. The eiliuent from the polymerization zone I2 ing my process, usually a suilìcient amount of it containing unr'eacted> nontertiary-base mono-ole can be dissolved in the material being treated ñns passes through pipe 22 and valve 23 to to promote the reaction. phase conditions will produce desirable results. However, under the same conditions except that separating means 24.- In separating means 24 un The> reaction temperature for conducting the conversion in the presence of a tin halide may be 40 reacted non-tertiary-base ole?lns are separated from polymers produced in unit I2. These poly chosen within a rather wide range. Higher tem mers may be removed with or without separa perature promote a -rapid polymerization but gention into various fractions, through suitable erally lresult in a, product of lower molecular means represented by a conduit 25 controlled by weight. A suitable temperature for any particu lar case may readily be determined by trial, by 45 valves 26 and 11. When these polymers, -or a one skilled in the art, in the light of the present fraction thereof, are suitable for use as a lubri disclosure, and will generally be found in the eating oil stock, such material may be passed from conduit `25 through conduit 10 controlled range between about 0 and about 240° F, A pre by a valve 28 for blending with a lubricating oil ferred range is between 30 and 200° F. AThe use of tin tetrahalides for the separation 50 stock produced i'n a subsequent part of the proc of oleñns in the manner described is not limited ess, as will be described. However, when the charge stock to my process contains some diole to any specific embodiment because it is evident ñns, reactive oxygen-containing compounds, re that the details of such a process will depend active sulfur compounds and/ or other gum form upon,y among other things, the nature of the charge stock and the use that is to be made of 55 ing material as well as tertiary-base olefins, other the »ñnal products. My invention will now be illustrated in connec high-boiling material will be produced besides that from tertiary-base olefins. When this is the case, a mixture containing such higher boiling material is removed from separator 24 through tion with the accompanying drawing which shows diagrammatically one arrangement of apparatus by lwhich my invention may be practiced. 60 conduit 25 and valve 2B and at least a part or all may be discharged from the process through A hydrocarbon mixture containing both ter valve 11 or passed through conduit 'I2 controlled tiary-base and nontertiary-base mono-olei'lns is by valve 13 to separating means 14. In separat introduced to the system through conduit I0 con ing means 14 desirable polymers produced from trolled by a valve II to polymerization unit I2, whereiny the mixture is treated with a tin tetra 65 tertiary-base oleñns may be removed through conduit 21 controlled by valve 'I8 and passed to halide catalyst, preferably -tin tetrachloride or conduit 10 for blending as herein described. Un ti'ritetrabromide, which acts as a catalyst for the desirable high-boilingv material can be removed selective polymerization of tertiary-base oleñns. Such a catalyst may be conveniently admitted to from separating means 14 through conduit 'I5 polymerization Zone I2 with the incoming feed 70 controlled by valve 16. High-boiling material re moved through valve 11 may be Vtreated in such a stock or; separately through conduit 49, controlled by a valve 50. A stabilizer for said catalyst se manner as appears desirable. For example, ter-Y tiary-base oleiin polymers so removed may be lected from the group consisting of nitro hydro passed to a catalytic alkylation step to react with carbons- and ketones having an alpha carbon atom to which is- attached. a single'hydrogen atom may 75 paraiîlin` hydrocarbons for the production of 2,403,779 ' 10 highly -branchedhigher boiling paraffin hydro tion suitable for allubricating oil` stock Ymay vbe carbons of superior antiknock quality, and suit Y passe-dl from-conduit '41 through conduit 5I Vcon able as constituents of motor fuel. Various alkyl ation catalysts such ashydrofluoric acid, sulfuric , acid,. aluminum chloride, silica> alumina, .and the like may be' employed in Vsuch a step. l A material containing Vvnontertiary-base mono oleflns and substantially free of tertiary-base ole ñns,.as herein discussed, is passedfromseparat ing means 24 `through a conduit 3| controlledv by 10 a valve 29 to apolymerizationunit 33 wherein la polymerization is ‘eñ‘ected to form vpolymers suit able for >use as a lubricating oil stock. The ole trolled' by a valve 48 toa hydrogenator 54 where in/»a major part of the polymer- fractionl is non destmctívely yhydrogenated .in the presence >of a suitable hydrogenation catalyst and. in the pres ence ¿of hydrogen added lthrough >conduit. 55 con trolled bya valve 56. A resulting saturated 'hy drocabon material is passed through conduit 51 controlled by a valve 58 to?separating means 6|. lll-saturated` `hydrocarbon* material suitable for use as» a lubricating oil stock may be recovered fromv 4separating v,means'tl through conduit 62 i'lns polymerized in unit 33 may be supplemented controlled byy valve :63 and> anyj vundesired mate by nontertiary-base mono-oleñhs added to the 15 rial maybe discharged from the system through system through a conduit 30 controlled by a valve aconduitiß‘d cont-rolled'by- a valve 65. ' _ 32 passing to conduit 3|, `and in some instances When the polymerization in unit |2 Vis such> a olei'lns so added mayconstitute the sole source to produce polymers suitable for use as lubricat of olelinic material charged to this step. Poly ' ingpoîlestoclc, such polymers ymay be blended with merization in unit 33 is carried. out in the pres polymers: producedinunit 33 to forma compos-.I ence offacatalyst active for the polymerization ite product of the ,two :types ofY polymerization. of nontertiary-base olefLns, such as aluminum When.-r arpolymer fraction fromunit |2 is recov chloride, zirconium chloride, boron fluoride or ered without. additional treatment, a polymer other halides of aluminum, ‘zirconium and boron fraction passing throughconduit 10 and valve 28 associated with a hydrogen halide which maybe 25 Ymay Vbe'passed Ythrough valve 1| to conduit 41 addedïthrough a conduit 31 controlled by a valve and ¿the `composite lubricating oil stock recov 38. However, it is to be understood that such ered vthrough valve 53,. When it is desired to catalysts are not to be considered as equivalents subject polymer passing'through conduit .10 to to one another, either in regardrto polymeriza subsequent hydrogenation, such polymermay be tion conditions >or characteristics of ' products 30 removed from conduit 1|!4 through a conduit 66 formed.. The polymerization conditions are such that al1-,optimum yield o-f rpolymers*suitable for >5| and hydrogenator 54 for further treatment use as .a lubricating oil kstock are produced as as previously discussed. controlled by a valvev 61Y andpassed` to conduit previously has been discussed, and the unit 33 -will , .Y A ~ It 'is to be appreciated that the drawing just lcomprise suitable catalyst chambers, âheaters, described is diagrammatic ' only. coolers, pumps, and the vlike as Vmay be supplied pieces of equipment illustrated and discussed are` for any particular case by, one skilledrin the art. The eiliuent of unit 33 passes througha con duit34 controlled by a valve 35 to separating mea-ns36 vand when the material passing through conduit 34 consists substantially only of hydro The various conventional in nature, ‘and in any application ` of my invention there will be associated with the individual units shown various pumps, heaters, coolers, reflux accumulators, heat exchangers, fractionating columns, temperature indicating carbons, the fractions recovered from the mate rial may> be separated by simple fractional dis' and control devices and the like known in the art and which may be suitably supplied for anyfpar tillation and one or more fractionating columns ticular case by one .skilled in the art following as'may be readily ascertained ‘by one skilled in 45 the teachings of the reaction conditions and ma fthe art. In some instances when a mobile poly terial flows disclosed and discussed herein. merization catalyst is used in unit 33, separating My invention will be further illustrated by the means36 may also Vinclude suitable equipment for following specific examples, which show various removal of the catalyst and >any impurities con advantages of the invention but which are not tained in the material> passing through conduit necessarily to be construed as hunting the'inven 34 as may be suited .to the particular material tion. being treated. Unreacted oleñns and/or .low boiling polymers may be removed from separat ~ Y EXAMPLE I ~ f , ~ Y Isobutene was passed in contact with approxi mately 100 parts by weight of tin tetrachloride at a valve 42 and returned for further reaction >in 55 roomtemperature and atmospheric pressure at` unit 33 by conduits 3U and 3|. Undesired low the rate of about 25 vparts by weight per hour. boiling material, which may include paranins, The isobutene was bubbled through the body of> is discharged from the system through a conduit the tin tetrachloride which was present as a 43 controlled by a valve 44. Heavy hydrocarbons, liquid and constantly agitated with a suitable tar and/or sludgemaybe discharged from the 60 stirring device. Polymerization began immedi system through a conduit 45 controlled by a valve ately. At said addition rate only a small amount 46. One or morefpolymer fractions »containing of isobutene passed through the system uncon polymers suitable for use as lubricating oil stock verted. The tin tetrachloride catalyst was slowly are recovered from separating means A36 through deactivated, so' that 'after' two hours a major por one or more conduitsk illustrated by conduit 41 65 tion'of the isobutene ~was passing through un and may be discharged from the system through converted, ' ing means 36 `through a conduit 4| ' controlled by valves 52 and 53. _f p . As previously discussed it isgenerally desirable F. The run was repeated ata temperature of 140° Under such conditions the corresponding ex to subject such polymers to further treatment tent of deactivation occurred in about a half hour, which may include alkylation with aromatic hy 70 showing the marked 4eiîect of reaction tempera drocarbons, >saturation with hydrogen by non ture on deactivation rate. destructive hydrogenation, or the like. Such EXAMPLE II further treatment will be illustratedby nonde structive hydrogenation and whensuch treat The run cited in Example I conducted at room ment is desired, anypart or all of a polymer frac 75 temperature was repeated. When the activity of 2,403,779 11 12 the catalyst had decreased considerably, ’0.1 mol merized With al catalyst consisting of aluminum per cent oaf nitrobenzene Was added. The cata lytic activity was increased only for a short time. Sixty-live mol per cent of nitrobenzene Was then liquid phase at. 86„to„95‘îVv F. The ’catalyst was rapidly deactivated With the formation of a dark added. During an eight hour reaction period, the catalytic activity did not decrease notice ably. The stabilizing effect of nitrobenzene was thus evident. . . _ EXAMPLE III chloride plus hydrogen ’ chloride promoter in colored insoluble residue. , The resulting polymer fraction in the lubricating voil viscosity range possessed viscosity indexgvalues of 10 to 35. ’t Another portionof this stockwas treated with 10 per cent -by weight ,of aV tin Ytetrachloride 10 nitrobenzene mixture vat 140° F; for -aftwo hour ` The run cited in Example I conducted at room period.` The unreactedoleñn-parañin constitu temperature WasV repeated using as catalyst tin tetrachloride plus 50 mol per cent of diisopropyl ketone. Isobutene was bubbled into the catalyst entswere separatedby distillation; .It was found that about 20 per cent ofthe total oleñn content mixture for 22 hours. of the charge Was removed in this treatment. _ The 15 remaining olefin-paraffin mixture in the'.,122 to The reactionV rate de creased only slightly throughout the entire reac 167? F. boiling range was treated with aluminum tion period. chloride plus hydrogen chloride promoterin liquid ' . ` ' 'EXAMPLE IV phase at`86 to 95° F. , Only a small'proportion of . The run in Example I conducted at room tem dark-colored sludgeV ÍWas formed Aduring poly merization. Theresulting polymer fractions'in - Y perature was repeated using as catalyst tin tetra chloride plus Y50 mol per cent nitromethane. The reaction was continued for eighteen hours. The activity of the catalyst vdid not noticeably the lubricating oil viscosity range, which were equivalent in volume to those produced `in the preceding experiment.' possessed viscosity index values of 40 to 65.r The tin tetrachloride treat increased to a maximum of 104° F. during the 25 ment thus removed from the olefin-containing decrease duringA` this period. The temperature experiment. charge stock materials which adversely affected the activity of the aluminum chloride catalyst and also materials which produced low viscosity About 24 per cent ofthe resultant polymer was in the viscosity range of lubricating oil. The characteristics of two fractions are given in Table I. index polymers. , . 30 Table I Viscosity n zag-21150. - v Fraction s ____ ______ Viscosit Y index .. . . Iniview of many possible modifications of the process that will be obvious to those skilled in the art, the invention should not be limited unduly by the foregoing speciñcation and examples, but it should be understood to ber extensivein scope 35 and equivalents, Within the limits of the appended _________________ __ 39.8 93 9 ____________________________________ __ 60. 6 85 claims, Without departing from Vthespirit of the disclosure and teachings. I claim: EXAMPLE V „ ' . ‘ t ‘ 1. In a process for the selective polymerization The -run cited in Example I conducted at room 40 oftertiary-base oleflns which are associated with nontertiary-base oleñns, the improvement which comprises subjecting a liquid hydrocarbon mix lowing materials: carbon tetrachloride, tertiary ture which contains such oleñns to the polymer butyl chloride, hydrogen chloride, water. None ofY these promoted the polymerization of iso izing actíon'of a tin tetrahalide associated with a 45 ketone in which there is an alpha carbon which butene, and they may actually have hastened the has a single hydrogen to polymerize only tertiary deactivation of the catalyst. . base oleñns, and recovering from said polymeriza temperature Was repeated adding each of the fol EXAMPLE VI tion a hydrocarbon mixture which contains unre Tin tetrachloride and liquid propene were acted nontertiary-base oleflns and is substantially sealed in a glass tube in a Volume ratio of ,1:15. 50 free Yfrom tertiary-base olefins.A ~ » ' After standing four days at room temperature, no polymer Was formed. 2.v In a process for the selective polymerization of tertiary-base oleñns which are associated with EXAMPLE VII nontertiary-base oleñns, the improvement which comprises subjecting a liquid` hydrocarbon mix The run cited in Example I conducted at room 55 temperature Was repeated using tin tetrachloride plus pentene-l. No polymervvas produced. This run was repeated adding each of the following ture which contains vsuch oleñns to the polymer izing action of a tin tetrahalide associated with diisopropyl ketone vto polymerize only tertiary base oleiins, and recovering from said polymeriza compounds: carbon tetrachloride, tertiary butyl tion a hydrocarbon mixture which contains unre chloride, water, nitromethane, and diisopropyl 60 acted nontertiary-base oleñns and is substantially ketone. YNo polymer Was obtained from any of free from tertiary-base oleñns. these runs. Y ' Y EXAMPLE VIII The oleñn li-methylpentene-Z was not poly ` - « ’ 3. A process for the polymerization of tertiary base oleñns > whichY comprises -subjecting such oleñns to the polymerizingaction of a tin tetra merized at room temperature using tin tetra 65 halide associated with a ketone in which there is chloride catalyst either alone or with stabilizersv an alpha carbon atom to whichV is attached a single such as employed in Example VII. hydrogen atom. v ~ ` EXAMPLE IX- . . An oleiin-containing charge stock boiling be tween 122 and 167° F., obtained from thermal conversion of low-boiling hydrocarbons, was poly ~ 4. A process according to claim 3 wherein said 70 tin tetrahalide is tin tetrachloride and said ketone is diisopropyl ketone. ‘ ` ' ` ‘ GRANT C. BAILEY.