CA1074775A - Process for the manufacture of a catalyst - Google Patents

Abstract

Process for the manufacture of a catalyst Abstract of the Disclosure A catalyst of high activity and stereospecificity in .alpha.-olefin polymerization is obtained by subjecting titanium Trichloride, obtained by reduction of titanium tetrachloride with aluminum alkyl halides, to two thermal treatments, the second thermal treatment being carried out in the presence of a dialkyl ether and optionally of a cyclopolyene, and optionally subjecting the treated product to an after-treat-ment with an aluminum alkyl halide, optionally in the presence of a small amount of a cyclopolyene and/or an olefin.

Description

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The prssent invention relates to a process for the manufacture of a catalyst suitabl0 for the polymerization of ~-olefins.
In tha polymerization of propylene or higher ~-olefins with Ziegler type catalysts there are obtained, besides ths technically ~ery interesting highly crystalline polymers, which are insoluble or sparingly soluble in ths hydrocarbons used as dispsrsion media under the polymerization condi-tions, also amorphous, readily soluble polymers, and oils. According to Natta, the highly crystalline polymers are sterically ordered and ar0 called "isotactic", while the soluble polymers are sterically disordered ( 10 and are called ~atactic~.
The formation of isotactic and amorphous poly~-olefins is regulated by the catalyst system. For an economically useful process catalyst sy9tems having a selactive action are required which lsad exclusively or almo9t exclusively to the formation of the desired pol~mers.
A process has become known (8ritish patent 895,595) according to which the selectivity of catalysts of the aforesaid type can be considerably im-proved with respect to the formation of polymers with high content of i~o-tactic fraction by subjecting ths reaction product of TiC14 and halogen-containing aluminum-organic compounds to a thermal treatment at a tempera-ture in the range of from ~0 to 150D C and after the treatment optionally washing the product several times with an inert solvent~ This heat treated and washed catalyst is then activated in the olefin polymerization with fresh diethyl aluminum monochloride. The efficiency of the heat treated catalysts can be further improved by effecting the thermal treatment in the presenc0 of complex forming compounds or compounds forming double salts, for example ethers and sodium chloride, It i9 a primary obj0ct of this invention to provide a procese for the manufacture of a catalyst suitable for olefin polymeri~ation by reacting titanium tetrachloride in an inert hydrocarbon solvent with an aluminum-~ 2 -- ' ' ', ` ~ :
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organic compound containing an aluminum dialkyl chloride~ tnermally treat-ing the TiC13 containing reaction product in the presence of an ether, sr--parating and washing ths reaction p~orJuct (component A) and mixing it with an aluminum dialkyl halide (component ~) and optionally with a cyclopolyene (component C) as stereoregulator, which comprises adding the aluminum-organic compound containing aluminum dialkyl chloride -to the TiC14 at a ten-perature of from -20 to ~20 C in a molar proportion of aluminum dialkyl chloride to TiC14 of from 0~8 1 to 1.5 to 1, subjecting the TiC13-contain-ing solid reaction product to a thermal treatmsnt at a temperature of from 40 to 150 C, effecting a further thermal treatment in the presence of a ( dialkyl ether and separating the solid reaction product (component A).
The invention also relates to the catalyst prepared by the afore-described process and to its use in the polymerization of~-olefins.
To prepare the catalyst in accordance with the inuention titanium tetrachloride is first reacted in an inert hydrocarbon solvent with an aluminum-organic compound containing an aluminum dialkyl chloride.
The aluminum-organic compound containing an aluminum dia]kyl chloride to be used is sither an aluminum dialkyl chloride carrying alkyl group~
with 1 to 6 carbon atoms9 praferably aluminum diethyl chloride, dipropyl chloride, diisopropyl chloride, diisobutyl chloride, more preferably alu-minum diethyl chloride, or an aluminum alkyl sesquichloride9 i.e. an squi-molocular mixturD of aluminum dialkyl monochloride andaluminum alkyl di-chloride, prefsrably aluminum ethyl sesquichloride9 propyl sesquichloride, isopropyl sesquichlorida or isobutyl sesquichloride) aluminum ethyl sesqui~
chloride being particularly preferred.
In the reaotion Df titanium tetrachloride and the aluminum-organic compound containing an aluminum dialkyl chlorida the molar proportion of aluminum dialkyl chloride to titanium tetrachloride is in the range of from oOa to 1.5 : 1~ prefr3rably 0.9 : 1 to 1.1 : 1. The alurninum compound i~

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addsd to the dissolved titanium tetrachlorids at a temperature of from -20 to +~0 CJ preferably O to 5 C.
As solvent an alkans or cycloalkane that is liquid at the reaction temperature is prefPrably used, for sxample hexane, heptane, octane, cyclo-hexans, or a hydrocarbon mixture, for example a gasoline fraction boilingin the range of from 130 to 170 C. Further suitable sol~ents are those which ars used as dispersion medium in the polymerization ofo!_olefins.
Ths amount of solvent is prsferably chosen in such a mannsr that a 4û to 60 % by wsight solution of ths titanium tetrachlorids and a 15 to 25 % by ( 10 weight solution of the aluminum-organic compound are ussd. rhe sama sol-vents are also used for the following reactions.
The TiCl3-containing solid reaction product formPd is separated from ths reaction products which are soluble in the hydrocarbon, washed with ths sol~ent and subjected to the first thsrmal treatment at a temperature of from 40 to 150 C, preferably ~0 to 110 C, in the form of a suspension and while stirring~ This first thermal treatment can likewiss be sffsctad prior to the separation of the reaction products soluble in tha hydrocarbon, i.e. in their presence. In this case, the ~iCl3-containing reaction pro-duct is washed with the inert hydrocarbon aPter the first thsrmal treatment.
2û It provad advantagèous to carry out the first thsrmal treatment in several stagas at diffsrent temperaturss, for example in the first staga at 80 to 95 C and in the second stage at 100 to 110 C. The duration of ths first thermal treatment depsnds on the temperature9 i.e. it lasts longer at a low temperaturs than at a high temperature, the treatment times preferably being in the range of from 30 to 600 minutes. The thermally trsated and washsd reaction product containing solid TiC13 is suspended in an inert hydrocarbon and subjscted to a further thermal treatment in the presence of a dialkyl ether and optionally a cyclopolyene.
If the solid reaction product has been separated from the mother liquo~

~7~775 ~IOE /4/F 0~1 K

and washed, it is now again suspended in the solvent in an amount such that the concentration of titanium in ths suspension is in the range of from 0.5 to 2.5 moles of TiC13, preferably 1.5 to 2.5 moles, per liter of sol-vent. The second thermal treatment is carried out at a temperature of from 40 to 150 C~ prefera~ly 40 to 120 C and more especially 60 to 90 O.
Suitable dialkyl ethers ars those having from 2 to 5 carbon atoms in each alkyl group~ for example diethyl ether, di-n-propyl ether9 diisopropyl sther~ di-n-butyl ether, diisobutyl ethsr~ preferably di-n-butyl sther.
The molsr proportion of titanium trichlorids to dialkyl ether in the sscond - 10 thsrmal treatmentis preferably in the range of from 1 : 0~6 to 1 : 1.2 more praferably 1 : 0,9 to 1 : 1.
Suitable cyclopolyenes are norcaradiene and thoss having 7 ring mem-bers an~ 3 non cumulated doubls bon~s in the ring as wEll as thoss having 8 ring members and 3 or 4 non cumulated double bonds in the ring, prefer-ably cycloheptatriene-1,3~5, cyclooctatriene-1~3~5~ and cyclooctatetraens~
1,3~5~7, as well as the alkyl- and alkoxy-substituted derivatives thereof in which the alkyl group contains from 1 to 4 carbon atoms~ cyclohepta~
triene-1~3,5 being preferred. The molar proportion of titanium trichloride to cyclopolyens is in the range of from 1 : 0.001 to 1 : 0015, preferably 1 : 0.005 to 1 : 0.08 and especially 1 : 0.05 to 1 : 0.1~
The dialkyl ether is addsd to the suspension of the solid reaction product or vice versa. In the second heat treatment the dialkyl ethsr can be dissolved in a sol~ent~ it is more advantageous~ however, not to diluts it. Ths dialkyl sthsr i8 addsd to the solid suspension or the solid sus-pension to th~ dialkyl ether at ths tempsrature of the second hsat treat-ment over a psriod of A few seconds to 5 hours, preferably 1 to 30 minutes~
Prior to th~ addition of the cyclopolyane the suspsnsion is preferably trsated first with the ether alone for 1 to ~5 and advantageously 5 to 30 minutos. After mixing of the reaction components9 the mixture is stirred .- ~. ' '- "-,'.. : .' '" ,. ': " '~', . ' '' 7~

for 5 to 300 and preferably 30 to 60 minutes at the temperature of this thermal treatment.
After the second thermal treatment ~he TiC13-containing reaction pro-duct is tho}oughly washed with a hydrocarbon solvent.
Th~ solid reaction produc~ can be treated in suspension at a concen-eration of 0.001 to 0.5 mole of TiC13~ preferably 0.05 to 0.1 mole TiC13 per liter sol~ent with an aluminum alkyl halide. To this effect aluminum alkyl halides of the formula AlR X3 in which R stands for an alkyl radi-cal having from 2 to 8 carbon atoms, X represents a halogen a~om and n is a number in the range of from 1 to 2 can ~e used, for example aluminum dialkyl halides, aluminum allcyl dihalides, and aluminum alkyl sesquihalides, more particularly aluminum diethyl chloride, aluminum ethyl dichloride and alu-minum ethyl sesquichloride. A very economic method consists in using the mother liquor obtained in the preparation of the TiC13-containlng reaction product and preponderantly containing aluminum alkyl dichlorides.
The molar proportion of aluminum alkyl halide to TiC13 in the suspen~
sion to be trea~ed is in the range of from 0.8 : 1 to 10 : 1 and preferably 1 : 1 to 5 : 1 and the treatment is Garried out at a temperature of from 0 to 60 C~ preferably 20 to 40 C while stirring.
The after-treatment with the alkyl aluminum halide is preferably carried out in the presence of a small amount of a cyclopolyene.Suitable cyclopolyenes are norcaradiene and those having 7 ring members and 3 non cumulated doubla bonds in the ring as well as those having 8 ring members and 3 or 4 non cumulated double bonds ~n the ring, preferably cyclohepta-triene-193,5, cyclooctatriene-1,395, and cyclooctatetraene-1,3~5,7, as well as the al~yl- and alkoxy-substituted derivatives thereof in which the alkyl group contains from 1 to ~ carbon atoms9 cycloheptatriene-1,375 being pre-ferred. The molar proportion of titanium ~richloride to cyclopolyene is in the range of from 1 : 0.001 to 1 : 1~ preferably 1 : 0~005 to 1 0.8 and .

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more preferably 1 : 0.075 to 1 : 0.5.
When the after-trsatment with an aluminum alkyl halide is carried out in the pressnce of a cyclopolyene the addition of a third catalyst componEnt (component C) in the polymerization can be wholly or partially dispensed with.
Tha aftsr-treatment with the aluminum alkyl halide can alsD be carried out in the presence of a small amount of an olefin, either in the presence or in the absencs of a cyclDpolyene as defined above. There can be ussd morio-olefins having from 2 to 10 carbon atoms~ preferably ethylene9 propy-lens, butene-1, or 4-methyl-pentene-1~ The molar proportion of titanium trichloride to olefin is in the range of from 1 : 1 to 1 : 100~ preferably 1 : 1 to 1 : 50 and more preferably 1 : 1.5 to 1 : 20.
When the after-treatment is carried out with an aluminum alkyl dihalide or aluminum alkyl sesquihalide the catalyst component A formed rnust be se-parated from the suspansion and washed with an inart hydrocarbon solvent.
With the use of an aluminum dialkyl monohalide, however~ the isolation and washing of component A can be dispensed with. Moreovar, in the latter case the amount of catalyst component B could be rsduc3d by the amount of alumi-num dialkyl monohalide used for the aftsr~treatment.
Aftar separation from the solvent by decantation or filtration, the catalyst component A can be dried with the exclusion of air and humidity and then stored, Component A is used either in the form of a suspension~ for axample 3S obtained in the after-traatrnent with an aluminum alkyl halide 9 or it is isolated~ washsd and suspended in an inert hydrocarbon solvent kogether with an aluminum dialkyl halide (~omponant B) and optionally a cyclopolyene (component C) and then used for the polymerization of ~~olefins. o~-ûlefins which can be polymeri~ed with tha catalyst of the invention are those of ihe formula Ci~2-CHR in which R stands for an alkyl radical having from 1 to - 7 ~
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II~E 74/F 081 K_ ~7~775 8 carbon atoms , preferably propylene9 butene-1, pentene-1, 3-methylbutene-1, 4-methyl-pentene-1 and 3-methyl-pentene-1, propylene being preferred. The catalyst according to the invention can be used for the homopolymerization as well as for the copolymerization of mixtures of tha aforesaid ole~ins with OnQ another and/or with ethylenL3. In the copolymerization the mixture contains at least 95 % by weight of one of the~-ole~ins and at most 5 % by weight of ethylene, each time calculated on tha total amount of the mono-mers. The catalyst is espscially favorablc for the polymerization of mixtures of propylene with small amounts of ethylene of from 0.5 to 5 and preferably 1.5 to 3 ~ by weight The catalyst of the invention can alsD be used for tho block polymerization of the saidÇ~-olefins with ona anothsr ~nd/or with ethylane. In this case the content of sthylsne is below 25 by weight. ~lock polymers of propylene and ethylene are preferably made.
Tl-o block polymers made with the catalyst of the invention are characterized by a high hardness and an excellent impact strength at a temperature below O C.
The polymerization is carried out continuously or discontinuously in suspension ar in the gaseous phase at a pressure of from 1 to 50 kg/cm , prsferably 1 to 40 kg/cm ~
Tho suspension polymerization is carried out in an inert solvent~ for exampls a petroleum fraction poor in olefins and having a boilino point in the range of from 60 to 250 C which must be carefully freed from oxygen, sulfur compounds and humidity, or saturated aliphatic and cycloaliphatic hydrocarbons such as butane, pentane~ hexane, heptane, cyclohexane, methyl-cyclohexane~ or aromatic compounds such as benzene~ toluene, and xylene~
The suspension polymerization can advantageously be carried out also in the ~-olefin to be polymerized9 for example liquid propylene, as dispersion medium.
It is likewise possibl~ to corry out the poylm~rization in thL3 absence ' ' ~ . ' ' -' -' ' -: , , . . ", . . . :
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of a solvent in the gaseous phase, for example in a fluidized bed.
If necessary, the molecular weight of the polymer is regulated by adding hydrogen.
The amount of the catalyst component A depends on the intended reac-tion conditions~ especially temperature and pressure~ In general~ û.05 to10 m/moles of TiCl3 and preferably 001 to 3 m/moles, are used per liter of solvent in the suspension polymerization or per liter of reactor volume in th~ gas phase polymerization~
Catalyst component 9 is an aluminum dialkyl monochloride of the formula ( 10AlR2Cl in which R is an aliphatic hydrocarbon radical having up to 8 carbon atoms, preferably aluminum disthyl monochloride. The amount of component is chosen in such a manner that the molar proportion oF component B to com-ponent A (calculated on TiCl3~ is in the ranga of from û.5 to 1 to 100 : 1, preferably 1 : 1 to 1û : 1.
15The catalyst consisting of components A and ~ has a high polymeriza-tion àctivity and a good stersosp2cificity which largely dspends on the polymerization temperatura~ When, for examplet propylene is polymerizsd at 60 C the dispersion medium contains less than 3~0 % by weight of soluble fractions, calculated on the total polymsr, preferably less than 2.0 ~ by wRight~ ~t a polymerization temperature of 7û to 80 C the undesired solubls fraction increases to up to 4 ~ by weight. On the other hand, a highar po~ymerization temperature is desirable with respect to the dissipa-tion of ths polymerization heat.
It is known that with increasing pressure and, hence, at a higher polymerization rate, the amount of solub]e fractions increases. When, For sxample, propylene is polymerized in liquid propylene under about 32 kg/cm and at 70 Cj up to 6 % of soluble fraGtions are obtained.
The good st~reo~pecificity of the catalyst at higheripolymerization pressure and tPmperaturc can bo further improved by using a cyclopolyene -.~. ,. ~ .....
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as catalyst component C, such as specified abovs. Component C is added to component A suitably together with componsnt 8 at the beginning of polyoor -zation. The molar proportion of component C to somponent ~ calculate~ as TiCl3, is in the range of from 0.1 ; 1 to 1 : 1, preferably 0,2 : 1 to 0.6 : 1.
The polymerization in the presence of the catalyst of ths invention is carried out at a temperature of from 20 to 120 C, preferably 50 to 90 (:.
Higher temperatures are also possible but in this case a higher fraction of solubla atactic polymer is formed.
9y the thermal treatment according to the invention in several stages of a titanium chloride containing reduced solid with th~ last stage of the thermal treatmont being carried ouk in the presence of a dialkyl ether and a cyclopolyene, a catalyst component (A) is obtained which already, in com-bination with an aluminum dialkyl halide as activator (component a), con-sidarably increases the polymerization rate of~-olefins with improvsd stereospecificity. As compared to the state of the art as disclosed in Oritish Specification ~95,595, the catalyst activity is ovar 100 ~0 higher at the same polymerization temperature and pressure with an equ~lly good stereospecificity. Owing to the higher catalyst activity (g polymer per ( ~ 20 9 catalyst~ the same space_time yield can be obtained with a smaller amount of catalyst, whereby the further processing of the polymer is considerably ll facilitated or a processing under like conditions ensurss a more efficient ;
removal of the catalyst. When the polymerization is carried our under elevated pressure~ for example above 20 kg/cm ~ either in the gaseous phase or in liquidOG-olefin~ for example liquid propylene~ ~he yields obtained arc so high that a catalyst ramoval can be dispensed with (more than 1,000 9 polym~r per millimole TiC13).
The following examples illustrate the invention~
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A) Prcparation o~ catalyst A 1) Reduction o~ TiC14 by using aluminum ethyl sesquichloride With the exclusion of air and moisture a 1û liter vessel with stirrer was charged with 1,090 ml of a hydrogenated, oxygen-free gasoline fraction boiling at 140 - 165 C and 550 ml of titanium tetrachloride (S moles) and at O C~ while stirring under nitrogen~ (250 rev/min) a solution of 1111,2 9 of aluminum ethyl sesquichloride containing 4.5 moles aluminum disthyl mono-chlorids in 3334 9 of the gasoline fraction was dropped in over a period of 8 hoursO A rud-brown fine precipitate separated. The mixture was stirred for another 2 hours at O C and then for 12 hours at room temperatLre.
The suspension was heated for 4 hours to 90 C and for anothsr 6 hours to 110 C. The separated precipitats was allowed to settle and the super-natant mothsr liquor was separatsd by d~cantation and washsd five timss, each time with 2~000 ml of the gasoline fraction. The washsd solid rsac-tion product was suspencled again in the gasoline fraction and the concen-tration of the suspension was adjusted to 2 moles TiCl3/liter. The content of trivalent titanium in ths suspension was determined by titration with a Ce-IV solution.
.

2) Second thermal treatment in ths pressnce of di-n-butyl sthsr 500 ml of the 2-molar suspension (currssponding to 1 mole TiC133 wsre heated to 85 C in a 2 liter vessel with stirrer, with the exclusion of air and humidity and undsr nitrogen and at said tempersture 161 ml di-n-butyl sthsr (0.95 mole) wsre dropped in while stirring over a period of 30 minu-tss. Ths suspension was kept at B5 C for one hour. On adding the ether ths mother liquor turnsd olive green. The treated catalyst component A
was then waahed five times, each tims with 500 ml of the gasoline fraction.
e) Polymerization of propylene A 1 liter glass autoclave was charged with the sxclusion of air and humidity, with-0.5 liter of th~ aforesaid hydrogenated gasoline fraction , .` - ' ', ' ' ~7~77~ HOE 7~/F 0~1 K

(b.p. 140 - 165 C) and th~ gasolin~ was saturat~d with propylsns a-t 55 C.
The amounts of Al(C2H5)2Cl (activator, component ~) indicated in the follow-ing Table 1 wsrs addsd and thsn componsnt A, i.e. thsrmally trsated solid reaction product according to A 2) (Examplos 1 and 2) and solid r~action product according to A 1), (ExampIe 3 = comparative Exampls A), respectively~
was added, each time in an amount corrssponding to 1 mmole TiC13. û~25 kg/
cm hydrogsn was forced in and over a period of 5 minutes propylene was introducsd in an amount such that a pressurs of 6 kg/cm2 was obtainsd.
During ths courss of polymerization this pressurs was maintained by adding ( 10 propylsne. After a time of polymsri2ation of 2 hours ths prsssurs in ths autoclave was rsleassd and ths polymer suspension was filter3d off with suction~ ths polymer on the filter was washed with 1 litsr of hot solvent (70 C) and drisd at 70 C undsr rsduced prsssurs.
To detsrmine the soluble fraction formed in the polymeri~ation (atactic polypropylsns) the mother liquor of ths polymer susp~nsion and the wash solutions wsrs combinsd and svaporated to drynsss undsr rsduced prsssurs.
The polymerization rssults ars listsd in ths following Tabls 1 E x a m p l s 4 (Comparativs Exampls ~) A) Preparation of catalyst TiCl4 was rsducsd with aluminum ethyl sssquichlorids under ths condi-tions spscifisd in Exampls 1, A 1~ but aftsr the rsaction ths prscipitats was not subjsctsd to a thsrmal trsatmsnt, it was only washsd, suspended and ths suspsnsion was adjustsd to a concsntration of 2 molss TiCl3/l. 500 ml of ths 2~molar suspension (corrssponding to 1 mole TiC13) were hsatsd to C5 C and at said tsmperature 161 ml di-n-butyl ethsr (û.95 mols) wers droppsd in whil3 stirring ovsr a psriod of 3D minutes. The suspension was maintained ~t C5 C for 1 hour. On adding th3 ether ths mother liquor turnsd oli~s grcen.
The solid rsaction proouct was washed ~ive timss, sach time with ` . : ` ~ ` :. ,: ., ~ `:
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1~000 ml of the gasoline frac~ion.
~) Polymerization Df propylene under pressure Th~ polymeri~ation with the catalyst component A obtained as described sub A was carried out under the conditions of Example 1 ~). The result is listed in the following Table 1.
E x a m p l_e 5 Polymerization of propylene in liquid monomer.
A 16 liter enamelled ~ess~l provided with stirrer, jacl<et heating and gas inlet was flushed at room tPmperature with pure nitrogen and th~n with propylsne. A pressure of 0.5 kg/cm2 of hydrogen was built up and through a valve a solution of 32 mmoles Al~C2H5)2Cl in 6 liter of liquid propylene end a suspension of the catalyst component A (4 mmoles TiC13) according to Ex-~mpl~ 1 A in 6 liters of liquid propylenewersaddsd~ The vessel was heated to 7û C whareby the pressure rose to about 32 kg/cm2. The internal tempe-rature was maintained at 7û C by cooling. Polymerization started after afsw minutes and was interrupted aft~r 6 hours by pressure release. After drying 5.5 kg of a freely flowing polymer having an apparent density of 52û g/l wsre obtained. The reduced specific viscosity tRSU) was 2,6 dl/g.
9y a 16 hour extraction with heptane a solublz fraction of 6.5 % by weight 2û was found. The ball indentation hardness according to DIN 53 456 was 670 kg/cm ~
E x a m p l e 6 Polymerization of 4-methylpentenP-1 A 2 litsr ~essel with stirrer, thermomEter and gas inlst was charged, with the exclusion of air and humidity, with 1 l of hydrogenated oxygen-free ga~oline fraction (b.p. 140 - 165 C) and scavenged with pure nitrogen. At C B mmolss of aluminum diethyl monoch]oride (0~97 ml) and an amount of the catalyst componsnt A prepared according to Example 1 A corrssponding to 5 mmoles of TiCl3 were added~ During the course of 3 hnurs 200 9 Df 4~m~thyl-~,' ' . ' ` " ' : ~ :.', . :

~7~775 Ho~ 74/F 081 K
-pentene-1 were added dropwise. The polymorization temperature was main-tained at 55 C. Polymerization started after a few minute3 and the noly-mer separated in the form of a fins prscipitats. Whsn ths dropwis~ addi-tion was terminatsd ths polymsrization mixture was stirred for annther 5 2 hours at 55 C and the polymerization was intarrupted by adding 5û ml of isopropanol, the mixture was stirrsd for 1 hour at 60 C, axtracted with ~!arm water and filtsred with suction while still hot. After thorough wt~sh-ing with hot solvent (gasoline) and acetone and drying under reduced pressurs at 70 C~ 190 9 of colorless poly-4-methylpentene-1 were obtained having an apparent density of 520 g/l. The mothsr liquor was found to con-tain a very small soluble fraction of 0.3 %.
E x a m p l e s 7 - 12 A) The catalyst component A was prepared as described in Example 1 A
0) Polymarization of propylene A 1 liter glass autoclaue was charged~ with the exclusion of air and hOmidity~ with 0.5 l of a hydrogenated gasoline fraction (b.p~ 140 ~ 165 C) and saturated with propylene at 55 C. The amounts of Al(C2H5)~Cl (acti-vatort component B), fre~hly distilled cyclohetatriene-1,3,5 (component C) and then tha above specified catalyst component A (sach time 1 mmola TiC13) ( 20 were added. 0.25 kg/cm2 of hydrogen was forced in and within 5 minutes propylene was introduced in an amount to build up a pressure of 6 kgjrm .
This pressure was maintained during the courss of polymerization by adding propylene. After a time of polymerization of 2 hours the pressure in the autoclave was releasad and the polymer suspension was filtered off with suction, the polymer was washed on the filter with 1 l of hot solvant (70 C) and dried under raduced prassure at 70 C.
At a polymerization tamperature above 60 C (cf. Table 2) the mixture was first polymarized for 10 minutes at 60 C whereupon the temperature was raised to the higher leval.
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E x a m p l e 13 Polymerization of propylens in liquid monomer A 16 l enamelled vessel provided with stirrer, ~acket heating and gas inl~t was flushed at room tRmperature with pure nitrogen and then with pro-pylens. A pressure of 0.5 kg/cm2 of hydrogen wa~ built up and through avalve a solution of 32 mmoles Al(C2H5)2Cl in 5 l of liquid propylene9 a suspension of the catalyst component A of Example 1 A (4 mmoles TiCl3~ and 1.6 ml of a 1-molar solution of cycloheptatriene-1J3,5 (component C) in hexane (1.6 mmoles) and finally 6 l of liquid propylene were added. The polymerization mixture was hsated to 70 C whereby the pressure rose to about 32 kg/cm2. The internal tsmperature was maintained at 70 C by cool-ing. The polymerization started after a few minutes. The experiment was intarrupted after 6 hours by releasing the pressure. After drying 5.R kg of a freely flowing polymer having an apparent density of 550 9/1 and an RS~ value of 2.i dl/g were obtained. Cy 16 hour extraction with heptane a soluble fraction of 2.8 % by weight was found. Tho ball indentation hard-nass of the polymer was 820 kg/cm (DIN 53 456), When the polymsrization was carried out under identical conditions but with a catalyst which did not contain component C9 the polypropylene con-tained a soluble fraction of 6.5 % (cf. Example 5).
E x a m_p 1 e 14 A) Preparation of catalyst A 1) Reduction of TiCl4 with aluminum ethyl sesquichloride A 10 liter vessel with stirrer was charged, with the exclusion of air and humidity~ with 1û90 ml of a hydrogenated, oxygen-free gasolina fraction (b.p. 140 - 165 C) and 550 ml titanium tetrachloride (S moles) and at O C
a solution of 1111.2 9 of aluminum sasquichloride (containing 4.5 moles aluminum diethyl monochloride) in 3334 9 o~ the ga~oline fraction were added dropwise while stirring t250 rev/min) over a period of B hours under .
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nitrogen A red-brown fine precipitate separated, The mixture was stirred for ~ hours at 0 C and for 12 hours at room temperature.
The suspension was heated for 4 hours to 90 C and for 6 hours to 110 C. After settling the precipitate was separated from ths mother liquor by decantation and washed five times, each time with 2,000 ml of ths gasoline fraction. The washed solid reaction product was suspsnded again in the gasoline fraction and the suspsnsion adjusted to a concentration of 2 moles TiC13/liter~ Ths content of trivalent titanium in the suspension was determined by titration with a Ce-IV solution.
A 2) Second thermal treatmsnt in ths presence of ~i-n-butyl ather In a 2 lit~r veSS8l with stirrer 500 ml of the 2-molar suspsnsion (corresponding to 1 mole TiC13) wsre heated to 80 C with the exclusion of air and humidity and undar nitrogen and at said temperature 161 ml di-n-butyl ethsr (0.95 mnle) wsre addsd dropwise while stirring within 30 minu-tes. The suspension was then maintained for 1 hour at 80 C. On adding the ether the mother liquor turned olive green~ Finally, the solid TiC13 containing reaction product was washed 5 times, sach tims with 500 ml of ths gasoline fraction.
A 3) After-treatmsnt with aluminum diethyl monochloride 1 mmole of the TiC13-containing react;on product A obtained according to A 1) and A 2) and 2 mmolss of aluminum diethyl monochloride were added, with the exclusion o~ air and humidity, to 100 ml of tha gasoline fraction and the mixturs was stirred for 1 hour at room temperatureO
~) Polymerization of propylene A 1 litsr glass autoclave was chargsd, with the exclusion of air and humidity, with 0.4 1 of a hydrogenated, oxygen-free gasoline fraction (o.p~
14û - 165 C~ and the hydrocarbon was saturated with propylene at 55 C~
2 mmoles aluminum disthyl monochloride (activator~ component 9) and 0.2 mole cycloheptatriene-1,3,5 (component C) and then the sfter-treated TiC13 sus-- 16 ~

: . ., . : . : :

: , ' : . ' . ' ,':
. : . . .

~7~77S HOE 74/F 0~1 K

pension obtained according to A 3) (1 mmolr?) were eddr~d. Hydrogen was introduced until a pressurs of 0.25 kg/cm2 had been reached and during the course of 5 minutes propylene was introduced to build up a total pr~ssurr3 of 6 kg/cm2. This pressure wag maintained during -the course of polymeri-zation by adding propylene. After a time of polymerization of 2 hours thr~pressura in the autoclave was released and the polymer suspension was fil-tered off with suction. The filter cake was washsd with 1 liter of hot solvent (70 C) and dried under reduced pressure at 70 C. 248 9 of poly-propylene insoluble in the dispersion medium were obtained. The apparent ( ~ 10 density of the freely flowing pulverulent polymer was 560 9/1J the RSV value was 2.6 dl/g and the ball indentation hardness 840 kg/cm tDIN SS 456)~ To determine the soluble fraction (atactic polymHr) formed ths polymerization mothr~r liquor and the wash solutions were combined and evaporated to dry-ness under raduced pressure. 1~4 9 of soluble polypropylene were found (0.57 ~, calrulated on total polymer).
E x a m p l e 15 A) After-treatment of the TiCl3-containing reaction product with AltC2H5)2Cl and cycloheptatriene-193~5 1 mmole (TiC13) of the reaction product prepared according to A 1j and A 2)~ 2 mmoles aluminum diethyl monochloride and 0.2 mmole cycloheptatriene-1,3~5 were added~ with the exclusion of air and humidity~ to 1ûO ml of the gasoline fraction and the mixture W3S stirred for 1 hour at room tempera~
ture.
B) Polymerization of propylene The polymerization was carried out under the conditions specified in Example 14 with the exception, however, that no further amount of cyclo-heptatriene-1,3,5 was added. 230 9 of polypropylena insoluble in the dis-persion medium and having an apparent density of 553 g/l, an RSV value of - 2.2 dl/g and a ball indentation hardnr33s of 850 kg/cm (DIN 53 456) were :. . , , - . : . ............. . ':. . ' '. : :
~:. . .................... .. . :

, -, , . . ~

HOL 74/F oa1 K
37~7~i obtained. The mother liquor contained 0.5 ~ of atactic polymer, calculated on thn total polymer~

A) Aftor-trsatment of ths TiCl3-containing reaction product with 5 Al(C2H5)2Cl and cyclooctatstraene-1,3,5,7 The aftsr-treatment was carried out as described in ExamplD 15 with the exception that cyclooctatetraene-1~3~5,7 was used instead of cyclo-heptatriene-1~3,5. With ths exclusion of air and humidity 1 mmole ~TiCl3) of ths oli~e green suspension of Example 14 A 2)9 0.2 mmole of cycloocta-tetraene-1,3,5,7 and 2 mmolss aluminum diethyl monochloride were added to 100 ml of the gasolins fraction and the mixture was stirred for 1 hour at room t~mperature.
C) Polymerization of propylene Propylene was polymerized under the conditions of Example 14. 252 9 of polypropylene insoluble in the dispersion medium and having an apparent density of 540 g/l~ an RSU value of 2,1 dl/g and a ball indentation hardneQs of 830 I<g/cm (DIN 53 456) were obtained. The fraction of soluble polypro-pylene amounted to 1.2 9 = 0.47 %~ calculatsd on the total polymsr.
E x a m p l e 17 The TiCl3-containing raaction product was prepared as described in Example 14 sub A 1) and A 2) and subjected to an after-treatment with alu-minum diethyl monochloride and cycloheptatriene-1,3,5 in the presence of an olefin as follows:
1ûO mmoles of the TiCl3 suspension A 2) were diluted to 0.1 mole TiCl3 per liter dispersion medium by adding about ~00 ml of the gasoline fraction and with the exclusion of air anô humidity~ 500 mmoles Al(C2H532Cl (62.92 ml) and 40 mmoles cycloheptatriene-1,3,5 (4.16 ml) were added and the mixture was stirred for 5 minutes at room temperature. At r~em temperature (with cooling) 300 mmoles (12.6 9) of gaseous propylcne (6,7 l) were then intro~

1EJ ' . ~.

. . . :
, .

~7~77S ~IOr 74/~ 081 K

duced over a period of 1 hour~ To avoid the formation of a vacuum tne llrn-pylene was dilu~ed with a small amount of argon. Subsequently, thn TiCI -containing suspension was stirred for 1 hour at room temperature and under argon. The content of trivalent titanium (as TiC13) was determined by titration with a Ce-IV solution.
A 1 liter glass autoclave was charged, with ths exclusion of air and humidity, with 0.5 1 of a hydrogenated, oxygen-free gasoline fraction (b.p.
140 - 165 C~ and the hydrocarbon was saturated with propylene at 70 C.
1 mmole of tha above suspension (10~9 ml) was added and hydrogen was intro-duced in an amount such that a pressurs of 0~25 kg/cm2 was reached. Over aperiod of 5 minutes propylene was then introducad until a total prassure of 6 kg/cm2 had built up. This preQsure was maintained during ths course of polymsrization by introducing propylene. Simultaneously, ths temperatura was increased to 80 C and maintained at said lsvel by cooling. After a polym~rization period of 2 hours the pressure in the autoclave was released and the polymerization mixture was worked up as described in Example 1 B).
230 9 of polypropylene insoluble in the dispersion medium were obtained in ths form of translucent grains. The RSU value was 2.2 dl/g~ ths apparent dsnsity 542 9/1 and the ball indentation hardness ~60 kg/cm2 (DIN 53 456).
In the mother liquor 5 grams of soluble atactic polypropylene were found, corresponding to 2.1 % by weight, calculated on the total polymer~ -E x a m e_~ e 18 Polymeri~ation of propylens in the liquid monomer A 16 1 snamelled vssssl provided with stirrer~ jackst heating and gas inlst was flushsd at room tsmperaturs with pure nitrogen and then with pro-pylsnn. A pressurs o~ 0 5 kg/cm2 was built up by introducing hydrogen and through a valva a solution of 20 mmoleQ Al(C2H5)2C1 in ~ 1 of liquid propy-lene wers addod. Th~n through nnoth~r valve 4 mmoles (as TiC1~) of the suspnnsion of compnnont A of ~xnmpln 17~ contain~ng 20 mmoles ~l(C2H5)2Cl, - '1 9 --.

~ 74~775 !IOE 7~/F 0~1 K

1.6 mmoles cycloheptatriene~ ,5 an~ a small amount of polypropyl~n~, diluted with fi l of liquid propylene were added. The polymerization mix-ture was heated to 70 C whereby ths pressure rose to 32 kg/cm ~ The in-ternal temperature was maintained at 70 C by cooling. Ths polymerization started after a few minutes. The experimsnt was interrupted after 3 hours by pressure release. After drying, 4 kg of a freely flowing polymer were obtained ha~ing an apparent density of 545 g/l. The polymer grains were translucznt, the RSV value was found to bs 1.9 dl/go ~y a 16 hour extrac-tion with hsptane a soluble fraction of 2.B % by weight was found. The product had a ball indentation hardnass of 780 kg/cm2 (DIN 53 456)o E x a m p l e 19 5 mmoles tTiCl3) of the reaction product according to Example 14, A 1) and A 2) were suspended, with the ex~lusion of air and humidity~ in 500 ml of the gasoline fraction and 10 mmoles alutninum diethyl monochloride and 1 mmole cycloheptatrisne-1,3,5 were added. ThH reaction mixture was then stirred for 1 hour at room temperature.
A 2 liter vessel with stirrer~ thermomater and gas inlet was charged with 1 l of the hydrogenatod, oxygen-fres gasoline fraction (b,p. 140 -165 C) and flushed with pure nitrogen. At a temperature of 50 C the sus-~0 psnsion described abovs was added and 200 9 of 2-methylpentene-1 were dropped in over a period of 3 hours. The polymerization temperature was maintained at 55 C. The polymerization set in after a few minutesO Th~
polymer separated in the form of a fine precipitate. When -the dropwise addition was terminated the mixture was stirred fcr anothsr 2 hours at 55 C.
Thereafter~ the po1ymerization was interrupted by adding 50 ml isapropanol, the mixture was stirred for 1 hour at 6n c~ extracted with warm water and filtered off with suction while still hotD After thorough washing with hot gasoline and acetone and drying under reduced pres~ure at 70 C~ 194 9 of colorless poly-4-methylpenten2-1 were obtained. Tho polymer had an apparent .. . . . .

.'~ ' ' ' .
, ' - ' ' . ' .
:. . : , .
., : .` .~ ' ' . ~ ', ~74~75 IICC 74/F 0~1 K

density of 515 g/l. The moth~r liquor containrd 0.6 ~ by weight of solubl~ polymEr.
E x a m p l e 2U
A) Preparation of catalyst A 1) Reduction of TiC14 by means of aluminum ethyl sesquichloride 1090 ml of a hydrogenated, oxygen-free gasoline frartion (b~p~ 140 -165 C) and 550 ml o~ titanium tetrachlorids (5 moles) were introduced in~o a 1û liter vessel with stirrer, air and humidity being excluded, and at û C a solution of 1111.~ 9 aluminum ethyl sesquichloride containing 4.5 moles aiuminum diethyl monochloride in 3334 9 of the gasoline fraction were added dropwise ouer a period of B hours while stirring (250 rev/min) under nitrogen. A red brown fine precipitate sHparated. The reaction mixture was stirred for 2 hours at 0 C and then for 12 hours at room temperature.
Thsn the suspension was heated for 4 hours at 90 C and for another 6 hours at 110 C. The separated precipitate was allowed to settle and tha supernatant mother liquor was removed by decantation. The solid reaction product was washsd five times, each time with 2noo ml of the gasoline frac-tion~ suspended in the gasoline fraction and the suspsnsion was adjusted to a concentration of 2 moles TiCl3/liter. The content of trivalent titanium in the suspension was dotermined by titration with a Ce-IV solution.
A 2) Second thsrmal treatment in the pro3ence of di_n_butyl ether and cyclohoptatriene-1,3,5 In a 2 liter vessel with stirrer 500 ml of the 2-molar suspension (corresponding to 1 mole TiC13) were heatsd to 80 C with the exclusion of air and humidity and under nitrogen and at said temperature 161 ml di-n-b~tyl ether (0.~5 mole) wero added dropwise while stirring over a period of 30 minutes, Thu suspension was maintained for 30 minutes at B0 C and at said temperature 75 mmoles cycloheptatriene-1,3,5 (7,8 ml) were added and the mixture was stirred for a further 4 hours at 80 C. Gn adding the .
'. ' ',;~ ' . ' ' . ~ ' : ' ' . . : ' ~ ' ' '' ': ~ "' ':
: ~
, ` ~7~775 HOE 74/F OB1 K

ether the mother liquor turned olive green. The solid TiCl3-containing reaction product was then washed five times, oach timE with 500 ml of the gasbline fraction.
A 3) After-treatment with aluminum diethyl monochloride 1 mmole (TiCl3) of the reaction product according to A 1) and A 2) and 2 mmoles of aluminum diethyl monochloride were added, with the exclusion of air and humidity, to 100 ml of thr~ gasoline fraction and the mixture was stirred for 1 hour at room tempsrature.
R) Polymerization of propylene ( 10 A 1 liter glass autoclave was charged, with the exclusion of air and humidity~ with 0.4 l of the hydrogenated,oxygen-free gasoline fraction (b.p.
140 - 165 C) and ths hydrocarbon was saturated with propylene at 55 C.
2 mmoles of aluminum disthyl monochloride (component ~, activator) and 0.2 mmols cyclohsptatrisne-1,3,5 (componsnt C) and then the after-treated TiCl3 suspehsion according to A 3) wsrs addsd. Hydrogsn was introduced until a prsssure of 0025 kg/cm2 had been rsachsd and then propylens was introduced within 5 minutes in ar amount to build up a total pr0ssure of 6 kg/cm .
This prassure was maintained during polymerization by adding propylene~
After a polymerization time of 2 hours~ the pressure in the autoclave was relsased~ the poly~er suspension was filtered off with suction, the filter cakr~ was washed with 1 l of hot solvent (70 C) and dried st 70 C under re-ducad pressure~ 228 9 of polypropylsne insoluble in the dispersion msdium were obtained. The frsely flowing pulverulsrlt polymer had an apparent den-sity of 545 g/l~ an RSV valur- of 2.1 dl/g and a ball indentation hardness of 850 kg/cm (DIN 53 456), To determine the soluble fraction formsd in the polymerization (atactic polypropylene) the mother liquor and the wash solu-tions wsrD com~inod and evaporatEri to dryness under reduced pressure. 1~2 9 of soluble polypropylene wr~re found~ corrsspondirlg to 0.52 %~ calculatad on the total polymsr.

.

.

. .

~74775 ~IOE 74/F 081 K

E x a m p l e 21 A) After-treatm~nt ~f the TiCl3-co~taining rsaction product with Al(C2H5)2Cl and cycloheptatriene-1,3,5 1 mmole (TiCl3) of the reaction product obtain~d according to Examplo S 20, A 1) and A 2), 2 mmoles aluminum diethyl monochloride and û.2 mmole cycloheptatri2ne-1~3~5 wera added, with the exclusion of air and humidity, to 100 ml of the gasolinR fraction and the mixture was stirred for 1 hour at room temperature.
a) Polymerization of propylene ( 1û The polymeri~ation was carried out under the conditions specified in Example 20, with the exception, however, that no cyclohept~triene-1,3,5 was added. 22fJ g of polypropylene insoluble in the dispersion medium were ob-tai.nud. The product had an apparent density of 543 g/l, an RSV value of 2 dl/g~ and a ball indentation hardness of 855 kg/cm (DIN 53 456). The mother liquor contained 0.55 ~ of atactic fractibn, calculated on the total polymer.
E x a m p 1 e 22 A) After-treatment of the TiCl3-containing reaction product with Al(C2H5)2Cl and cyclooctatetra~ne-1~3,5~7 2û Tha after-treatment was carried out as described in Exampie 21 with the use of cyclooctatetraene-1,3,5,7 instead of cycloheptatriene~1~3,5~
With tha exclusion of air and humidity 1 mmole (TiC13) of the olive gre~n suspension according to Example 20, A 2), 0.2 mmole cyclooctatetraene 1,3,5,7 and 2 mmole aluminum diethyl monochloride were added to 100 ml of 25 tha gasoline fraction and the mixture was stirred for 1 hour at room tem-paratureO
. f~) Polymarizatiun of propylena Propylana was polymerlzed under tha condltions of Exampla 20~ but with~
out the addition of oycloheptatriena-1,3~5 (compon~nt C). 2~0 9 of polypro- :

. -- - ' - . . : ' ' ~

,- :

- . :
.. - : ~ -:
. . ::: . ... . ..

~74775 ~OE 74/F 0~1 K

pylene insoluble in the dispersion medium were obtained having an apparent density of 538 g/l, an RSV value of 1.1 dl/g ar,cl a ball indentation hard~s of 84û kg/cm2 (DIN 53 456). The proportion of solubls polypropylene amount-ed to 1.5 9 = 0.57 ~0, calculated on ths total polymer.
E x a m p l B 23 The TiCl3-containing reaction product was prepared as described in Ex-ampls 20~ A 1) and A 2), The aftsr-treatment with aluminum diethyl mono-chloride and cycloheptatriene-1,3,5 was carried out in the presence of an olsfin as follows 100 mmoles of the TiC13 suspension were dilutsd to about ( 1û 0.1 mole TiCl3 psr liter by adding about 800 ml of the gasoline fraction and, with ths exclusion of air and humidity; 500 mmoles Al(C2H5)2Cl (62.92 ml) and 4û mmoles cycloheptatriens-1~3,5 (4.16 ml) were added and the mixturs was stirred for 5 minutes at room tampsrature. Then, 300 mmoles (12.6 9 gas~ous propylene ~6.7 l) were introduced at room tempsratura (cooling) over a psriod of 1 hour. To avoid the formation of a vacuum the propylens was diluted with a small amount of argon. The catalyst suspension was then stirrsd for 1 hour at room temperature and under argon. The content of tri-valent titsnium was dstermined by titration with a Ce-IV solution.
A 1 litsr glass autoclavs was chargsd, with the exclusion of air and 2û humidity, with 0.5 l of a hydrogenated, oxygen frse gasoline fraction (b.p~
140 - 165 C) and the hydrocarbon was saturated with propylsns at 7û C.
1 mmole o~ the above suspension (10.9 ml) wa~ addsd, hydrogsn was introduced until a pressurs of 0.25 kg/cm2 had been reached and thæn within 5 minutes propylens was introduced in such an amount that a total pressura of 6 kg/cm was built up. This pressure was maintainad during ths coursa of the polyms rization by introducing propylene~ Simultaneou~ly, the temperature was raisad to SO C and maintained at snid lavèl by conling. Aftsr a time nf polymsrization of 2 hours tha pressure in the autoclave was rsleassd. Ths polymerization mixtura was further processed as daqcribed in Example 1 3).

_ 24 ' ~: ~ . . - ., ~7~7~5 HOE 74/F 0~1 K

225 9 of polypropylene insoluble in the disperslon medium wers obtained in the form of translucent grains having an RSV value of 2.5 dl/g, an apparent density of 548 g/l and a ball indentation hardness oF 830 kg/cm t~IN 53 456).
The mother liquor contained 4.5 9 of soluble atactic polypropyl~ns, corre-S sponding to 1096 % by weight, calculated on the total polymer.
E x a m_p 1 e 24 Polymerization of propylene in the liquid monomsr A 16 liter snamelled vessel provided with stirrer, jacket heating and gas inlat was flushed at room temperature with pure nitrogen and then with propylene. 8y th~ introduction of hydrogen a pressure of 0.5 kg/cm waQ
built up snd through a val~s a solution of 20 mmoles Al~C2H5)2Cl in 6 litr3rs of liquid propylena and through another valve thereafter 4 mmole3 ~as TiCl3) of the suspension according to Example 23 (component A~ containing 20 mmoles Al(C2H5)2Cl, 1.6 mmolss cycloheptatriene-1,3,5 and a small amount of polypro-pylane dilutsd with 6 l of liquid propylene wsrs added. The polymerization mixturs was heatsd to 70 C whsr~by the pressurs rose tn 32 kg/cm . The in-ternal tsmperature was maintained at 70 C by cooling, Polymerization ~tart~
ed after a few minutes and was intsrrupted sfter 3 hours by relea3ing the pressure of thæ autoclave~ After drying, 3.8 kg of a frsely flowing polyrner were obtainr~d having an apparent density of 545 g/l. The polymer grain waR
translurent~ The RSU valus was 2~2 dl/g. 3y a 16 hour extrac~ion with hap~
tane a solubls ~raction of 3 % by weight was found. Ths ball indentation hardness was found to be 760 kg/cm (DIN 53 456).
E x a m p l e 25 With the cxclusion o~ air and humidity, 5 mmoles (TiCl3) of the reaction product according to Example 20~ A 1) and A 2) were suspsndsd in 50û ml of the gasolins fraction and then 10 mmoies aluminum diethyl monochloride and 1 mmols cycloheptatriene-1,3,5 wers added and the mixture wa~ ~tirred for 1 hour at room tempsraturs _ 25 -- . : . . .:

- . : , : : - :

1~374775 llnE 74/F oe1 ~

A 2 lit~r vessel provide~ with stirrer, thermn~eter and gas inlet was charged with 1 liter of a hydrogenated, oxygen-free gasoline rraction (b.p.
140 - 165 C) and the vessel was flushed with pure nitrogen, At a tsmpera-ture of 50 C the above suspsnsion of component A was added and 200 9 of 4-methylpentene-1 were added dropwise over a period of 3 hours. The pnly-merizfltion start~d aftsr a fsw minutes, The polymerization te~perature was maintainad at 55 C, The polymer separated in the form of a fine precipi-tate. When the dropwise addition was terminated~ the mixturs was stirred ror another 2 hours at 55 C, whereupon the polymerization was interrupted by adding 5û ml isopropanol, the mixture was stirred for 1 hour at 60 C~
oxtractsd with water and filtsred off with suction while still hot. AT ter thoroùgh washing with hot sol~ent (gasoline) and acetone and drying at 70 C
und~r reduced pressure~ 190 9 of colorless poly-4-msthylpentene-1 were ob-tained, The polymer had an apparent dsnsity of 505 g/l. The mother liquor contained 0.7 ~ by weight of soluble fraction.

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Claims (16)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A process for the preparation of a catalyst in which (1) an aluminum-organic compound selected from the group of aluminum dialkyl chlorides and aluminum alkyl sesquichlorides is reacted with titanium tetrachloride in an inert hydrocarbon solvent at a temperature of from -20 to +20°C in a molar proportion of aluminum dialkyl chloride to titanium tetrachloride of from 0.8:1 to 1.5:1, (2) the resultant titanium trichloride-containing reaction product is subjected to a thermal treatment at a temperature of from 40 to 150°C, (3) the product is sub-jected to a further thermal treatment in the presence of a dialkyl ether, (4) the reaction product is separated and (5) the separated product is activated by being mixed with an aluminum dialkyl halide.

2. A process as claimed in claim 1 in which in step (5) the product is also mixed with a cyclopolyene.

3. A process as claimed in claim 1 in which in step (1) the aluminum organic compound is an aluminum dialkyl chloride having alkyl groups of 1 to 6 carbon atoms.

4. A process as claimed in claim 1, claim 2 of claim 3 in which in step (3) a cyclopolyene is also present.

5. A process as claimed in claim 1, claim 2 or claim 3 in which prior to step (5) the reaction product is treated with an aluminum alkyl halide.

6. A process as claimed in claim 1, claim 2 or claim 3 in which prior to step (5) the reaction product is treated with an aluminum alkyl halide in the presence of a small amount of at least one member of the group of cyclopolyenes and olefins.

7. A process as claimed in claim 1, claim 2 or claim 3 in which in step (2) the product in the form of a suspension in an inert solvent is subjected to a thermal treatment at a temperature of from 90 to 110°C.

8. A process as claimed in claim 1, claim 2 or claim 3 in which in step (3) the resultant product is subjected to thermal treatment at a temperature of from 60 to 90°C in the presence of a dialkyl ether having from 2 to 5 carbon atoms in each alkyl group.

9. A process as claimed in claim 1, claim 2 or claim 3 in which prior to step (5) the reaction product is treated with an aluminum alkyl halide selected from the group of aluminum alkyl halides of the formula AlRnX3-n wherein R represents an alkyl radical having 2 to 8 carbon atoms, X represents a halogen atom and n is a number in the range of from 1 to 2.

10. A process as claimed in claim 1, claim 2 of claim 3 in which prior to step (5) the reaction product is treated with an aluminum alkyl halide selected from the group of aluminum dialkyl halides and aluminum alkyl sesquihalides and the product is also mixed with at least one member of the group of cyclo-polyenes selected from the group of norcaradiene, cyclopolyene shaving 7 ring members and 3 non-cumulated double bonds in the ring, and cyclopolyenes having 8 ring members and 3 or 4 non-cumulated double bonds in the ring, and the alkyl and alkoxy-substituted derivatives thereof; and olefins selected from the group of mono-olefins having 2 to 10 carbon atoms.

11. A catalyst for the polymerization of olefins, whenever obtained according to a process as claimed in claim 1, claim 2 or claim 3.

12. A process for the preparation of a homo-polymer of an .alpha.-olefin of the formula CH2=CHR wherein R is an alkyl radical having from 1 to 8 carbon atoms, a copolymer of said .alpha.-olefins with one another and copolymers of said .alpha.-olefins with ethylene, in which the olefins are subjected to polymerization at a temp-erature of from 20 to 120°C and at a pressure of from 1 to 50 kg/cm in the presence of a catalyst prepared by a process in which (1) an aluminum-organic compound selected from the group of aluminum dialkyl chlorides and aluminum alkyl sesquichlorides is reacted with titanium tetrachloride in an inert hydrocarbon solvent at a temperature of from -20 to +20°C in a molar proportion of aluminum dialkyl chloride to titanium tetrachloride of from 0.8:1 to 1.5:1, (2) the resultant titanium trichloride-containing reaction product is subjected to a thermal treatment at a temperature of from 40 to 150°C, (3) the product is subjected to a further thermal treatment in the presence of a dialkyl ether, (4) the reaction product is separated and (5) the separated product is activated by being mixed with an aluminum dialkyl halide.

13. A process as claimed in claim 12 in which in step (5) of the preparation of the catalyst the product is also mixed with a cyclopolyene.

14. A process as claimed in claim 12 in which in step (1) of the preparation of the catalyst the aluminum organic com-pound is an aluminum dialkyl chloride having alkyl groups of 1 to 6 carbon atoms or an aluminum alkyl sesquichloride.

15. A process as claimed in claim 12, claim 13 or claim 14 in which the .alpha.-olefin is propylene.

16. A process as claimed in claim 12, claim 13 or claim 14 in which the monomer is a mixture of propylene with 0.5 to 25% ethylene.