CA1118748A - Titanium and vanadium trichloride catalysts for polymerization of olephins - Google Patents
Titanium and vanadium trichloride catalysts for polymerization of olephinsInfo
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Abstract
METHOD FOR THE POLYMERIZATION OF OLEPHINES AND MEANS
ADAPTED THERETO
ABSTRACT OF THE DISCLOSURE . -A novel catalyst system for the polymerization or copolymerization as the case may be, of alpha-olephines is disclosed, which comprises a cocatalyst which is an aluminum-organic compound and a catalyst proper which is obtained by reacting metal vapors (such as vapors of Mg, Al, Ti, V, Cr, Mn, Fe or their alloys) with Ti or V compounds, a halogen donor and a hydrocarbonaceous inert diluent being possibly present. Another aspect of the invention is the conduct of the polymerization, or copolymerization, run proper. Numerous examples of practical application of the catalyst preparation and use are given and the advantages of the novel approach shown.
ADAPTED THERETO
ABSTRACT OF THE DISCLOSURE . -A novel catalyst system for the polymerization or copolymerization as the case may be, of alpha-olephines is disclosed, which comprises a cocatalyst which is an aluminum-organic compound and a catalyst proper which is obtained by reacting metal vapors (such as vapors of Mg, Al, Ti, V, Cr, Mn, Fe or their alloys) with Ti or V compounds, a halogen donor and a hydrocarbonaceous inert diluent being possibly present. Another aspect of the invention is the conduct of the polymerization, or copolymerization, run proper. Numerous examples of practical application of the catalyst preparation and use are given and the advantages of the novel approach shown.
Description
This invention rela-tes to a novel catalytic composition based on transition metals and adapted to the polymeriza-tion of mono- and diolephines, as well as to the method o its preparation.
A second object of the present invention is the application of said catalytic composition to the polymerization and copo-lymerization of ethylene with higher alpha olephines, with high yields of polymer relative to the employed transition metalO
Such a catalytic composition is composed by an organic-metal-lic compound of aluminum (co-ca-talyst) and by a second compound ~catalyst) as obtained by reaction of vapors o- metals, to be specified hereinafter, with compounds of titanium or vanadium possibly in the presence of a halogenated compound and of an inert hydrocarbonaceous diluent.
In order to simplify the -oregoing, and without any limita-tion :
1 The organic-me-tallic compound of aluminum has the general formula Al R X3 4~ wherein R is an alkyl~ an aryl or a hydrogen atom, X is a halogen, and _ is an integer from 1 to 3.
A second object of the present invention is the application of said catalytic composition to the polymerization and copo-lymerization of ethylene with higher alpha olephines, with high yields of polymer relative to the employed transition metalO
Such a catalytic composition is composed by an organic-metal-lic compound of aluminum (co-ca-talyst) and by a second compound ~catalyst) as obtained by reaction of vapors o- metals, to be specified hereinafter, with compounds of titanium or vanadium possibly in the presence of a halogenated compound and of an inert hydrocarbonaceous diluent.
In order to simplify the -oregoing, and without any limita-tion :
1 The organic-me-tallic compound of aluminum has the general formula Al R X3 4~ wherein R is an alkyl~ an aryl or a hydrogen atom, X is a halogen, and _ is an integer from 1 to 3.
2 The metal vapor, as obtained by heating the metal concerned in a high vacuum~ is preferably selected from among Mg~ Al~
Ti, V3 Cr, ~In, Fe or their alloys.
Ti, V3 Cr, ~In, Fe or their alloys.
3 The compounds of Ti, or of V, are composed by inorganic or organic salts, complexes or compounds of the above listed metals, in which -the metal has a valency higher -than 3,
4 The halogenated compound can be either organic or inorganic, provided -that it is capable of yielding halogen (mobile halogen) to the metal indicated a-t 2) above or to -the Ti- or V-compound indica-ted a-t 3) above under the working conditions which are used~
5 The inert carbonaceous diluen-t is composed by aliphatic~ aroma-~.
tic or mixed compounds, provided tha-t they are liquid under the adopted working conditions.
Under the adopted operative conditions the metal as at ~) above is vapori~ed, preferably in a vacuo~ by an appropriate heating system (with electric resistors, electron beams, by in~
duc-tion and also by using high frequencies, by laser beams, by electric sparks, by voltaic arc and so forth). The vapors emer-ging from the metal surface are quenched in a liquid which con-tains the compounds indica-ted at 3) possibly in union with the compounds at 4) and 5) above.
Such a liquid must be cooled a-t a temperature which is low enough as to limit it evaporation 30 as co~sequently to permit the maintenance o~ the degree o~ vacuum which is required for the va-porization of the me-tal at temperatures which can be attained by the as adopted heating systemO Such a catalyst composition is capable of polymerizing and copolymerizing with very good yields ethylene and higher alpha olephines to high-density polyethylene, and to isotactic polypropylene, respectively, and is likewise capable of polymerizing butadiene to 1~-trans- polybutadiene~
and isoprene to 1,4-cis-polyisoprene.
~s regards ethylene, and this is a second object of the present invention, a few of the catalyst compositions in question are capable of displaying an exceptional activity in polymeriza-tion runs. ~ore particularly~ when the catalyst is prepared from ~Ig vapors, the compound as per i-tem 3) above is based on Ti, and the halogenated compound as per 4) above is present~ it has been su~risingly fountl that extremely high yields can be obtained when working w];th an atomic ratio of Mg to Ti equal to or higher than 4 and with an atomic ratio of X to ~Ig equal to~ or higher -than 2~ whereiIl X is -the mobile halogen as defined at 4) above.
The above specified catalyst affords substantial advantages over other ca-talysts adapted to the polymerization of ethylene~
~LI 3748 in high yields and of ethylene with other higher alpha-ole-phines, More detailedly; the act;ivity (in terms of kilograms of polymer per gram of Titanium as produced in one hour with an atmosphere of ethylene under the conditions set forth in the examples) is extremely high, in t;he order of magnitude of 230 kilograms; the synthesis of the catalyst resorts to raw mate-rials which are particularly simple and which can be standard-ized (differently from many supports as employed in other catalyst compositions which can be difficult to characterize from a phisico-chemical standpoint) and thus gives rise to catalysts ha~ing an activity which is both homogeneous and reproducible-.
The preparation technology of the catalyst is both simple and quick.; the catalyst can be employed such as it has been pre-pared, in union with the cocatalyst, in the slurry polymerization of ethylene without any subsequent separations~ filtrations or elutions. ~ore partlcularly, all the transition metal put to react is converted into an active catalyst ; the catalyst .can be employed, after having been dispersed on an inert support, which latter can even be the polyolefin as such, in::the polymerization ~0 of ethylene in the gaseous state and thus without any hydrocarbo-naceous dispersant being present; the adjustment of the molecular weight with hydrogen on a wide molecular weight range (MFI 0.1 to ~IFI 15~ does not involve yield losses of polymer with respect to the transition metal.
~lore detailedly, an object of the present invention is a catalyst system having the above indicated composition which per-mits to overcome the above enumerated drawbacks and which, in use, affords -the following advantages :
- obtention of high yields of polymer relative to the transition metal;
- a morphologically homogeneous polymer;
- an easy adjustment of the molecular weight of the polymer ;
87~3 - use in th~ polymeri~ation in ~a6eous phaæe wlSh t}le ob-ten-tion oE hi~h yields.
As outlined above 3 such a c~talyst sy3-tem compr.ise~ an organic metallic compound of aluminum and a composition as obtained by reaction betwecn vapors of metallic ma~nesium~
the -titanlum compound a halo~en-donor~ selected -~rom amon~
the halogenatcd organic and inorganic compounds~ It ls known~
inter alia, that ti-tanium -trichlorlde~ ~an be prepared by re-duction of TiC14 with the followin~ procedures :
a) with hydrogen under drastic cQnditions (SOOC-700C), ~he products obtalned, due to the hi~h temperature whlch ha~ been usecl~ are poorly ac-tive in the polymerization oP olephines.
b) with metals such as aluminum~ antimony~ and others~ at temperatures equal to or hi~her than 200C. In thls cas~ not all o~ the metals are ~uitable in that ~er mAr~y o-E them the reaction take~ place i.n a llmited manner only or lt does not ~o on at all. It ls correct that ~uch a depuot can be obviated by u~in~ polar solvents, ~uch a~ ~MF, THF~ dlmothoxyheptane7 but in 3uch a case -the final titRnium triohloride is complexed wi~h ~0 the polar ~olvent and exhibits no lnterest ~rom a cataly~ ta~d-point. Also the u~e oP a liquid amal~am oan prevent thi~ draw~
back (U.S.PatO 3 658 723 to DOW CH~M~) bu~ all tho m~tal~ hav~
a very limited solubility in meroury so that such a prooadure r~qulres a large use o~ this metal which can be dl~iculty ~0pa-rated ~rom the titanlum trichloride. These products~ however~ are not much active ln polymerization, o) with metal-alkyls, a method which permits to use moderate temperatures~ but whlch uses comparatively expensive materials~
which also are extremely reactive and hazardous. With thi~
method it is not pos~ible to use tran~itlon metals the alkyl~ nP
which have no suE~icient stabllity to be prac-tically used~
d) with carbonyls of low~valency transition metRls~ as de~cri-~ ~ ~8~8 bed in the Canadian Patent Application No. 224799 of 16.4.1975.
There is the advantage oE obtaining the reduction with metals which would not react as such, but this method is limited to the transition metals and, among these, only to those which give stable carbonyls. The as-obtained titanium chlorides display a fair catalyst activity in the polymerization of unsaturated hydrocarbons, either alone or in admixtures.
An important object of the present inven-tion is thus also a method which permits to obtain titanium trichlorides without suffering from any of the shortcomings indicated above.
Such a method consists in providing soluble atoms of a metal by a procedure of vaporization in a vacuum, e.g. a high vacuum and condensation in an MC14 (M being either Ti or V), either pure or diluted in inert solvents, these latter being kept at a low temperature.
The principal advantage of such a procedure is that it can be applied generally, that is to say that any metal can be used, either a transition metal or another metal.
In addition, there is the advantage of obtaining products which have had a controlled thermal hystory and thus have differentiated physical properties, and consequently different catalytic activities, many metals being controllably and simul-taneous co-vaporizable.
The products thus obtained, which are yet a further object of the present invention, c~an found their use as catalysts for the polymerization and copolymerization of olpehines using the aluminum-alkyls as cocatalysts.
Thus, according to the presen-t invention, there is, in particular, provided a method for the preparation of a catalyst containing titanium trichloride or vanadium trichloride and useful in the polymerization and copolymerization of ethylene with higher alphaolefines, which comprises vaporizing another Ç3 ~i!37~8 metal selected from the group consisting of Al, Mg, Cr, Mn, Fe, V and Ti under vacuum and reacting the vapor thus obtained with TiC14 or VC14 at a low temperature.
The vaporization can be carried out in a very high vacuum, preferably between 10 3 Torr and 10 6 Torr a-t temperatures which vary according to the metal which is used, usually from 800C
to 2500C, as disclosed by P.L. Timms, Angew. Chem., 14, 273 ~1975).
The metal vapors can be reacted with an MC14 at a temperature in the range from -80C to +20C, preferably between -60C and --20C .
The reaction can take place with MC14, either pure or dilu-ted with inert solvents selected from among aliphatic or aromatic, saturated or unsaturated hydrocarbons and the halogenated hydro-carbons, such as chlorohexane and fluorobenzene.
The choice of the solvent or the solvent mixture is govern-ed by the conditions of use (temperatures of solidification and vaporization under the pressure which has been adop-ted).
It has been found, moreover, that, if in the above mentioned preparation, a high ratio of Mg to Ti is adopted and the reaction is carried out in the presence of a halogen donor, it becomes possible to obtain a composition which, together with an organic metallic compound of aluminum, provides outstandingly good results in the high-yield polymerization of alpha-olephines, particularly of ethylene, as such or in admixture with one or more of its higher homologs.
More particularly, such a composition is obtained by vaporizing magnesium or an alloy thereof, then condensing it in an inert diluent: which contains the titanium compound and the halogen-donor.
The vaporization of magnesium is preferably carried ou-t in a vacuo, from 10 Torr to 10 Torr, at a variable temperature, :;~
37~8 consistently with the pressure used, of from 500C to 1200C.
The metallic vapors are condensed within a colution, kept stirred, of the -titanium compound and the halogen-donor, at a temperature higher than -the freezing point and lower -than the boiling - 7a -, ~ ~J
8~413 point of the solution.
As outlined above, resul-ts useful to -the ends of a high-yield polymerization of alpha-olephines are obtained if a high ratio o-f ~Ig to Ti is adopted~ especially if such a ratio is equal -to, or higher -than, 4. Concurrently, the presence is ne-cessary of a halogen-donor, select;ed from among the organic or inorganic halogenated compounds~ which is employed in an e~cess over the magnesium; it is preferred -to use ra-tios of the haloge-nated compound -to the magnesium equal to, or higher than, 2.
The condensation of the magnesium vapors is carried out in an inert diluent~ selected from among the aliphatic, or the aromatic hydrocarbons.
In its turn, the titanium compound is selected from among the compounds of tetravalent titani~l (trivalent or met.allic-organic), preferably soluble in -the selected diluent, whereas the halogenated compound~ as outlined above~ can be selected from among the organic or inorganic hali~es; a special emphasis can be pu-t on the alkyl and aryl halides. At the end of the reaction~
a very fine slurry is obtained, which can be used as such in poly-merization.
The polymerization reaction, as outlined above, is carriedout in the presence of a catalyst system composed by the suspension as obtained beforehand, in union with an organic metallic compound of aluminum, in a hydrocarbonaceous solvent, which can be the same as that employed in the above described preparationO
The working temperatures vary -~rom 20C to 200C, preferably between 50C and 200C~ under pressures which are comprised bet-ween 1 and 20 at:mospheres. As an alternative~ when it is desired to carry out the polymerization reaction in the gaseous state~ it is enough -to scatter the catalyst within a low-boiling solven-t~ so that the lat-ter can easily be withdrawnO The catalys-t, in such a case, can also be dispersed on an inert solid support, and the 8.
E374~3 latter can be composed even by the polyol~phine itself~ The conditions which can be adopted for the polymerization in the ~aseous phase provicLe a temperature range ~lhich is maintained below the melting point of the olephine and in the par-ticular case of the polymerization of e-thylene, the -temperature range which ~s preferred i3 between 40C and 90~C Pressures are pre-ferably selected between 1 and 40 atmospheres. Hydrogen can be emplcyed as a regulator of the molecular weight.
E~IPLE
Preparation of the mi~ture 3 TiC13 1 AlC13 . A rotary flask is used, at the center of which a tungsten filament is arranged, ~hich is connected to a source of electric powerO Under the flask~ a cooling bath is horizontally positioned~ In the top portion of the apparatus there are a nitrogen and a vacuum -it-ting, ~ithin the spirally wound tungsten filament there are placed loO milligrams of pure aluminum in flakesD The flask is charged under nitrogen with 250 mls of anhydrous decane, containing TiC14 equal to 30% of the solvent. The rotary flask is cooled with the -40C bath, then vacuum is applied with a diffusion pump until reaching 10-4 Torr. Once these conditions have been attained, the filament is heated until the metal is vaporized~ The vaporized metal immediately reacts with TiC14, giv1ng a very fine dark-brown precipitate. On completion of the VapOrizatiOn~ the flask is pressurized again and brought to ambient -temperature by feeding ni-trogeng then the suspension is brought -to 150C during three hours. Upon filtra-tion and drying, the as-obtained violet product is analyzed For Alcl3-3 TiC13Ti % Al% Cl%
Calcd. 24.12 4.52 71036 Found 24O01 4.90 69O80 E~A~IPLE 2 The same appara-tus and procedure of E~cample 1 are used. There 4i5 are charEed l~0 milli~rams of metallic pure ~Ig in wire form and 250 mls octane, containing 2% o TiCl~ IJpon cooling at -600C and a-ttaining a vacuum of 10 4 Torr, the vaporization o-~the metal is starteda and it takes five minutes. The forma-tion is experienced o-~ a fine brown-violet precipita-te. The flask is restored to ambien-t pressure and tempera-ture. A sample is broug.ht to 125C during 4 hours, whereafter the slurry is filt-ered and the violet precipitate is washed with n-heptane until completely discharging the TiCl~, then the solid product is ana-lyzed after having dried it in a vacuo (2 grams):
For MgC12 2 TiCl3 ~i~ Mg% Cl%
Calcd 23076 5-94 70028 Found 22.97 5-~ 67.1 The two samples~ the untreated one ancl the treated one, have~
as seen through ~-ray analysis, a gamma structure.
E~ lPLE 3 The same apparatus and the same procedure as in Example 2 arc used~ adopting a concentration of TiC14 in n-octane of 14%.
A brown-violet product is obtained~ which is filtered~ washed with n-heptane until TiC14 is discharged~ then re-slurried in n-heptane and analyzed. The analysis gives MglTil 84C14.
E~lPLE 4 The same apparatus and -the same procedure as disclosed for Example 1 are used9 There are charged 00240 grams of metallic magnesium in wire form and 300 mls of n-octane containing 0~07%
of TiC14 and 12% o-f n-chlorohexaneO Upon cooling at -60C~ a vacuum of 10 4 Torr is made and magnesium is vaporized during 7 minutes. A solid, pale-brown product is formed~ which is collect-ed on a fil-ter~ washed with n-heptane and kept at 100C in such a solvent during two hours. The analysis shows the following molar composi-tion : l~lg3 lTil C17 8 10 .
~' ~L3L18~
E ~\MPLE 5 The same apparatus ancl procedure as clescribed in Example 1 are usedr There are char~ed O.180 grams o-f metallic Mn in flakes and ?50 mls o octane containing 2% of TiC14. Upon cooling at -60C, a vas::uum of 10 ~ Torr is at-tained ancl the vaporization of the me-tal is started3 which is completed within 3 minutes. The orma-tion is experienced a brown-violet precipitate. The flask is brought back -to ambien-t -temperature and pressure, then the suspen-sion is iltered~ washed with n-hexane until discharging the TiC14 completely, whereafter the product is dried in a vacuo and analyzed.
The analysis gives:
For 2 TiCl30~InCl 2Ti% C17o~ Mn~
Calcd. 22~0 65030 12063 Found 22~0 6304 14.4 EX~lPLE 6 The same apparatus and procedure as disclosed in Example 1 are used~ There are charged 0. 25 grams o metallic Fe in shavings and 250 mls of anhydrou;~ n-octane containing -the 5% of TiC14 .
Upon cooling at -50C~ a vacuum of 10 Torr is reached and the vaporization of the metal is started, that which takes 5 minutes.
The formation is experienced of a solid red-brown product which is collected on a filter~ washed with anhydrous hexane and dried under vacuumO There are obtained 1~ 87 grams o a product which has the following analysis:
2 3 Ti~ Fe~ Cl~
Calcld 21099 12n81 65.19 Found 21~73 12~70 66~90 E ~YAMPLE 7 The same apparatus and procedure as disclosecl in Example 1 are used There are charged 0~120 grams of Mg wire and 250 mls of n-octane containing 3 mls of VCl~. Upon cooling a-t -60"C, a vacuum of 10-3 Torr is reached and the vaporiza-tion of the metal is s-tartedg -that which -takes 5 minutes The formation is experienced of a solid dark-brown productg which is washed with n~heptane -to remove the e~c:ess VC14 and reslurried in n-heptaneO The analysis gives MglV2 ~C13 80 E~IPLE 8 The same apparatus and procedure as disclosed in E~ample 1 are used. There are charged 1 gram of metallic chromium in lumps and 250 mls~ of n-heptane~ containing 10 mls of TiC14~
Upon cooling at -80C, a vacuum of about 10-4 Torr is reached and the vaporization of the metal is starte~, which takes 20 minutes to be completedO The formation is experienced of a solid greenish product, which is collected on a filter and washed with heptane to remove the excess of TiC14 and reslurried in heptane The analysis gives :
For CrCl303TiCl3 Ti% Cr% Cl%
Calcd 23.19 8.37 68.44 Found 23.40 8.20 67.60 E~SPLE 9 A 5-liter autoclave is charged with 2 liters of anhydrous n-heptane~ containing the catalyst as prepared according to Example 3 in the concentration of 0.03 milligramatoms of Titan.ium and 4 milligramatoms of Al(iso_Bu~30 The mixture is brought to 850C, then there are charged 5 kilograms per sq. centimeter of hydrogen and as much of e-thylene~ Polymerization is carried out during four hours, while maintaining the total pressure constan-t by addition of e-thylene On completion of the polymerization~ the slurry is centri.fuged and the polymer is dried in a vacuo at 50C
during four hours, -then weighed.
There are obtained 400 grams of a white polymer, equivalent ~1~874~3 to a specific ~vielcl of 6,440 grams of polymer per gram of Ti per hour and per atmosphere of C~ ,having an MFI = 0 60.
E~IPLE lO
The procedure is the same as in Example 9, using as the catalyst the sample described in E~Yample 1,in the concentration of o~o6 milligramatoms per liter of titanium and as co-catalyst Al(iso Bu)3 in the concentration of 4 milligramatoms per liter.
There are charged 5 kilograms per sqOcentimeter of hydrogen and 5 kilograms per sq.centimeter of ethylene;the polymerization is car-ried out under a constant pressure by feeding-in ethylene during four hours and there are obtained 120 grams of a white polymer, ~hich corresponds to a specific yield of 1,030 grams of polymer per gram of Ti per hour and per atmosphere of C-2, having an MFI2 16 =
1,5 (~IFI21 6/P~FI2.16 = 49-4)-E~IPLE llA 2-liter autoclave is charged with 1 liter of anhydrous and deaera-ted n-hexane, containing 2008 milligrams of a catalyst according to Example 6,equal to 0.0941 milligramatoms of titanium and 4 milligram-atoms of Al~iso Bu)3~per liter. 20 kg sq~cm of hydrogen and 20 kg/sq.
cm of ethylene are charged. The temperature is raised to 85C and the pressure is maintained constant by continuously feeding-in ethy-lene. After 2 hours of polymeriza-tion,the reaction is cooled~ the autoclave is vented and the polymer is centrifuged,dried under vacuum at 50C and weighed. There are obtained 320 grams of a poly-mer having MFI2 16 = 0-12 (~FI21.6/MFI2-16 44 7) grams per gram of Ti per hour and per atmosphere of C-2 .
EXA~IPLE 12 .
The procedure is -the same as in Example 9, using as the cata-lyst the product described in Example 5, in the concentration of 0.10 milligramatoms per liter of ti-tanium. As cocatalyst there is used Al(iso Bu)3 in the concentration of 4 milligramatoms per liter.
Polymeri~ation iS carried ou-t during 3 hours with 5 kilograms/sq.cm 13.
374~3 o hydrogen and 5 kgs/scOcm of e-thylene. There are obtained 390 grams of a polymer having an MFI2 16= ~35 and an MFI21 6/MFI2 16=
= 350 Yield 2,700 grams per gram of Ti per hour and per abmosphere f C-2 .
EI~PLE 13 The procedure is the same as or Example 9 using as the catalyst the sample as described in Example 8 in the concentra-tion of 0.026 milligramatoms per liter of -titanium and 2 milligram-atoms per liter o Al(iso Bu)30 There are charged 5 kilograms/
sq.cm of hydrogen and 5.5 kilograms/sqOcm of ethylene. The tempe-rature is raised to 85C and the pressure is main-tained cons-tan-t by feeding-in ethylene continuously After two hours of polymeri-zation, the reaction is cooled, the autoclave is vented and the polymer is collected on a filter and dried in a vacuo at 50C and weighed. There are obtained 108 grams of a polymer having an ~IFI = 0.11 corresponding to a yield of 3,900 grams of polymer per gram of Ti per hour and per atmosphere of ethyleneO
T~BLE 1 tabulates the specific activi~ties as obtained in the pol~merization of ethylene with the samples of TiC13 as prepared according to the Examples from 1 to 8 inclusive~
T A B L E
Catalyst Example Specific activity MFI2Dl MFI21 cat.polymO grjpolym /gr.Ti/ min~a. 2,1 3 TiC13.AlC13 1 10 1~030 0062 49 2 ~iC130~1gC12 3 9 6,440 ~).60 36 2 TiC13.MnC12 l5 12 2,700 0.35 35 2 TiC13.FeC12 6 11 1,750 0012 35 3 TiC13.CrC13 3 13 3~900 0.11 47 14.
E.YAMPLE_ 14 A 100-ml, two-necked flask which has been purged before-hand with an iner-t gas is chargecl in an iner-t atmosphere with 30 mls of anhydrous n-hexane and then with 0.1 millimol of Ti according to Example 3~ 0.1 millimol of Al(iso C4H9)3 and subse-quently with 7 grams of anhydrous isoprene twice distilled over LiH. The mixture contained in the flask is stirred during two hours at the temperature of 20C and then poured in 300 mls. of methyl alcohol containing 1% of an antioxidant. The coagula-ted polymer is dried under vacuum at room temperature overnight.
Under these conditions, the yield of solid polymer is 6~3 grams~
corresponding to 90% of the introduced monomer. The N~IR analysis has shown the predominant presence of a structure of the 194-cis type.
EXA~IPLE 15 A 200-ml pop bottle, which has previously been purged with an inert gas~ is charged in an inert atmosphere with 90 mls of anhydrous n-hexane and then with 0.5 millimol of V according to ~xample 7 and 1 millimol of AlEt3. The bottle is stoppered with a neoprene plug and with a perforated crown cap so as to be able to introduce a hypodermic needle. At this stage, by means of a hypodermic needle directly welded to a metal bottle which contains butadiene, there are introduced 14 grams of a monomer in liquid form. The pop-bottle is placed in a rotary bath thermostatically maintained at the temperature of 20C during one and a half hour.
On completion, the pop-bottle is opened and its contents is dis-charged in half liter of methanol which contains 1% of ionolO The coagulated polymer is dried in a vacuo during 16 hours. Under these conditions~ the yield of solid polymer is 1.8 grams~ corre-sponding to 13% of the introduced monomer. The IR examination has shown a structure which was essentially integrally 1~4-trans.
37~33 E~Y~PLE 16 A 2-liter au-toclave is charged with one li-ter o-f anhydrous and deaerated n-he~ane con-taining 340 milligrams of ca-talyst made according to E~ample 8, corresponding to 1.66 milligram-atoms of titanium and 7 milligramatoms of AlEt3 per li-ter. There are charged 8 kilograms/sq. centimeter of propylene The -tempera-ture is raised to 65~C and the pressure is kept constant by feed-ing-in propylene during 6 hours. Upon cooling the autoclave, the polymer is collected on a filter and dried in a vacuo a-t 50C.
There are obtained 135 grams of a polymer having a crystallinity ~RX) of 42% and a residue of 85% after e.Ytraction with hexane.
E~IPLE 17 - Preparation of the catalys-t at a ra-tio Mg/Ti higher than 0 5 The same appara-tus as described in Example 1 is usedO The tungsten spiral is charged with 800 milligrams of ~Ig in needles.
The 500-ml flask is charged under nitrogen wi-th 130 mls. of anhy-drous and deaera-ted n-heptane, 20 mls of l-chlorohexane equal to 146 millimol and 0.15 ml o-f TiC14 corresponding to 1.35 millimol.
The flask is cooled t;o -70C, a 10-3 Torr vacuum is applied~ then the spiral is heated so as to vaporize the metal. A very fine grey-brown precipitate is formedO On completion of the vaporization (about 15 minutes) nitrogen is introduced in the apparatus and the flask is brought back to ambient temperature~ stirring being not discontinuedO The analysis on the slurry has given the following molar ratios :
-~Ig to Ti = 24 ; Cl to Ti = 45 Polymerization A 5-liter autoclave having an anchor-stirrer is charged with 2 liters of anhydrous and deaerated n-heptane~ 4 millimols of Al(iso Bu)3 and a quantity of catalyst~ prepared according to the present Example~ corresponding to 0.01 milligramatoms of elemental titanium. The temperature is raised to 850C, then there are charged 5 kgs/sq.cm of hydrogen and 3.5 kgs/sq.cm of ethylene. Ethylene is 16.
7~13 continuously -fed in so as to keep the total pressure constant during one hour. There are obtained 350 grams of polyethylene having MFI = 9.8 grams/10 mins and d = 0.9690 grams per cubic centimeter. The specific activity is 200~000 grams o-f polymer per gram of titanium per hour and per atmosphere of ethylene.
EYA~IPLE 18 The same method of synthesis of Example 17 is carried out, using bromohexane as the halogen-alkyl. A slurry is obtained, having the following analysis :
~Ig to Ti ratio = 16.5; (Br + Cl) to Ti ratio = 33.
In the polymerization of ethylene, under the conditions of Example 17, there have been obtained 165 grams of a polymer having an ~FI = 4.18 grams/10 mins. corresponding to a specific ac-tivity of 98,000 grams per gram of Ti per hour and per atmosphere of ethylene.
~XA*~LE 19 ~ith the procedure of Example 17 and the same reactants, -there have been prepared several catalysts having different Mg to Ti ratios3 the activities of which in the polymerization of ethylene, carried out under the conditions of Example 17, are tabulated in TABLE 2.
Mg Specif.activity in MFI App~d MFI
Ti grams polym. pergrams~/10 mins. (sp.grav.) MFI
gram polym. per hour grs/cu.cm 2.1 and per atmos.of C2 5.0 47,000 16,0 0.25 22 9.0 57,000 6.8 0.23 34 13.4 90,000 11.4 0.22 35 16.5 95,000 11.3 0.24 28 22.7 125,000 10.3 0.22 36 25.0 200,000 9.8 0.24 23 35- 280,000 10.1 0.20 35 17.
EXA~PLE 20 The same syntllesis procedure of Example 17 is usecl, with the following reactants :
~Ig : 1,100 milligrams (46 milligramatoms) TiCl2(0i Pr)2 = 0.2 ml corresp. to o.68 millimol, and C6H16Br = 20 mls corresp. to 142 millimols in 200 mls nor.octane.
After the reaction, the analysis in the suspension is :
to Ti = 48 ; (Br ~ Cl) to Ti = 83.5 In the polymeriza-tion of ethylene under the conditions of Example 17 there have been obtained 265 grams of a polymer having an MEI = 8.5 grams per 10 minutes, equal to a specific activity of 157,000 grams of polymer per gram of Ti per hour and per atmo-sphere o~ ethylene.
The same synthesis procedure as in Example 17 is used with the following reactants :
~Ig : 1,050 milligrams (~3 milligramatoms) C6H13Cl 15 mls (~10 milligramatoms) Ti (O iso Pr)~ 0.2 ml (0.67 milligramatoms) in 170 mls nor.octane.
P = 0005 mmHg ; t = -50C.
On completion of the vaporization of the magnesium, the flask is filled with nitrogen and allowed to stand overnight. The suspension~ upon analysis, gives :
Mg to Ti ratio = 52 ; Cl to Ti ratio = 90 In the polymerization of ethylene~ as carried out under the conditions described in Example 17, there are obtained 125 grams of a polymer having an ~lFI = 6.7 grams per 10 minsO and a specific activity of 75,000 grams of polymer per gram of Ti per hour and per atmosphere of ethylene.
EXA~lPLE 22 An appara-tus similar to that described in Example l is usedO
, 7~8 In the tungsten filament there are arranged 1~096 grams of pure metallic magnesium wire, whereas the one-liter flask is charged with 130 cu.cm of anhydrous ligroin containing 1 millimol of TiC14 together with 66~7 millimols of SnC14~ The magnesium is completely vaporized within 40 mins. with a vacuum of 0 09 Torr~
by keeping the flask in rotation at; -60C - - 70C. The flask is restored to the ambient temperature and pressure and s-tirring is continued during one hour approximately. During this time, the slurry disoharges its color from dark brown to grey-w}iite~ Filtra-tion is carried out on a porous G3 diaphragm, then washing with anhydrous heptane is effected and the solid is reslurried in heptane.
The analysis of the slurry gives the following results :
Ti = 5.77 millimols per liter ; ~Ig = 181 millimols per liter Sn = 170 millimols per liter ; Cl = 731 millimols per liter E~PLE 23 In the tungsten filament there is arranged 1.0 gram of pure magnesium wire. The flask is charged, in the order given, with 130 mls of anhydrous toluene and 1 millimol of TiC14~ which imparts a yellow hue to the solvent . Then, there are added, at -780C~
2 millimols of die~hylphthalate, dropwise. The solution passes from yellow to light green, There are then added 66.7 millimol of anhydrous SnC14 which imparts a yellow-orange hue: an orange oily substance settles on the flask bottom. Magnesium is vaporized during 40 mins. under a vacuum of 0.06 Torr by maintaining the flask in rotation at -780C. The flask is brought back to ambient temperature and pressure and kept stirred for about one hour.
During this time the slurry passes from dark brown to yellow. The slurry is collected on a filter, washed on anhydrous heptane and re-slurried in heptane.
The analysis of -the slurry gives the following results :
Ti = 7.74 millimols per liter ; ~Ig = 235 millimols per liter Sn = 190 millimols per liter ; Cl = 897 millimols per li-ter 19.
87 ~
EIYA~IPLE 24 In the tungsten filament there are arranged 809.5 milli-grams of pure magnesium wire whereas the flask is charged wi-th 100 mls of anhydrous toluene and one millimol of TiC14 which colors the solvent in yellow. Then there are added at room tempe-rature and with stirring 2 millimols of diethylphthalateO The solution takes a light green hue. There are further added 43~3 millimols of SnC13nBut which imparts a yellow-orange hue and an oily substance is deposited on the flask bottom. Magnesium is evaporated during 40 mins. under a vacuum of 0.07 Torr by maintain-ing the flask in rotation at -78C. The flask is brought back to ambient pressure and temperature and stirring is continued during about 2 hours at room temperature. The filurry passes from dark bro~n to light grey during this period of time. Filtration, wash-ing with anhydrous heptane and reslurrying in heptane are carried out.
The analysis of the slurry gives the following results :
Ti = 7.18 millimols per liter Mg = 66 millimols per liter Sn = 80 millimols per liter Cl = 349 millimols per li-ter EYA~LE 25 970 milligrams of pure magnesium wire are placed on the tung-sten. In the flask which contains 100 mls of anhydrous heptane and 1 millimol of TiC14~ there are added at room temperature and with stirring 60 millimols of SbC15~ distilled. The solution remains clear. By vaporizing magnesium, the suspension becomes yellow-brown: thenj a white powder is formed which gradually darkens and passes to grey and eventually to black. Filtration, washing with anhydrous heptane and reslurrying in such solvent are carried out. The analysis o the slurry gives the following results :
Ti = 4.60 millimols per liter Mg = 226 millimols per liter Sb = 95 millimols per liter Cl = 1~058 millimols per liter 20.
EIY~MPLE 26 There are placed on the -tungsten filamen-t 831,8 milligrams of pure magnesium wire. In the flask which con-tains 100 mls of anhydrous nor.heptane there are added at room temperature and with stirring, 5103 millimols of distilled POC13 and 1 millimol o TiCl40 A yello-~ precipitate is formedO Magnesium is vaporized while keeping the flask at -780C. The suspension is yellow-brown.
The flask is brought back to ambient temperature and pressure and stirring is continued during 2 hours at room -temperature . The suspension becomes pale yellow. Filtration~ washing with nor, heptane and reslurrying in this latter solvent are efec-ted.
The analysis of the slurry gives the following results :
Ti = 9.62 millimols per liter Mg = 126 millimols per liter P = 390 millimols per liter Cl = 655 millimols per liter Ethylene polymerization tests with the catalyst mixtures as prepared according to Examples from 22 to 26 have been carried out according to Example 17 ~ith a polymerization time of 2 hours with a pressure o hydrogen of 5 kilograms square centimeter and a pressure of ethylene of 5 kilograms per sq.cm. The results which have been obtained are tabulated in TABLE 3.
. . _ . . , Catalyst Specific activity in MFI21 MFI21 Apparent spec.
accordDto grams of polym,per grams/ gravity grams/
Example gram of Ti per hour 10 min~ MFI2.1 cu.cm and per a-tmosph.of C-2 ~ . . ._ 22 34,700 5.oo 36 o.3o 23 32,500 5-7 31 not determ.
24 13,000 2~90 32 no-t determ, 34,000 6g98 27 0~0 3 26 8,300 ~.32 31 no-t determ.
_ . _ _ . .
EX~IPLE ~.7 A two-necked flask, purged with nitrogen is charged wi-th lO grams of powdered polyethylene9 50 mls of anhydrous and deaera-ted nor.hexane and ~.5 milligramatoms of Al(isoBu)3.
Upon homogeneization the mixture is allowed to s-tand during two hours~ whereafter there are added, still under a nitrogen stream, 0.0075 milligramatoms of a catalyst such as titanium when prepared as disclosed in Example 17 together with 1.5 milligram-atoms of Al(isoBu)3~ Hexane is completely dis-tilled off in a vacuo at 600C. The thusly prepared material is charged under nitrogen in a well dried 2-liter autoclave, which has been deaera-ted and kept under nitrogen atmosphere. The autoclave is evacuated to remove nitrogen, whereafter ethylene is fed until reaching a gauge pressure of 1.5 kilograms per square centimeter and the tempe-rature is raised to 80C. During progress of polymerization, ethylene is fed in so as to keep constant the gauge pressure of ~.5 kilograms per square centimeter. The absorption o-~ ethylene is checked by a rotameter. Polymerization is discontinued after 5 hours. During this period of time the absorption remains constant.
There are obtained 84 grams of polyethylene corresponding to a specific activity of 16~500 grams of polymer per gram of Ti per hour and per atmosphere of ethylene~
EXA~LE 28 The exact procedure as disclosed in the previous Example has been followed~ with 2 kilograms per sq~cm of hydrogen as a mole-cular weight adjuster~ After three hours of polymerization there are obtained 56 grams of a polymer having an MFI of 2.1 grams per lO minutes.
EXA~LE 29 Copolymerization of ethylene with butene-l is carried out~using the catalyst disc:losed in Example 17, the same procedure~ the same polymeriz.ation condition and the same concentrations of catalys-t 22.
~18748 as described in tha-t Example~ The feed of butene-l is carried out concurrently with that of e-thylene by introclucing a quantity of butene-l equal -to 5% of tha-t of ethylene~ the gases being metered with calibra-ted fluxmeters 9 A-ter one hour of polymeriza-tion there are obtained 290 grams of a copolymer having an MFI of 10 grams per 10 mins. and an apparent specific gravity~ d = o~9580 grams per cu.cm. The speci-fic activity is 170~000 grams of copoly-mer per gram of Ti per hour and per atmosphere of ethyleneO
E.YAMPLE 30 Copolymerization of ethylene with hexene-l is effected using the catalyst described in Example 17 under the same conditions and concentrations as disclosed in the same Example.
The procedure is as follows :
- an autoclave is charged wi-th 1.8 liters of norOheptane containing 8 grams of anhydrous and deaerated hexene 1.
- the tempera-ture is thermostatically main-tained at 85OC.
- the catalyst is charged (~ millimols of Al(isoBu~3 and OoOl milli-gramatom of catalyst such as titanium diluted with 200 mls of n-heptane. There are charged 5 kgs/sqOcm of hydrogen and 305 kgs/sq.cm of ethylene~ During the feed of ethylene which is car-ried out continuously during the entire polymerization time (1 hour) to keep constant the total pressure, there are fed 8 grams of hexene-l diluted in 100 mls.nor.heptane by a metering pump.
After one hour of polymerization the gases are vented off, the co~
polymer is collected on a filter and driedO There are obtained 230 grams of a copolymer having an MFI = 8.5 grams/10 mins and an app.spec.grav., d = 0.9576 grams per cubic cen-time-ter. The obtain-ed specific activity is : 136,000 grams of copolymer per gram of Ti per hour and per atmosphere of e-thylene.
tic or mixed compounds, provided tha-t they are liquid under the adopted working conditions.
Under the adopted operative conditions the metal as at ~) above is vapori~ed, preferably in a vacuo~ by an appropriate heating system (with electric resistors, electron beams, by in~
duc-tion and also by using high frequencies, by laser beams, by electric sparks, by voltaic arc and so forth). The vapors emer-ging from the metal surface are quenched in a liquid which con-tains the compounds indica-ted at 3) possibly in union with the compounds at 4) and 5) above.
Such a liquid must be cooled a-t a temperature which is low enough as to limit it evaporation 30 as co~sequently to permit the maintenance o~ the degree o~ vacuum which is required for the va-porization of the me-tal at temperatures which can be attained by the as adopted heating systemO Such a catalyst composition is capable of polymerizing and copolymerizing with very good yields ethylene and higher alpha olephines to high-density polyethylene, and to isotactic polypropylene, respectively, and is likewise capable of polymerizing butadiene to 1~-trans- polybutadiene~
and isoprene to 1,4-cis-polyisoprene.
~s regards ethylene, and this is a second object of the present invention, a few of the catalyst compositions in question are capable of displaying an exceptional activity in polymeriza-tion runs. ~ore particularly~ when the catalyst is prepared from ~Ig vapors, the compound as per i-tem 3) above is based on Ti, and the halogenated compound as per 4) above is present~ it has been su~risingly fountl that extremely high yields can be obtained when working w];th an atomic ratio of Mg to Ti equal to or higher than 4 and with an atomic ratio of X to ~Ig equal to~ or higher -than 2~ whereiIl X is -the mobile halogen as defined at 4) above.
The above specified catalyst affords substantial advantages over other ca-talysts adapted to the polymerization of ethylene~
~LI 3748 in high yields and of ethylene with other higher alpha-ole-phines, More detailedly; the act;ivity (in terms of kilograms of polymer per gram of Titanium as produced in one hour with an atmosphere of ethylene under the conditions set forth in the examples) is extremely high, in t;he order of magnitude of 230 kilograms; the synthesis of the catalyst resorts to raw mate-rials which are particularly simple and which can be standard-ized (differently from many supports as employed in other catalyst compositions which can be difficult to characterize from a phisico-chemical standpoint) and thus gives rise to catalysts ha~ing an activity which is both homogeneous and reproducible-.
The preparation technology of the catalyst is both simple and quick.; the catalyst can be employed such as it has been pre-pared, in union with the cocatalyst, in the slurry polymerization of ethylene without any subsequent separations~ filtrations or elutions. ~ore partlcularly, all the transition metal put to react is converted into an active catalyst ; the catalyst .can be employed, after having been dispersed on an inert support, which latter can even be the polyolefin as such, in::the polymerization ~0 of ethylene in the gaseous state and thus without any hydrocarbo-naceous dispersant being present; the adjustment of the molecular weight with hydrogen on a wide molecular weight range (MFI 0.1 to ~IFI 15~ does not involve yield losses of polymer with respect to the transition metal.
~lore detailedly, an object of the present invention is a catalyst system having the above indicated composition which per-mits to overcome the above enumerated drawbacks and which, in use, affords -the following advantages :
- obtention of high yields of polymer relative to the transition metal;
- a morphologically homogeneous polymer;
- an easy adjustment of the molecular weight of the polymer ;
87~3 - use in th~ polymeri~ation in ~a6eous phaæe wlSh t}le ob-ten-tion oE hi~h yields.
As outlined above 3 such a c~talyst sy3-tem compr.ise~ an organic metallic compound of aluminum and a composition as obtained by reaction betwecn vapors of metallic ma~nesium~
the -titanlum compound a halo~en-donor~ selected -~rom amon~
the halogenatcd organic and inorganic compounds~ It ls known~
inter alia, that ti-tanium -trichlorlde~ ~an be prepared by re-duction of TiC14 with the followin~ procedures :
a) with hydrogen under drastic cQnditions (SOOC-700C), ~he products obtalned, due to the hi~h temperature whlch ha~ been usecl~ are poorly ac-tive in the polymerization oP olephines.
b) with metals such as aluminum~ antimony~ and others~ at temperatures equal to or hi~her than 200C. In thls cas~ not all o~ the metals are ~uitable in that ~er mAr~y o-E them the reaction take~ place i.n a llmited manner only or lt does not ~o on at all. It ls correct that ~uch a depuot can be obviated by u~in~ polar solvents, ~uch a~ ~MF, THF~ dlmothoxyheptane7 but in 3uch a case -the final titRnium triohloride is complexed wi~h ~0 the polar ~olvent and exhibits no lnterest ~rom a cataly~ ta~d-point. Also the u~e oP a liquid amal~am oan prevent thi~ draw~
back (U.S.PatO 3 658 723 to DOW CH~M~) bu~ all tho m~tal~ hav~
a very limited solubility in meroury so that such a prooadure r~qulres a large use o~ this metal which can be dl~iculty ~0pa-rated ~rom the titanlum trichloride. These products~ however~ are not much active ln polymerization, o) with metal-alkyls, a method which permits to use moderate temperatures~ but whlch uses comparatively expensive materials~
which also are extremely reactive and hazardous. With thi~
method it is not pos~ible to use tran~itlon metals the alkyl~ nP
which have no suE~icient stabllity to be prac-tically used~
d) with carbonyls of low~valency transition metRls~ as de~cri-~ ~ ~8~8 bed in the Canadian Patent Application No. 224799 of 16.4.1975.
There is the advantage oE obtaining the reduction with metals which would not react as such, but this method is limited to the transition metals and, among these, only to those which give stable carbonyls. The as-obtained titanium chlorides display a fair catalyst activity in the polymerization of unsaturated hydrocarbons, either alone or in admixtures.
An important object of the present inven-tion is thus also a method which permits to obtain titanium trichlorides without suffering from any of the shortcomings indicated above.
Such a method consists in providing soluble atoms of a metal by a procedure of vaporization in a vacuum, e.g. a high vacuum and condensation in an MC14 (M being either Ti or V), either pure or diluted in inert solvents, these latter being kept at a low temperature.
The principal advantage of such a procedure is that it can be applied generally, that is to say that any metal can be used, either a transition metal or another metal.
In addition, there is the advantage of obtaining products which have had a controlled thermal hystory and thus have differentiated physical properties, and consequently different catalytic activities, many metals being controllably and simul-taneous co-vaporizable.
The products thus obtained, which are yet a further object of the present invention, c~an found their use as catalysts for the polymerization and copolymerization of olpehines using the aluminum-alkyls as cocatalysts.
Thus, according to the presen-t invention, there is, in particular, provided a method for the preparation of a catalyst containing titanium trichloride or vanadium trichloride and useful in the polymerization and copolymerization of ethylene with higher alphaolefines, which comprises vaporizing another Ç3 ~i!37~8 metal selected from the group consisting of Al, Mg, Cr, Mn, Fe, V and Ti under vacuum and reacting the vapor thus obtained with TiC14 or VC14 at a low temperature.
The vaporization can be carried out in a very high vacuum, preferably between 10 3 Torr and 10 6 Torr a-t temperatures which vary according to the metal which is used, usually from 800C
to 2500C, as disclosed by P.L. Timms, Angew. Chem., 14, 273 ~1975).
The metal vapors can be reacted with an MC14 at a temperature in the range from -80C to +20C, preferably between -60C and --20C .
The reaction can take place with MC14, either pure or dilu-ted with inert solvents selected from among aliphatic or aromatic, saturated or unsaturated hydrocarbons and the halogenated hydro-carbons, such as chlorohexane and fluorobenzene.
The choice of the solvent or the solvent mixture is govern-ed by the conditions of use (temperatures of solidification and vaporization under the pressure which has been adop-ted).
It has been found, moreover, that, if in the above mentioned preparation, a high ratio of Mg to Ti is adopted and the reaction is carried out in the presence of a halogen donor, it becomes possible to obtain a composition which, together with an organic metallic compound of aluminum, provides outstandingly good results in the high-yield polymerization of alpha-olephines, particularly of ethylene, as such or in admixture with one or more of its higher homologs.
More particularly, such a composition is obtained by vaporizing magnesium or an alloy thereof, then condensing it in an inert diluent: which contains the titanium compound and the halogen-donor.
The vaporization of magnesium is preferably carried ou-t in a vacuo, from 10 Torr to 10 Torr, at a variable temperature, :;~
37~8 consistently with the pressure used, of from 500C to 1200C.
The metallic vapors are condensed within a colution, kept stirred, of the -titanium compound and the halogen-donor, at a temperature higher than -the freezing point and lower -than the boiling - 7a -, ~ ~J
8~413 point of the solution.
As outlined above, resul-ts useful to -the ends of a high-yield polymerization of alpha-olephines are obtained if a high ratio o-f ~Ig to Ti is adopted~ especially if such a ratio is equal -to, or higher -than, 4. Concurrently, the presence is ne-cessary of a halogen-donor, select;ed from among the organic or inorganic halogenated compounds~ which is employed in an e~cess over the magnesium; it is preferred -to use ra-tios of the haloge-nated compound -to the magnesium equal to, or higher than, 2.
The condensation of the magnesium vapors is carried out in an inert diluent~ selected from among the aliphatic, or the aromatic hydrocarbons.
In its turn, the titanium compound is selected from among the compounds of tetravalent titani~l (trivalent or met.allic-organic), preferably soluble in -the selected diluent, whereas the halogenated compound~ as outlined above~ can be selected from among the organic or inorganic hali~es; a special emphasis can be pu-t on the alkyl and aryl halides. At the end of the reaction~
a very fine slurry is obtained, which can be used as such in poly-merization.
The polymerization reaction, as outlined above, is carriedout in the presence of a catalyst system composed by the suspension as obtained beforehand, in union with an organic metallic compound of aluminum, in a hydrocarbonaceous solvent, which can be the same as that employed in the above described preparationO
The working temperatures vary -~rom 20C to 200C, preferably between 50C and 200C~ under pressures which are comprised bet-ween 1 and 20 at:mospheres. As an alternative~ when it is desired to carry out the polymerization reaction in the gaseous state~ it is enough -to scatter the catalyst within a low-boiling solven-t~ so that the lat-ter can easily be withdrawnO The catalys-t, in such a case, can also be dispersed on an inert solid support, and the 8.
E374~3 latter can be composed even by the polyol~phine itself~ The conditions which can be adopted for the polymerization in the ~aseous phase provicLe a temperature range ~lhich is maintained below the melting point of the olephine and in the par-ticular case of the polymerization of e-thylene, the -temperature range which ~s preferred i3 between 40C and 90~C Pressures are pre-ferably selected between 1 and 40 atmospheres. Hydrogen can be emplcyed as a regulator of the molecular weight.
E~IPLE
Preparation of the mi~ture 3 TiC13 1 AlC13 . A rotary flask is used, at the center of which a tungsten filament is arranged, ~hich is connected to a source of electric powerO Under the flask~ a cooling bath is horizontally positioned~ In the top portion of the apparatus there are a nitrogen and a vacuum -it-ting, ~ithin the spirally wound tungsten filament there are placed loO milligrams of pure aluminum in flakesD The flask is charged under nitrogen with 250 mls of anhydrous decane, containing TiC14 equal to 30% of the solvent. The rotary flask is cooled with the -40C bath, then vacuum is applied with a diffusion pump until reaching 10-4 Torr. Once these conditions have been attained, the filament is heated until the metal is vaporized~ The vaporized metal immediately reacts with TiC14, giv1ng a very fine dark-brown precipitate. On completion of the VapOrizatiOn~ the flask is pressurized again and brought to ambient -temperature by feeding ni-trogeng then the suspension is brought -to 150C during three hours. Upon filtra-tion and drying, the as-obtained violet product is analyzed For Alcl3-3 TiC13Ti % Al% Cl%
Calcd. 24.12 4.52 71036 Found 24O01 4.90 69O80 E~A~IPLE 2 The same appara-tus and procedure of E~cample 1 are used. There 4i5 are charEed l~0 milli~rams of metallic pure ~Ig in wire form and 250 mls octane, containing 2% o TiCl~ IJpon cooling at -600C and a-ttaining a vacuum of 10 4 Torr, the vaporization o-~the metal is starteda and it takes five minutes. The forma-tion is experienced o-~ a fine brown-violet precipita-te. The flask is restored to ambien-t pressure and tempera-ture. A sample is broug.ht to 125C during 4 hours, whereafter the slurry is filt-ered and the violet precipitate is washed with n-heptane until completely discharging the TiCl~, then the solid product is ana-lyzed after having dried it in a vacuo (2 grams):
For MgC12 2 TiCl3 ~i~ Mg% Cl%
Calcd 23076 5-94 70028 Found 22.97 5-~ 67.1 The two samples~ the untreated one ancl the treated one, have~
as seen through ~-ray analysis, a gamma structure.
E~ lPLE 3 The same apparatus and the same procedure as in Example 2 arc used~ adopting a concentration of TiC14 in n-octane of 14%.
A brown-violet product is obtained~ which is filtered~ washed with n-heptane until TiC14 is discharged~ then re-slurried in n-heptane and analyzed. The analysis gives MglTil 84C14.
E~lPLE 4 The same apparatus and -the same procedure as disclosed for Example 1 are used9 There are charged 00240 grams of metallic magnesium in wire form and 300 mls of n-octane containing 0~07%
of TiC14 and 12% o-f n-chlorohexaneO Upon cooling at -60C~ a vacuum of 10 4 Torr is made and magnesium is vaporized during 7 minutes. A solid, pale-brown product is formed~ which is collect-ed on a fil-ter~ washed with n-heptane and kept at 100C in such a solvent during two hours. The analysis shows the following molar composi-tion : l~lg3 lTil C17 8 10 .
~' ~L3L18~
E ~\MPLE 5 The same apparatus ancl procedure as clescribed in Example 1 are usedr There are char~ed O.180 grams o-f metallic Mn in flakes and ?50 mls o octane containing 2% of TiC14. Upon cooling at -60C, a vas::uum of 10 ~ Torr is at-tained ancl the vaporization of the me-tal is started3 which is completed within 3 minutes. The orma-tion is experienced a brown-violet precipitate. The flask is brought back -to ambien-t -temperature and pressure, then the suspen-sion is iltered~ washed with n-hexane until discharging the TiC14 completely, whereafter the product is dried in a vacuo and analyzed.
The analysis gives:
For 2 TiCl30~InCl 2Ti% C17o~ Mn~
Calcd. 22~0 65030 12063 Found 22~0 6304 14.4 EX~lPLE 6 The same apparatus and procedure as disclosed in Example 1 are used~ There are charged 0. 25 grams o metallic Fe in shavings and 250 mls of anhydrou;~ n-octane containing -the 5% of TiC14 .
Upon cooling at -50C~ a vacuum of 10 Torr is reached and the vaporization of the metal is started, that which takes 5 minutes.
The formation is experienced of a solid red-brown product which is collected on a filter~ washed with anhydrous hexane and dried under vacuumO There are obtained 1~ 87 grams o a product which has the following analysis:
2 3 Ti~ Fe~ Cl~
Calcld 21099 12n81 65.19 Found 21~73 12~70 66~90 E ~YAMPLE 7 The same apparatus and procedure as disclosecl in Example 1 are used There are charged 0~120 grams of Mg wire and 250 mls of n-octane containing 3 mls of VCl~. Upon cooling a-t -60"C, a vacuum of 10-3 Torr is reached and the vaporiza-tion of the metal is s-tartedg -that which -takes 5 minutes The formation is experienced of a solid dark-brown productg which is washed with n~heptane -to remove the e~c:ess VC14 and reslurried in n-heptaneO The analysis gives MglV2 ~C13 80 E~IPLE 8 The same apparatus and procedure as disclosed in E~ample 1 are used. There are charged 1 gram of metallic chromium in lumps and 250 mls~ of n-heptane~ containing 10 mls of TiC14~
Upon cooling at -80C, a vacuum of about 10-4 Torr is reached and the vaporization of the metal is starte~, which takes 20 minutes to be completedO The formation is experienced of a solid greenish product, which is collected on a filter and washed with heptane to remove the excess of TiC14 and reslurried in heptane The analysis gives :
For CrCl303TiCl3 Ti% Cr% Cl%
Calcd 23.19 8.37 68.44 Found 23.40 8.20 67.60 E~SPLE 9 A 5-liter autoclave is charged with 2 liters of anhydrous n-heptane~ containing the catalyst as prepared according to Example 3 in the concentration of 0.03 milligramatoms of Titan.ium and 4 milligramatoms of Al(iso_Bu~30 The mixture is brought to 850C, then there are charged 5 kilograms per sq. centimeter of hydrogen and as much of e-thylene~ Polymerization is carried out during four hours, while maintaining the total pressure constan-t by addition of e-thylene On completion of the polymerization~ the slurry is centri.fuged and the polymer is dried in a vacuo at 50C
during four hours, -then weighed.
There are obtained 400 grams of a white polymer, equivalent ~1~874~3 to a specific ~vielcl of 6,440 grams of polymer per gram of Ti per hour and per atmosphere of C~ ,having an MFI = 0 60.
E~IPLE lO
The procedure is the same as in Example 9, using as the catalyst the sample described in E~Yample 1,in the concentration of o~o6 milligramatoms per liter of titanium and as co-catalyst Al(iso Bu)3 in the concentration of 4 milligramatoms per liter.
There are charged 5 kilograms per sqOcentimeter of hydrogen and 5 kilograms per sq.centimeter of ethylene;the polymerization is car-ried out under a constant pressure by feeding-in ethylene during four hours and there are obtained 120 grams of a white polymer, ~hich corresponds to a specific yield of 1,030 grams of polymer per gram of Ti per hour and per atmosphere of C-2, having an MFI2 16 =
1,5 (~IFI21 6/P~FI2.16 = 49-4)-E~IPLE llA 2-liter autoclave is charged with 1 liter of anhydrous and deaera-ted n-hexane, containing 2008 milligrams of a catalyst according to Example 6,equal to 0.0941 milligramatoms of titanium and 4 milligram-atoms of Al~iso Bu)3~per liter. 20 kg sq~cm of hydrogen and 20 kg/sq.
cm of ethylene are charged. The temperature is raised to 85C and the pressure is maintained constant by continuously feeding-in ethy-lene. After 2 hours of polymeriza-tion,the reaction is cooled~ the autoclave is vented and the polymer is centrifuged,dried under vacuum at 50C and weighed. There are obtained 320 grams of a poly-mer having MFI2 16 = 0-12 (~FI21.6/MFI2-16 44 7) grams per gram of Ti per hour and per atmosphere of C-2 .
EXA~IPLE 12 .
The procedure is -the same as in Example 9, using as the cata-lyst the product described in Example 5, in the concentration of 0.10 milligramatoms per liter of ti-tanium. As cocatalyst there is used Al(iso Bu)3 in the concentration of 4 milligramatoms per liter.
Polymeri~ation iS carried ou-t during 3 hours with 5 kilograms/sq.cm 13.
374~3 o hydrogen and 5 kgs/scOcm of e-thylene. There are obtained 390 grams of a polymer having an MFI2 16= ~35 and an MFI21 6/MFI2 16=
= 350 Yield 2,700 grams per gram of Ti per hour and per abmosphere f C-2 .
EI~PLE 13 The procedure is the same as or Example 9 using as the catalyst the sample as described in Example 8 in the concentra-tion of 0.026 milligramatoms per liter of -titanium and 2 milligram-atoms per liter o Al(iso Bu)30 There are charged 5 kilograms/
sq.cm of hydrogen and 5.5 kilograms/sqOcm of ethylene. The tempe-rature is raised to 85C and the pressure is main-tained cons-tan-t by feeding-in ethylene continuously After two hours of polymeri-zation, the reaction is cooled, the autoclave is vented and the polymer is collected on a filter and dried in a vacuo at 50C and weighed. There are obtained 108 grams of a polymer having an ~IFI = 0.11 corresponding to a yield of 3,900 grams of polymer per gram of Ti per hour and per atmosphere of ethyleneO
T~BLE 1 tabulates the specific activi~ties as obtained in the pol~merization of ethylene with the samples of TiC13 as prepared according to the Examples from 1 to 8 inclusive~
T A B L E
Catalyst Example Specific activity MFI2Dl MFI21 cat.polymO grjpolym /gr.Ti/ min~a. 2,1 3 TiC13.AlC13 1 10 1~030 0062 49 2 ~iC130~1gC12 3 9 6,440 ~).60 36 2 TiC13.MnC12 l5 12 2,700 0.35 35 2 TiC13.FeC12 6 11 1,750 0012 35 3 TiC13.CrC13 3 13 3~900 0.11 47 14.
E.YAMPLE_ 14 A 100-ml, two-necked flask which has been purged before-hand with an iner-t gas is chargecl in an iner-t atmosphere with 30 mls of anhydrous n-hexane and then with 0.1 millimol of Ti according to Example 3~ 0.1 millimol of Al(iso C4H9)3 and subse-quently with 7 grams of anhydrous isoprene twice distilled over LiH. The mixture contained in the flask is stirred during two hours at the temperature of 20C and then poured in 300 mls. of methyl alcohol containing 1% of an antioxidant. The coagula-ted polymer is dried under vacuum at room temperature overnight.
Under these conditions, the yield of solid polymer is 6~3 grams~
corresponding to 90% of the introduced monomer. The N~IR analysis has shown the predominant presence of a structure of the 194-cis type.
EXA~IPLE 15 A 200-ml pop bottle, which has previously been purged with an inert gas~ is charged in an inert atmosphere with 90 mls of anhydrous n-hexane and then with 0.5 millimol of V according to ~xample 7 and 1 millimol of AlEt3. The bottle is stoppered with a neoprene plug and with a perforated crown cap so as to be able to introduce a hypodermic needle. At this stage, by means of a hypodermic needle directly welded to a metal bottle which contains butadiene, there are introduced 14 grams of a monomer in liquid form. The pop-bottle is placed in a rotary bath thermostatically maintained at the temperature of 20C during one and a half hour.
On completion, the pop-bottle is opened and its contents is dis-charged in half liter of methanol which contains 1% of ionolO The coagulated polymer is dried in a vacuo during 16 hours. Under these conditions~ the yield of solid polymer is 1.8 grams~ corre-sponding to 13% of the introduced monomer. The IR examination has shown a structure which was essentially integrally 1~4-trans.
37~33 E~Y~PLE 16 A 2-liter au-toclave is charged with one li-ter o-f anhydrous and deaerated n-he~ane con-taining 340 milligrams of ca-talyst made according to E~ample 8, corresponding to 1.66 milligram-atoms of titanium and 7 milligramatoms of AlEt3 per li-ter. There are charged 8 kilograms/sq. centimeter of propylene The -tempera-ture is raised to 65~C and the pressure is kept constant by feed-ing-in propylene during 6 hours. Upon cooling the autoclave, the polymer is collected on a filter and dried in a vacuo a-t 50C.
There are obtained 135 grams of a polymer having a crystallinity ~RX) of 42% and a residue of 85% after e.Ytraction with hexane.
E~IPLE 17 - Preparation of the catalys-t at a ra-tio Mg/Ti higher than 0 5 The same appara-tus as described in Example 1 is usedO The tungsten spiral is charged with 800 milligrams of ~Ig in needles.
The 500-ml flask is charged under nitrogen wi-th 130 mls. of anhy-drous and deaera-ted n-heptane, 20 mls of l-chlorohexane equal to 146 millimol and 0.15 ml o-f TiC14 corresponding to 1.35 millimol.
The flask is cooled t;o -70C, a 10-3 Torr vacuum is applied~ then the spiral is heated so as to vaporize the metal. A very fine grey-brown precipitate is formedO On completion of the vaporization (about 15 minutes) nitrogen is introduced in the apparatus and the flask is brought back to ambient temperature~ stirring being not discontinuedO The analysis on the slurry has given the following molar ratios :
-~Ig to Ti = 24 ; Cl to Ti = 45 Polymerization A 5-liter autoclave having an anchor-stirrer is charged with 2 liters of anhydrous and deaerated n-heptane~ 4 millimols of Al(iso Bu)3 and a quantity of catalyst~ prepared according to the present Example~ corresponding to 0.01 milligramatoms of elemental titanium. The temperature is raised to 850C, then there are charged 5 kgs/sq.cm of hydrogen and 3.5 kgs/sq.cm of ethylene. Ethylene is 16.
7~13 continuously -fed in so as to keep the total pressure constant during one hour. There are obtained 350 grams of polyethylene having MFI = 9.8 grams/10 mins and d = 0.9690 grams per cubic centimeter. The specific activity is 200~000 grams o-f polymer per gram of titanium per hour and per atmosphere of ethylene.
EYA~IPLE 18 The same method of synthesis of Example 17 is carried out, using bromohexane as the halogen-alkyl. A slurry is obtained, having the following analysis :
~Ig to Ti ratio = 16.5; (Br + Cl) to Ti ratio = 33.
In the polymerization of ethylene, under the conditions of Example 17, there have been obtained 165 grams of a polymer having an ~FI = 4.18 grams/10 mins. corresponding to a specific ac-tivity of 98,000 grams per gram of Ti per hour and per atmosphere of ethylene.
~XA*~LE 19 ~ith the procedure of Example 17 and the same reactants, -there have been prepared several catalysts having different Mg to Ti ratios3 the activities of which in the polymerization of ethylene, carried out under the conditions of Example 17, are tabulated in TABLE 2.
Mg Specif.activity in MFI App~d MFI
Ti grams polym. pergrams~/10 mins. (sp.grav.) MFI
gram polym. per hour grs/cu.cm 2.1 and per atmos.of C2 5.0 47,000 16,0 0.25 22 9.0 57,000 6.8 0.23 34 13.4 90,000 11.4 0.22 35 16.5 95,000 11.3 0.24 28 22.7 125,000 10.3 0.22 36 25.0 200,000 9.8 0.24 23 35- 280,000 10.1 0.20 35 17.
EXA~PLE 20 The same syntllesis procedure of Example 17 is usecl, with the following reactants :
~Ig : 1,100 milligrams (46 milligramatoms) TiCl2(0i Pr)2 = 0.2 ml corresp. to o.68 millimol, and C6H16Br = 20 mls corresp. to 142 millimols in 200 mls nor.octane.
After the reaction, the analysis in the suspension is :
to Ti = 48 ; (Br ~ Cl) to Ti = 83.5 In the polymeriza-tion of ethylene under the conditions of Example 17 there have been obtained 265 grams of a polymer having an MEI = 8.5 grams per 10 minutes, equal to a specific activity of 157,000 grams of polymer per gram of Ti per hour and per atmo-sphere o~ ethylene.
The same synthesis procedure as in Example 17 is used with the following reactants :
~Ig : 1,050 milligrams (~3 milligramatoms) C6H13Cl 15 mls (~10 milligramatoms) Ti (O iso Pr)~ 0.2 ml (0.67 milligramatoms) in 170 mls nor.octane.
P = 0005 mmHg ; t = -50C.
On completion of the vaporization of the magnesium, the flask is filled with nitrogen and allowed to stand overnight. The suspension~ upon analysis, gives :
Mg to Ti ratio = 52 ; Cl to Ti ratio = 90 In the polymerization of ethylene~ as carried out under the conditions described in Example 17, there are obtained 125 grams of a polymer having an ~lFI = 6.7 grams per 10 minsO and a specific activity of 75,000 grams of polymer per gram of Ti per hour and per atmosphere of ethylene.
EXA~lPLE 22 An appara-tus similar to that described in Example l is usedO
, 7~8 In the tungsten filament there are arranged 1~096 grams of pure metallic magnesium wire, whereas the one-liter flask is charged with 130 cu.cm of anhydrous ligroin containing 1 millimol of TiC14 together with 66~7 millimols of SnC14~ The magnesium is completely vaporized within 40 mins. with a vacuum of 0 09 Torr~
by keeping the flask in rotation at; -60C - - 70C. The flask is restored to the ambient temperature and pressure and s-tirring is continued during one hour approximately. During this time, the slurry disoharges its color from dark brown to grey-w}iite~ Filtra-tion is carried out on a porous G3 diaphragm, then washing with anhydrous heptane is effected and the solid is reslurried in heptane.
The analysis of the slurry gives the following results :
Ti = 5.77 millimols per liter ; ~Ig = 181 millimols per liter Sn = 170 millimols per liter ; Cl = 731 millimols per liter E~PLE 23 In the tungsten filament there is arranged 1.0 gram of pure magnesium wire. The flask is charged, in the order given, with 130 mls of anhydrous toluene and 1 millimol of TiC14~ which imparts a yellow hue to the solvent . Then, there are added, at -780C~
2 millimols of die~hylphthalate, dropwise. The solution passes from yellow to light green, There are then added 66.7 millimol of anhydrous SnC14 which imparts a yellow-orange hue: an orange oily substance settles on the flask bottom. Magnesium is vaporized during 40 mins. under a vacuum of 0.06 Torr by maintaining the flask in rotation at -780C. The flask is brought back to ambient temperature and pressure and kept stirred for about one hour.
During this time the slurry passes from dark brown to yellow. The slurry is collected on a filter, washed on anhydrous heptane and re-slurried in heptane.
The analysis of -the slurry gives the following results :
Ti = 7.74 millimols per liter ; ~Ig = 235 millimols per liter Sn = 190 millimols per liter ; Cl = 897 millimols per li-ter 19.
87 ~
EIYA~IPLE 24 In the tungsten filament there are arranged 809.5 milli-grams of pure magnesium wire whereas the flask is charged wi-th 100 mls of anhydrous toluene and one millimol of TiC14 which colors the solvent in yellow. Then there are added at room tempe-rature and with stirring 2 millimols of diethylphthalateO The solution takes a light green hue. There are further added 43~3 millimols of SnC13nBut which imparts a yellow-orange hue and an oily substance is deposited on the flask bottom. Magnesium is evaporated during 40 mins. under a vacuum of 0.07 Torr by maintain-ing the flask in rotation at -78C. The flask is brought back to ambient pressure and temperature and stirring is continued during about 2 hours at room temperature. The filurry passes from dark bro~n to light grey during this period of time. Filtration, wash-ing with anhydrous heptane and reslurrying in heptane are carried out.
The analysis of the slurry gives the following results :
Ti = 7.18 millimols per liter Mg = 66 millimols per liter Sn = 80 millimols per liter Cl = 349 millimols per li-ter EYA~LE 25 970 milligrams of pure magnesium wire are placed on the tung-sten. In the flask which contains 100 mls of anhydrous heptane and 1 millimol of TiC14~ there are added at room temperature and with stirring 60 millimols of SbC15~ distilled. The solution remains clear. By vaporizing magnesium, the suspension becomes yellow-brown: thenj a white powder is formed which gradually darkens and passes to grey and eventually to black. Filtration, washing with anhydrous heptane and reslurrying in such solvent are carried out. The analysis o the slurry gives the following results :
Ti = 4.60 millimols per liter Mg = 226 millimols per liter Sb = 95 millimols per liter Cl = 1~058 millimols per liter 20.
EIY~MPLE 26 There are placed on the -tungsten filamen-t 831,8 milligrams of pure magnesium wire. In the flask which con-tains 100 mls of anhydrous nor.heptane there are added at room temperature and with stirring, 5103 millimols of distilled POC13 and 1 millimol o TiCl40 A yello-~ precipitate is formedO Magnesium is vaporized while keeping the flask at -780C. The suspension is yellow-brown.
The flask is brought back to ambient temperature and pressure and stirring is continued during 2 hours at room -temperature . The suspension becomes pale yellow. Filtration~ washing with nor, heptane and reslurrying in this latter solvent are efec-ted.
The analysis of the slurry gives the following results :
Ti = 9.62 millimols per liter Mg = 126 millimols per liter P = 390 millimols per liter Cl = 655 millimols per liter Ethylene polymerization tests with the catalyst mixtures as prepared according to Examples from 22 to 26 have been carried out according to Example 17 ~ith a polymerization time of 2 hours with a pressure o hydrogen of 5 kilograms square centimeter and a pressure of ethylene of 5 kilograms per sq.cm. The results which have been obtained are tabulated in TABLE 3.
. . _ . . , Catalyst Specific activity in MFI21 MFI21 Apparent spec.
accordDto grams of polym,per grams/ gravity grams/
Example gram of Ti per hour 10 min~ MFI2.1 cu.cm and per a-tmosph.of C-2 ~ . . ._ 22 34,700 5.oo 36 o.3o 23 32,500 5-7 31 not determ.
24 13,000 2~90 32 no-t determ, 34,000 6g98 27 0~0 3 26 8,300 ~.32 31 no-t determ.
_ . _ _ . .
EX~IPLE ~.7 A two-necked flask, purged with nitrogen is charged wi-th lO grams of powdered polyethylene9 50 mls of anhydrous and deaera-ted nor.hexane and ~.5 milligramatoms of Al(isoBu)3.
Upon homogeneization the mixture is allowed to s-tand during two hours~ whereafter there are added, still under a nitrogen stream, 0.0075 milligramatoms of a catalyst such as titanium when prepared as disclosed in Example 17 together with 1.5 milligram-atoms of Al(isoBu)3~ Hexane is completely dis-tilled off in a vacuo at 600C. The thusly prepared material is charged under nitrogen in a well dried 2-liter autoclave, which has been deaera-ted and kept under nitrogen atmosphere. The autoclave is evacuated to remove nitrogen, whereafter ethylene is fed until reaching a gauge pressure of 1.5 kilograms per square centimeter and the tempe-rature is raised to 80C. During progress of polymerization, ethylene is fed in so as to keep constant the gauge pressure of ~.5 kilograms per square centimeter. The absorption o-~ ethylene is checked by a rotameter. Polymerization is discontinued after 5 hours. During this period of time the absorption remains constant.
There are obtained 84 grams of polyethylene corresponding to a specific activity of 16~500 grams of polymer per gram of Ti per hour and per atmosphere of ethylene~
EXA~LE 28 The exact procedure as disclosed in the previous Example has been followed~ with 2 kilograms per sq~cm of hydrogen as a mole-cular weight adjuster~ After three hours of polymerization there are obtained 56 grams of a polymer having an MFI of 2.1 grams per lO minutes.
EXA~LE 29 Copolymerization of ethylene with butene-l is carried out~using the catalyst disc:losed in Example 17, the same procedure~ the same polymeriz.ation condition and the same concentrations of catalys-t 22.
~18748 as described in tha-t Example~ The feed of butene-l is carried out concurrently with that of e-thylene by introclucing a quantity of butene-l equal -to 5% of tha-t of ethylene~ the gases being metered with calibra-ted fluxmeters 9 A-ter one hour of polymeriza-tion there are obtained 290 grams of a copolymer having an MFI of 10 grams per 10 mins. and an apparent specific gravity~ d = o~9580 grams per cu.cm. The speci-fic activity is 170~000 grams of copoly-mer per gram of Ti per hour and per atmosphere of ethyleneO
E.YAMPLE 30 Copolymerization of ethylene with hexene-l is effected using the catalyst described in Example 17 under the same conditions and concentrations as disclosed in the same Example.
The procedure is as follows :
- an autoclave is charged wi-th 1.8 liters of norOheptane containing 8 grams of anhydrous and deaerated hexene 1.
- the tempera-ture is thermostatically main-tained at 85OC.
- the catalyst is charged (~ millimols of Al(isoBu~3 and OoOl milli-gramatom of catalyst such as titanium diluted with 200 mls of n-heptane. There are charged 5 kgs/sqOcm of hydrogen and 305 kgs/sq.cm of ethylene~ During the feed of ethylene which is car-ried out continuously during the entire polymerization time (1 hour) to keep constant the total pressure, there are fed 8 grams of hexene-l diluted in 100 mls.nor.heptane by a metering pump.
After one hour of polymerization the gases are vented off, the co~
polymer is collected on a filter and driedO There are obtained 230 grams of a copolymer having an MFI = 8.5 grams/10 mins and an app.spec.grav., d = 0.9576 grams per cubic cen-time-ter. The obtain-ed specific activity is : 136,000 grams of copolymer per gram of Ti per hour and per atmosphere of e-thylene.
Claims (8)
1. A method for the preparation of a catalyst containing titanium trichloride or vanadium trichloride and useful in the polymerization and copolymerization of ethylene with higher alphaolefines, which comprises vaporizing another metal selected from the group consisting of Al, Mg, Cr, Mn, Fe, V and Ti under vacuum and reacting the vapor thus obtained with TiCl4 or VCl4at a low temperature.
2. A method for the preparation of a catalyst as claimed in claim 1, wherein the vaporization of said other metal is carried out under a vacuum in the range between 10-1 and 10-6 Torr.
3. A method for the preparation of a catalyst as claimed in claim 1, wherein the reaction between the metallic vapors and TiCl4 or VCl4 takes place at a temperature in the range between -80°C and +20°C.
4. A method for the preparation of a catalyst as claimed in claim 1, wherein the reaction takes place at a temperature in the range between -60°C and -20°C.
5. A method for the preparation of a catalyst as claimed in claim 1, wherein the reaction between the metallic vapor and TiCl4 or VCl4 takes place in the presence of an inert diluent selected from the group consisting of aliphatic, saturated, unsaturated and halogenated hydrocarbons.
6. A method for the preparation of a catalyst as claimed in claim 2, wherein the reaction between the metallic vapors and TiCl4 or VCl4 takes place at a temperature in the range between -80°C and +20°C.
7. A method for the preparation of a catalyst as claimed in claim 2, wherein the reaction takes place at a temperature in the range between -60°C and -20°C.
8. A method for the preparation of a catalyst as claimed in any one of claims 2, 6 and 7, wherein the reaction between the metallic vapor and TiCl4 or VCl4 takes place in the presence of an inert diluent selected from the group consisting of aliphatic, saturated, unsaturated and halogenated hydrocarbons.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT1974876A IT1054583B (en) | 1976-01-30 | 1976-01-30 | Titanium or vanadium trichloride prepn. - by reacting the tetrachloride with metal vapour, partic. magnesium, for obtaining olefin polymerisation catalyst |
| IT19748A/76 | 1976-01-30 | ||
| IT25257A/76 | 1976-07-13 | ||
| IT2525776A IT1065073B (en) | 1976-07-13 | 1976-07-13 | Titanium or vanadium trichloride prepn. - by reacting the tetrachloride with metal vapour, partic. magnesium, for obtaining olefin polymerisation catalyst |
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| IT1080687B (en) * | 1977-06-30 | 1985-05-16 | Snam Progetti | TRIALHYGEN TITANIUM-BASED CHEMICAL COMPOSITIONS, PROCEDURE FOR THEIR PREPARATION AND USE |
| IT1113421B (en) * | 1979-03-07 | 1986-01-20 | Anic Spa | METHOD FOR THE REDUCTION OF METALLIC ALCOXIDS AND USE OF THE COMPOUNDS SO OBTAINED |
| IT1130243B (en) * | 1980-02-01 | 1986-06-11 | Anic Spa | CHEMICAL COMPOSITION BASED ON TRIALHYGEN TITANIUM, METHOD FOR ITS PREPARATION AND PROCESS OF POLYMERIZATION OR COPOLYMERISATION OF UNSATURATED COMPOUNDS USING THE SAME |
| IT1137631B (en) * | 1981-07-29 | 1986-09-10 | Anic Spa | PROCEDURE FOR HIGH YIELD POLYMERIZATION AND COPOLYMERIZATION OF HYDRAULICALLY UNSATURATED COMPOUNDS AND MEDIA SUITABLE FOR SOCPO |
| IT1210855B (en) * | 1982-02-12 | 1989-09-29 | Assoreni Ora Enichem Polimeri | LINEAR STRUCTURE ETHYLENE POLYMERS AND PROCESSES FOR THEIR PREPARATION. |
| FR3033565B1 (en) | 2015-03-09 | 2017-03-24 | Centre Nat Rech Scient | IRON PRECATALYST AND USE THEREOF IN THE POLYMERIZATION OF OLEFINS |
| RU2707362C1 (en) * | 2019-04-05 | 2019-11-26 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Российский химико-технологический университет имени Д.И. Менделеева" (РХТУ им. Д.И. Менделеева) | Method of producing titanium trichloride |
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| DE1302122C2 (en) * | 1954-12-03 | 1979-09-13 | Montecatini Edison S.pA, Mailand (Italien); Ziegler, Karl, Dr.Dr.eh, 4330 Mülheim | METHOD FOR MANUFACTURING LINEAR HEAD-TAIL POLYPROPYLENE OR -POL-ALPHA- BUTYLENE |
| NL215885A (en) * | 1956-04-02 | |||
| AT218733B (en) * | 1957-05-28 | 1961-12-27 | Titan Gmbh | Process for the production of a new, homogeneous, anhydrous aluminum-titanium-chlorine compound |
| DE1168876B (en) * | 1962-04-28 | 1964-04-30 | Basf Ag | Process for the preparation of a complex compound of titanium trichloride and aluminum chloride |
| DE1268598B (en) * | 1964-03-04 | 1968-05-22 | Rexall Drug Chemical | Process for the preparation of a catalyst for the polymerization of alpha-olefins |
| DE1229050B (en) * | 1965-01-13 | 1966-11-24 | Basf Ag | Process for the preparation of a catalyst component which is particularly active in the polymerization of propylene using Ziegler catalysts |
| GB1299862A (en) | 1969-01-23 | 1972-12-13 | Shell Int Research | Improvements in or relating to the catalytic polymerisation of olefins |
| GB1359547A (en) | 1970-12-04 | 1974-07-10 | Naphtachimie Sa | Based catalysts |
| BE785673A (en) | 1971-06-30 | 1973-01-02 | Naphtachimie Sa | POLYMERIZATION CATALYZERS OF OLEFINS PREPARED FROM DECOMPOSED ORGANOMAGNESIANS |
| DE2158956A1 (en) * | 1971-11-27 | 1973-05-30 | Basf Ag | Prepn of violet titanium trichloride - by plasma chemical conversion of titanium tetrachloride |
| BE794323A (en) | 1972-01-20 | 1973-07-19 | Naphtachimie Sa | PROCESS FOR THE MANUFACTURE OF ATACTIC POLYOLEFIN WAXES |
| IT998599B (en) | 1972-09-18 | 1976-02-20 | Naphtachimie Sa | PROCEDURE OF POLYMERIZATION OF OLEFINS USING PRE ACTIVATED CATALYSTS |
| GB1467051A (en) * | 1974-01-03 | 1977-03-16 | Shell Int Research | Process for the production of polyolefins and catalyst therefor |
| JPS5724361B2 (en) | 1974-03-27 | 1982-05-24 | ||
| IL46858A (en) | 1974-04-17 | 1979-01-31 | Snam Progetti | Process for the polymerization of alpha-olefins,catalyst employed in said process and method for the preparation thereof |
-
1977
- 1977-01-18 GR GR52596A patent/GR60862B/en unknown
- 1977-01-18 IL IL51283A patent/IL51283A/en unknown
- 1977-01-20 CA CA000270122A patent/CA1118748A/en not_active Expired
- 1977-01-20 AU AU21472/77A patent/AU512820B2/en not_active Expired
- 1977-01-23 YU YU230/77A patent/YU39988B/en unknown
- 1977-01-25 DK DK30877A patent/DK147620C/en not_active IP Right Cessation
- 1977-01-25 TR TR19781A patent/TR19781A/en unknown
- 1977-01-26 EG EG51/77A patent/EG13429A/en active
- 1977-01-27 GB GB3437/77A patent/GB1576431A/en not_active Expired
- 1977-01-27 FR FR7702334A patent/FR2345467A1/en active Granted
- 1977-01-27 AR AR266342A patent/AR217821A1/en active
- 1977-01-27 NO NO770274A patent/NO150208C/en unknown
- 1977-01-28 SU SU772446350A patent/SU1056905A3/en active
- 1977-01-28 DE DE2759512A patent/DE2759512C2/en not_active Expired
- 1977-01-28 ES ES455759A patent/ES455759A1/en not_active Expired
- 1977-01-28 PH PH19393A patent/PH15890A/en unknown
- 1977-01-28 DD DD7700197143A patent/DD130130A5/en unknown
- 1977-01-28 IE IE189/77A patent/IE45018B1/en not_active IP Right Cessation
- 1977-01-28 JP JP52007909A patent/JPS6050806B2/en not_active Expired
- 1977-01-28 PT PT66123A patent/PT66123B/en unknown
- 1977-01-28 DE DE2703604A patent/DE2703604C3/en not_active Expired
- 1977-01-28 DD DD77205331A patent/DD138218A5/en unknown
- 1977-01-28 CH CH108477A patent/CH628597A5/en not_active IP Right Cessation
- 1977-01-28 MX MX167866A patent/MX142961A/en unknown
- 1977-01-28 LU LU76666A patent/LU76666A1/xx unknown
- 1977-01-29 IN IN133/CAL/77A patent/IN145866B/en unknown
- 1977-01-31 NL NLAANVRAGE7701005,A patent/NL172329C/en not_active IP Right Cessation
- 1977-06-14 FR FR7718179A patent/FR2345212A1/en active Granted
-
1981
- 1981-01-27 NO NO810263A patent/NO152562C/en unknown
-
1982
- 1982-07-29 YU YU1658/82A patent/YU44359B/en unknown
- 1982-07-29 YU YU1657/82A patent/YU44358B/en unknown
- 1982-12-30 MY MY212/82A patent/MY8200212A/en unknown
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