CA1137069A - Catalyst components and catalysts for the polymerization of alpha-olefines - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

Catalyst components which comprise the reaction product of a Ti compound and a Mg dihalide and which are in the form of spherical particles having an average diameter of 1 to 100 microns, a surface area of 300 to 500 m2/g, and a porosity of 0.3 to 0.4 cc/g are disclosed, as are catalysts also in the form of spherical particles prepared therefrom and useful in the polymeriztion of ethylene and of alpha-olefins CH2 = CHR in which R is alkyl radical having from 1 to 6 carbon atoms, and the polymerization of the alpha-olefins therewith.

Description

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Catalysts endowed with hi~h activity and high stereo-specificity in the polymer~zation of alpha~olefins are known.
Components essential for the preparation o~ said catalysts are:
an Al-alkyl compound partially complexed with an electron-donor compound, and a halo~enated Ti compound, preferably in the form of a complex with an electron~donor compound supported on a Mg dihalide. Some examples o~ these catalysts are described in Belgian Patent No. 848,527 The high stereospeci~ ity and the hi~hly active catalysts known sofar do not allow~ however, to obtain polymers having a controlled morpholog~ and, more particularly, in the ;~
form of particles havin~ a hi~h flowability and a narrow partic-le size distribution~ In ~eneral~ the polymers prepared .

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~3'~'~&~ , , with such catalysts have a rather broad particle size distribu-tion c~lrve and do not possess a high flo~ability.
`~ The greatest part of the particles have a size com-' prised between 1000 ana 100 microns; However, there are ll present also si~nificant fractions having a size ~bove 1,000 !I microns and below 100 microns.
I Therefore, there has been a definite need in the art j Eor the polymerization of olefins, of catalysts wlth a high I activity ~hich would allow to obtai~ polymers in the form of j particles with high 1owability -and a narrow particle size dlstribution. Moreover, in -the case of the alpha-olefins, the catalysts must also have a high stereospecificity.
USP No. 3,953,41~ describes polymerization catalysts i tha-t allow to obtain olefin polymers in the form of spheroidal '' particles having a controlled particle size distribution.
~¦ The activity and stereospecificity oE said catalys~s re not, hG~qeve~, sufIiciently high for practical use~
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THE P~ESENT INVhNTION ~;

An object of this invention is to prepare catalysts I ha~ing a hiyh acti~ity and endowed also ~ith a high stereo-specificity ~hen required, that are use Eul for preparing olefin polymers havilig high flowability and in the form of ¦ particles having a controlled particle size distribution.
¦ This and other objects are achieved by the catalysts 1:~ 25 ¦¦ pxeE~ared from the carriers and from the catalytic components of this invention.
The new catalytic components which comprise -the .
reac';ion product of a r.i compound with a Mg dihalide are in the ¦ forrn of spherical particles havinq an average diameter . , . . ' ~ i ,~ -,. I . -~-, , .
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comprised between 1 and 100 ~icrons~ a surf~ce area comprised between 300 and 500 m2/g and.a porosity comprises between 0.3 and 0.4 cubic cm/g, and are capable of forming catalysts for the polymerization of olefins. Said catalysts, ~hen used in a standard test ~or the polymerization of propylene~ yield polymers in the form of spherical particles having a flowability comprised between 12 and lS seconds (determined according to AST~I 1895-69 Method A) and a bulk density higher than 0~4 g~cm3, The catalyst cornponents that are the object oE this application are prepared by reactiny a Ti compound with a carrier consisting of or comprising an anhydrous Mg dihalide in the form of spherical particles having an average diameter comprised ; between 1 and 100 micron, a sur~ace area greater than 500 m2/g, mora particularly comprised between 700 and 900 m2~g/ and a porosity greater tllan 0.5 cc~g, . . .
Said components can be also prepared by reacting a halogenated Ti compound contalnlng at least one Ti=halogen bond, more particularly a Ti tetrahalide, such as for example, TiC14, ~:
~: with an adduct MgX2n.ED, wherein X is a halogen, n is a number :~ 20 from 1 to 3 and ED is an:electron-donor compound pre~erably containing active hydrogen atoms, such as or example alcohols, : phenol~ and water, obtained accordiny to the method described in Canadian patent application No~ 32S~269 filed June 7, 1979 and having the same assignee as the present application~
~; This method consists essentially in forming an emulsion : of an adduct by causing a homogeneous mixture of the molten - adduFt and of a liquid that is immiscible wlth and does not react i`~
with the adduct, to pass through a pipe under turbulent conditions ` and in quenching the emulsion at the outlet of the pipej thereby : - 3 ~ l ms/~~`
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causing an immediate solidific~tion of the addllct~
Among the catalyst components o~ thi's invention, those suitable ~or the' stereospecific polymerization of the alpha-ole~in$
are prepared by reacting (:a) a Ti compound, (b) a support as abo~e de~ined and ('c~ an eIectron~donor compound capable of ~orming addition compounds with the Ti compound.
Catalytic components particularly suitabl'e for the stereospecific polymerization of the alpha-ole~ins comprise the reaction products obtained by reacting (a) a Ti compound selected ~rom the halogenated compounds containing at least one ~.
Ti halogen bond, especia~ly ~hose of tetravalent Ti, with (b) ' a carrier whose surface area and porosity are'respectively '~
comprised between 700 and 90.0 m2/g and between 0.5 and 0~7 cc/g, .' in which at least 80~ o~ the particles have a particle size ~ .
: comprised be~ween.10 and 30 micron, or with ~bl) which is an adduct MgX2.nED, wherein X, n and~ED are as defined above, .
~: obtained according.to the method described in. said Canadian application No. 329,269, and with (c) an electron-donor compound ~ which does not contain active hydrogen atomst preferably selected 20 from the class of esters of organic and inorganic oxygenated acids, in particular from the es~ers o~ aromatic acids.
Halogenated Ti compounds particularly suitable for : the preparation o~ ~he catalyst components o$ this invention .
are the Ti tetrahalides, more particularly TiC14~ TiBr4 and :. I4 However, the haloalcoholates and halophenolates, such .~ as, ~or instance Ti(o n-C4H9~2Cl2~ TiOC2H5C15, and Ti(OC6H5?2C12, may also convenlently be used~ Examples of non-halo~enated Ti compounds are the: tetra-alcoholates~ for :.
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instance Ti~O-n-C~1~9)~. Tlle non-haloyenated Ti compounAs ar~
used in general Lor preparing catalysts for the polymeriza-tion I of ethylene.
The carrier may contain~ besides M~ dihalides, also S '~ OrgalliC OI' inorganic solid co-carriers which are inert to~ards the Mg compounds, especially compounds of a metal of the III
and IV group of the Mendelyeev Periodic System, such as, for instance~ SiO2~ A123' ~23' Zr2l Ti2 ', metal of Group I and IIJ such as, for instance, Na2C03, NaCl, ¦
Na2SO~, MgO, ~5gC03, Mg(OH)Cl, CaC12.
- ,, Elec-tron-donor compounds (c) suitable for the above indicated purpose are, besides the esters of oxygenated acids, - ket~nes, aldehydes, ethers, amides, compounds of phosphorus ~uch as phosphines and phosphoramides. The preferred compounds ~`~15 l are the alkyl esters of aromatic acids. Typical e~amples of these esters are the alkylbenzoates, alkyl-toluates and alkyl-anisates. ~
E-thylbenzoate, methyltoluate and methylanisate are I compounds representative of those preferred compounds. The j 20 1 esters may also be used in the form of adducts with halides of Lewis acids different from the Mg dihalides.
The Al- and Sn-halides, and in particular AlC13, are examples of useul Lewis acids.
l The electron-donor compound ~c) is preferably reacted l with the carrier before the reaction wi-th the Ti compounds. It ¦¦ is possible, however, to react the Ti compound, the carrier and ¦¦ the electron-donor compound (c) simultaneously.
It is also possible to react the Ti compound with the ¦ carrier and then to treat the solid reaction produc~ th the ¦ electron-donor compound ~c~.
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The Ti compound may also be reacted in the form o an addition compound with the electron-donor compound (~).
,~ The reaction between (a), (b) and (bl) and (c) is I condllcted under such conditions that the quantlty of eIectron-1 donor compound (c), presen-t in a combined form in thc solid product separated from the reaction mixture, is less than 1 ~i .
j~ mole per gram atom o Mg, in particular so that the quantity is comprised between 0.1 and 0.3 moles per gram atom of Mg. ¦~ I
The molar ratio between the electron--donor compound ~, (c) and the Ti compound is comprlsed between 0.2 and 3 preferably between O.S and l.S.
In order to increase the catalytic acti~ity and the stereospecificity, it is important that less than 50% by weight , !l of the tetravalent Ti compounds contained in the catalyst lS i component is extractable with TiC14 at 80C. Preferably~ the extractable Ti compounds should be less -than 20~ by weight.
¦¦ It has no~- been found, and this is another aspect of this invention, that the reaction product of the Ti compound `~ 1, and the carrier, containing or not containing the electron- -~
ll donor compound tc), maintains the morphology of the carrier, - I while the surface area and -the porosity are decreased. The ;-porosity is comprised be-t~7een 0.3 and 0.4 cc/g while the sur-face area is comprised between 300 and 500 m2/g, preferably between 350 and 400 rn2/g.
l It hasfurthermore been found that the catalyst com-¦ ponents thus obtained form catalysts for the polymerization of ¦ oleEins, which catalysts, when used in a standard polymeriza-¦ tion test as defined infra, yield polymers in the form cf l ~ spherical partlcles endowed with a flowability lower than 16 .
;~1 30 ! seconds, more particularly comprised within the range of 12-15 ~ l~ sec:nds, and showing a bulk denslty higher than 0.4 g/cc, ~'. I .

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preferably compri.sed between 0.45 and 0,5 g~cc, By the texm "standard polymerization test" is ~eant a propylene polymeri~ation test is carried out in Example 1, infra~
The carrier is prepared from adducts of formula '~ MgX2.nED, wherein X is a halogen atom~ n is a nu~ber from 2 to : 6 and ED i5 an electron-donor compound pre~erably containing active hyd.rogen atoms, such as fox instance alcohols; phenols and water, which adducts are in the form of spherical particles having an average diameter comprised between 1 and 100 microns and are obtained according to the method described in'said Canadian Patent Application No. 3~9 ~ 269~o Still another method for prepaxing adducts suitable for obtaining the carrier consists in formin~ an emulsion of the adduct with an immiscible liquid that does not react with the ' adduct, under conditions of vigorous stirring, such as for ' ~ ~ :
instance those obtainable with an Ultra Turrax T-45 ~N rotating at 10,000 RPM ~anke &~KunkeL K~Go IKA Werke) apparatus~ and ': : then hy quenching the emulsion~ the'reby causing an immediate solidification of the~adduct~
. The adducts thus abtained may be 'treated by various . methods in order to obtain the components of the catalysts of this invention. One of these methods is described in British .
Patent No. lt387~890O~

~s already indicated, the catalyst components of this ~ invention may be obtained also by reacting the adducts directly .~ with the Ti compound~ In this instance, the adduct contains :~
preferably less than 3 moles.o~ electron-donorr for instance ~ from 2 to 2.5 moles. ~hese adducts m~y be prepared by removing :,~ electron~donor ~rom the adducts containing more than 3 moles of electron-donor.

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The reaction with the Ti compound is carried out either by adding the solid adduct to undiluted TiC14 maintained at a temperat~re between about 0C and 100C or by operating in !
a hydrocarbon diluent, at rela-tively low temperatures, for : 5 example lower than 40C. The solld reaction product separated i .
: ' Erom the reaction mixture is then caused to react with a liquid Ti compound, preferably TiC14, at temperatures comprised between 80 and 135C.
I The solid reaction product is separated from the 1 e~cess of the Ti compound, at temperatures at which the undesirable Ti compounds that are extractable at 80C with h~t~ remain dissolved in the reaction medium and are removed - together therewith. When the TiCl~ is used as a reaction medium, the separation of the sOlia is carried out at tempera~
tures usually higher than 80C. It is possible, however, to ; operate at lower temperatures, provided that there are used . quantities of TiC14 sufficient for dissolving the undesired Ti ¦
compounds. It is also convenient to carry out the treatment with TiC14 more than onceO
¦I The solid is separated from -the reaction mi.xture and is then washed with an inert hydrocarbon diluent (hexane, :;
heptane, etc.,) in order to remove the last traces of unreacted Ti compound. ¦~
ahen the adduct is directly reacted with the Ti com- ~:;
1 pound in order to prepare a catalytic component for the stereo-I regular polymerization of alpha-olefins, the adduct, before tlle ~1 I reaction with the Ti compound, is reacted with an electron-,I donor compound (c) at a temperature `oetween about 0C and 100C
or the electron-donor compouna (c) is reacted simultaneously .
~: 30 with the Ti compo~md ana with the adduct. The electron-donor compound (c) can be introduced durin~ rhe preparati.on of the 'I .

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microspheroidal adduct. In these reactions, it is necessary that the quantity of electron-donor compound (c) that remains fixed on the catalyst component after ex~raction with TiCl~ at 80C for 2 hours, is at least comprised between 0.5 and 3 moles/
' gram atom of Ti. ~loreover, it is important that the catalyst `` component contains less than 50%, but pre~erably less than 20%, 1 of the Ti compound extractable with TlC~4 at 80C. I ;
~ I In both cases (after direct reaction oE the adducts - 1 with the Ti compound and in the case of the product resulting ~0 ;, from the treatments according to the British Patent No.
1,387,890), the particle size distriblltion is comprised within ~ i a narrow range of values. In general, at least 80% of the ¦ --~ ~ particles have dimensions comprised within the range of 10-30 micron, bùt in particular between 15-and 25 micron. ¦
l When the adduct is made to react according to the method described in British Patent No. 1,387,890, the adduct, , before said reaction, may be treated-with an electron-donor compound (c) or the elec~ron-donor compound (c) may be present during the treatment according -to said British patent, or it 1~ may be caused to react at the end of s~id treatmentO
The reaction between the Ti compound and the carrier, I or the adduc-t thereof with an alcohol, a phenol or with water, ¦~ l is carried out by suspending the carrier in a liquid reaction - I medium which may cor.sist of said liquid ~l~i compound or of the solution thereof in an inert hydrocarbon diluent. The reaction is preferably conducted by using~ as reaction medium,the liquid Ti co~ipound. ~ ;
~;~ I The temperature is in general comprised between room ¦i temperature and 1500C.~ In the case of TiC14, it is possible to ¦ 30 operate at its boiling tempera-ture or at lower tempeFatures, ~ I , , 9_ ~,' . . . .
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for instance between 80 and 120C. In general, it is prefer-able to ol~erate between 110 and 135C.
The reaction between the eleetron-donor compound te) and the earrier or the aciduet Mc~Xz.n~D (in the case in which the , electron--donor compound ~c) is made to react befo~e the reaction with the Ti compound) is in general earried out by suspending the earrier in a hydroearbon 501uti.0n containing the electron-donor compound (e) and by eondueting the reaction at tempera-tures comprised between room -temperature and 100C, prefer~bly between 40 and 80C.
The solid-reaction product, separated or not, from l ~1 the liquid phase, is reaeted with the Ti compound.
- , The reaetion between the adduet and the halogenated agent, as described in British Patent No. 1,387,890, is also ;l carried out by~suspending the adduct in a liquid medium con-sisting of said halogenating agents, or ~rom a solution tliereof and by eonducting the reaction generally within a temperature range comprised between room temperature and 150C.
~ The solid product is separated from the reaction 1 20 1¦ mixture, then washed and lastly reacted with the electron-donor~
¦I compound (c) an~/or with the Ti compound.
~ ll As explained above, the eleetron-donor eompound ~e~
I l¦ may also be added during the treatment with a halogenating ¦ ~agent, as described in the above-cited Bri-tish patent.
2S I The catalyst eomponents according to this invention i are mixed with organometallic compounds of a metaI belonging to ; ll grol,ps II and III of the Mendelyeev Periodic System to form eatalysts partieularly ac-tive in the polymerization of olefins.
! The polymers obtained using said eatalysts are in the il form of spherical particles of high flowability, show a flow ; ll index below 16 seeonds, more par-ticularly between 12 and 15 : . Il ., . . .
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! . ' seconds (the index was measurcd accordlng to ASTM 1~95-69 Me~hod ~. The bulk density is comprised between 0.4 and 0.5 . g/cm (determined according to ~STM 1~95-69 Method A).
More particularly, whe.n the catalyst solid component contains an electron-donor compoulld ~c) and when as co-catalyst there is used an Al-organometallic compound partially complexed.
with an electron-donor compound (c), it is possible to obtain catalysts suitable for the polymerization of alpha-olefins, that show a high activity and stereospecificity and which, moreover, ,, :
yie].d polymers, such as polypropylene, iD the forrn of particles ` having a high flowabil.ity and a narrow particle size distribu-. tion.
-~ . The electron-donor compounds (c), suitable for being complexed with the Al organometallic compounds, belong to the ~ same classes as the prevlously described electron-donor com-, polmds (c).
The quantity of electron-donor compound tc) is preferably such that at least 10% or more, in particular between 20% and 80~, of the organome-tallic Al-compound is in ~: 20 ¦1 -the form of a complex.
! Preferably there are used the alkyl esters ofaromatic acids such as, for i.nstance, the esters of benzoic or tol.uic acid and -the lilse.
l As Al compounds there are pxeferably used ~1- ~ ;
I tri.alkyls, such as for instance ~l-triethy:L, ~l-triisobutyl, etc .

I Furthex examples of useful Al-alkyl cornpounds are described in ¦ British Patcnt No. 1,387,890. The Al-trialkyls can also be l ;
¦ used in admixture with dialkyl-Al hali.des. , The Al-Ti ratio in the catalysts suitable for the ! stereospecific polymerization of the alpha-olefins in general is comprised betwee~ 10 and 1,000. ~l/Ti ratios lower than 10 I . , -11-. - I

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may be used provided that the electron-donor compound (c) i~ , not used or that it is used in a quantity below 20~ by m~les with respect to the Al alkyi compound~
In the polymerization of the olefins with the catalysts according to this invention the polyrnerization conditions are those known in the priox art.
The polymerization may be conducted in the liquid phase either in the presence or absence of an inert hydrocarbon solvent te.g., hexane, heptane, etc.), or in the gaseous phase. i ~1 The polymerization tempera-ture in general is comprised ~-, be-tween 40 and 150C, particularly be-tween 50 and 90C.
` More particularly, propylene or mixtures thereof with minor quantities of ethylene, for example lower than 25~, are polymerized with -the stereospecific catalysts of -this invention.
I The alpha-oleCins CH2 = CHR in which R is an alXyl containing from 1 to 6 carbon atoms include prop~lene, butene-l, ¦ ~;
4-Methyl-pentene-l. Mixtures of th- alpha-olefins with minor al~ounts of ethylene can be polymerized with the aid of the ,. I
present catalysts, as noted supra.
~0 - ll The polymers obtained with the catalysts of this l invention, besides being in the form of spheric particles having high characteristics of flowability, are endowed with high ¦¦ characteristics of surface area and of porosity, whereby they ¦ offer the advantage, with respect to the polymers known hereto-ij fore, of fixing more easily t:he additives such as stabilizers, dyes, etc., used generally in this field.
The examples that follow herewith are given for purely illustrative and not limiting purposes.

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EX~MPLE 1 , 49 g of anllydrous magneslum chloride, 7a . 1 g of ~- anhydrous ethyl alcohol and 1,155 ~nl of vaseline oil, produced by Montedison S.p.A. under the trade name of ROL oB/3o~ were loaded under ~n inert gas a-tmosphere and at room temperature, I
into a 2 liter autoclave fitted with a turbine stirrer and drawing pipe.
The xeaction mass was then he~lted to 120C under stirring and an adduct was obtained of MgC12 with 3 moles of i ethyl alcohol, which melted and remained mixed with the disper-sant ~vaseline oil). The autoclave was thereupon brought up to a pressure of 10 kg/cm2 by introduction of inert nitro~3en gas.
The drawing pipe of the autoclave is connected I ~
; thorugh a cock with a pipe having an inside diameter of 1 rnm ! ~i , and a length of 3 meters, said pipe being externally heated at `~ 120C.
The cock was then opened to allow the mixture to flow ! ::
through the pipe. The linear outflow rate of the mixture in the pipe was equal to about 4.5 m/sec.
11 At the outle-t oE the pipe, the dispersion was gathered in a stirred 5 liter flask containing 2.5 liter of anhydrous heptane, externally cooled and maintained at an I initial temperature of -40C. The final temperature, after collecting the emulsion coming from the au-toclave, was 0C.
1ll The spheroidal solid product that forms the dis-perse;l phase o~ the emulsion, was separa*ed by decan-ting and il filtering, was then washed ~ith heptane. ~
A11 these operations were carried out under an . I
atmosphere of an inert yas.

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After drying, carried out under vacuum and at room temperature, there wexe obtained 102 g of a solid, spherical product MgC12.2.77 C21i5OH, which, subjected to screeni.ng, ; yielded the following particle size analysis~
. micron 74-105 ~.g ., ~50 94.1 ` 11.7 y of the <50 micron fraction of the above described adduct were suspended in 80 ml of anhydrous n-heptane in a 500 ml test tube fitted with a porous diaphragm and a i . stirrer. While maintaining the temperature between 0C and 5C, ~ . ~ 20~ ml of a 0.85 molar heptane so].ution of triethyl aluminum .` we~e dripped in 1 hour, and under stirring, into the test tube.
~ 15 The whole was then heated at 80C for 2 hours. Thereafter the ' .
~ mixture was filtered and then washed five times with 120 m]. of .
, n-heptane at 80C, each time stirring for~20 minutes. The MgC12 ~1 : I tllus obtained, after drying at 45C unaer vacuum showed a ¦
~ l, specific surface~area of 844 m2/g and a porosity of 0.61 cc/g.
.~ 20 ¦ The product thus activated was suspended in ].00 ml of n-heptane :~ ¦' and into this suspension there were dripped, at room tempera-¦I.ture, in 1 hour and under stirring, 7.5 ml of a lleptane solution .. il con-taining 1.1 g of ethyl ben~oate, whereafter the whole was . heated at.80C for 2 hours. The mixtllre was then filtered and - 25 1I washed 5 times with 120 ml of heptane at 80C, each:time ~:
~ ll stirring for 20 minutes. The miY~ture was -then filtered and 1 1l dried under vacuum at 45C........ ; ~-~
li To the MgC12 were then admixed 80 ml of TiC14 under ¦ stirring, and the mix-ture was heated at 110C for 2 hours~ The .
I product was then filtered and the treatment on the solid product ~:
as repeated with further 100 ml of TiC14 for 2 hours, also at ii l~ 110C. .

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The mass was filtered, cooled down to 80~C and then washed with portions of 120 ml of heptane at 80C until attaining complete disappearance of C1 ions in the filtrate.
~rhe whole was then dried under vacuum at 45C, thereby obtain-3 ing 6.8 cJ of a solid catalytie component containing 1~64~ by ; weight of Ti and 7.3~ by weight of ethylbenzoate and showing the following characteristic~:
porosity 0.391 cc/g specific surface 393. m2/g mean pore radius 20. A.
The solid catalytic component thus prepared has been used for the suspension polymeri.zation of the propylene. 5 . millimols of a heptane solution of an Al-trialkyl mixture, having a gas composition, after hydrolysis, of~
~ ~ by volume ethane 9.
; ` isobutane 49.4 .
:, ! i ' - n-butane 41.2 I , . propane ~0.16 ~ 20 !, isobutene 0.24 are reacted at room temperature with 1.25 millimoles of methyl 1~ paratoluate diluted in 80 ml of anhydrous and de-sulphurated for 5 minutes in n-hcptane. 50 ml of this solution were put ¦
- into contact with 61 mg of the catalytic component prepared I .
. 25 l~ according to the above~described system. The remaining ~ml were Il diluted with n-heptane to 1,000 ml and were then introduced '¦ under nitrocJen pressure into a stainless steel 3,000 ml auto-:~ ~, clave, fitted with a magnetic anchor stirrer and provided with Il a thermometer, heat-regulated at 50C, into which autoclave 1¦ the yaseous propylene was caused to flow.

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The suspension of the catalytic component was then introduced in the same way. After sealing the autoclave, hydrogen was fed into it until attaining a partial pressure of 0.3 atmospheres after which the .suspension was heated up to 70C
while simultaneously feeding in propylene up to attainin~ a total pressure of 7 atmospheres. Said pressure was maintained constant for the whole duration of the polymerization while continuing -to feed in the monomer. ~fter 4 hours the poly-merization was interxupted. 220 g of polypropyelne were ; obta;ned which were separated for treatment with methanol and I I
` acetone. The results of the polymerization test are recorded in ~able I.
,' ~ - Ex~MæLE 2 ?
.
28.4 g of anhydrous MgC12 and 49.5 g of anhydrous ;; 15 , ethanol, 100 ml of vaseline oil ROL OB/30 and 100 ml of silicone oil (viscosi-ty 350 cs) were introduced, under an inert atmosphere, into a ~lask immersed in a heat stabiiized bath at 120C and under stirring until the MgC12 was completely dissolved. Thereby there was formed the MgC12 adduct with ; 20 i ethanol in admixture wi~th the oils. The hot mixture was then ¦
transEerred, still under an inert atmosphere, -to a 1,500 ml ¦¦ vessel provided with a heating jacket, and containing 150 ml of j ¦I vaseline oil and 150 ml of silicone oil. This mixtuxe was ¦ -I! maintained at 120C and kept under stirring by means of a jl stirrer of the Ultra Turrax T-45 N type produced by Janke &
~unkel K.G. Ika Werke. The mixture was stirred for 3 minutes ¦
at 10,000 rpm. Thereupon, -the mixture was discharged into a

2 liter vessel containing 1,000 ml of anhydrous n-heptane which was kept under stirring and cooled so that the final ¦
¦ temperature did not eY.ceed 0C.

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Thc Mg~12.3EtOII microspheres thus obtained, after filtering, were dried under vacuum at room tcmperature and then screened, whe~ellpon they yielded a fraction <50 micron corres-ponding to 78~ by weight. By activation as described in Exanlple 1, these microspheres yielded a solid catalytic - componen~ containillg 1.95~ by weight of Ti and 7.5~ by weight o~ ethylbenzoate, while showing the following characteristics:
porosity 0.322 cc~g speciflc surface 397. m2/g ~ mean pore radius 16. A.
- 46.3 mg of this catalytic component were used in the polymerization of propylene under the conditions indicated in Example 1. There were thus obtained 170 g of polypropylene.
The results are recorded in Table I.

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25.25 g of MgC12.2.77 C2H5OH, in the .onn of mioro~
spheres with a particle size lower than 50 micron, obtained by operating according to the process described in Example 1, were suspended in 150 ml of anhydrous n--heptane in a 500 ml ~ 20 1 flask fitted with a stirrer and immersed in a hea-t stabilized I I batb kept at 00C
In this suspension there were dissolved 21.6 ml of a l molar heptane solution of e-thylbenzoate, and it was then il allowed -to react under stirring for 10 minutes. To the suspen- ¦
1l sion, still at 0C, there were admixed 100 ml of undiluted TlCl~
The heat regulated bath was removed and the suspen- ¦
sion was allowed to warm up for 1 hour to room temperature.

Thereupon, there ~ere admixed further 150 ml of Ticl4 and the ~`, .

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suspel-sion was then heated up to 100C. The suspension was allowed to rcact for 2 hours at 100C; it was then iltered and made to react with 203 ml of undiluted TiCl~ in absence of I -solvent, under stirring for 2 hours at 135C. TiC14 was removed, the solid cooled down to 80C and then washed with n-heptane at 80C until the elimination of the Cl ions in the filtrate and the solid product was then dried under vacuum at 40C. The solid catalytic component thus obtained showed the following composition and characteristics: , ;
Ti = 3.4% by weight ethylbenzoate = 11.5% by wcight porosity = 0.30 cc/g ' 2 - , specific surace = 372. m /g mean pore radius = 16.2 A. , ;
~ 40 mg of the catalytic component were then used in a ;l heptane suspension in the polymerization of propylene according . I
to the method described in Example 1. There were obtained 225 g of polymer. The results are recordcd in Table I.

¦! EXAMPLE 4 1 9 g of MgC12.2.77 C2H5OH in the form of microspheres of less than 50 micron diameter, obtained according to the process described in Example 1, were introduced, undex a ! nitrogen atmosphere, into a 500 ml flask. Thereupon, the Ij product was kept under a stabilized heat of 60C arld a vacuum 1l was applied until the content in ethyl alcohol of the ¦ spheroidi~ed adduct was reduced from the initial 2.77 moles to ~- I residual 2 moles. The product was suspended in 150 ml of ` ! anhydrous n-heptane, whereupon it was proceeded with the titanation acc~rding to the procedures described in Example 3, -18- . ;
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e~cept that instead of 21.6 ml there were used only 7.5 ml of a I
heptane solutlon of 1 molar ethylben~oate. A catalytic solid compound was obtained sho~;ng the following composition ~nd char,lcteristics:
Ti = 1.96% by weight ethylbenzoate ~ 9.0~ by weight porosity = 0.39 cc/g specific surface = 386. m2/g ' mean pore radius = 20.2 A.
43 mg of thls catalytic component were used in heptane suspension in the polymerization of propylene according as described in E~ample 1 . I . .
There were thus obtained 182 g of polypropylene and the results are recorded in Table I.

I EXA~I,E 5 ~ ~ !
- 12 g of MgC12.2.77 C2H5V~ in the form of microspheresof less than 50 micron dlameter, obtained according to the process described in Example 1I were suspended in lOO ml of , anhydrous n-heptane in a 500 ml test tube fitted with a porous l, diaphragm and a stirrer. Main-taining the temperature at 20C, 100 ml of TiC14 were dripped into this suspension. Thereupon, the temperature was brought up to 100C and the mass was li allowed to react for 2 hours. After filtering at 100C, the solid was once again suspended in 200 ml of 'riC19 and this suspension was then maintained under stirring at 130C for 2 ! hours. Thereafter, the suspension was filtered and the solid cooled down to 80~C and repeatedly washed at 80C with fractions , !l of n-heptane until achieving the disappearance of the chlorine - i ions in the filtrate. Af~er drying, the solid catalytic ,1 .
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component contained:
Ti = 7.~3 by weight, Cl = 6.32% by ~eightO
` 8 ~ of the solid catalytic component thus prepared (c~rrespondin~ to 0.6 mg of Ti) and 1,000 ml of anhydrous ; n-heptane were introduceA, together with 2 ml of triisob~tyl aluminum, and under nitrogen atmosphere, into a stainlcss steel 3 Liter autoclave fitted with an anchor stirrer and heat stabiliæed at 85C. ¦ I
Thereupon, there were added fi atm. of H2 and ethylene up -to a total pressure of 13 atm., which was maintained con- I
stant for the whole duration of the test continuing feeding of I ;
- ~ monomer.
After 4 hours, the polymerization was interrupted and there were obtained 860 grams of microspheroidal polyetllylene, ~ corresponding to a yield of 1,430,000 g of polyethylene/g Ti, ~ith an intrinsic viscosity ~n] = 2.12 dl/g.

1l EX~ ~LE 6 i :~ ,! Into a 1,000 ml flask were introcluced 229 ml of TiC14 !
and allowed to react with 2.42 ml of ethylbenzoatel at 15~C
1l for 10 minutes. Tllereupon, at the same temperature and in 50 minu-tes, into this reac-tion mass was dripped a suspension con- l ~
taining 17.6 g oE MgC12.2.47 C2ll5OH in 25 ml o n-heptane, in 1;
the form o microspheres with a particle size of Iess than 50 microns, ob-tained by operating according to tlle process !I described in Example i. ~-I . . ':
; I On comple~ion of the addition, the telllperature was brought up to 100C and ~he reaction was completed in 90 l~ minutes. The reaction product was thereupon filtered on a ; I porous diaphragm at reaction temperature and, t1len, there were .-!
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added to the filtrate 100 ml of undiluted TiC14 after which it was allowed to react for further 2 hours at 120C.
The product obtained was filtered, the solid cooled down to ~0C ar~d washed with n-heptane at 80C, un-til chlorine 1.
ions i.n thc filtrate disappeared. The solid, i.solated by drying under vacuum, contai.ned: Ti = 3.26~ by weight, Ethylbenzoate - ~ff~ by weight. ~;
The results of the polymerixation test of propylene ; carried out under th~ same conditions as in Example 1 are recorded in Table I.
~!
. EXAMPLE 7 - ~ ;
Into a 1,000 ml flask there were introduced 437 ml of ~:
TiC14 and then cooled down-to 0C. At this temperature, in 50 ; minutes, there were introduced in small portions, alternatively, 16.90 g of MgC12.2.44 C2~I5OH (in form of microspheres with a ; particle size of less than 50~ diameter, obtained by operating -I according to the process of Example lj, and 16.3 ml of a heptane solution 1 M of ethylbenzoate. The mixture waa allowed i to react for 60 minutes, bringing the temperature slowly up to , 20C, and then, in 30 minutes, the reaction mass was heated up ¦
to 100C, at which temperature it was allowed to react for 90 minutes. Thereupon, the reaction product was filtered on a i l¦ porous cliaphragm at reaction temperature, after which there ¦ were added 200 ml of undiluted TiC14 and it was then al].owed ; 25 ,I to react at 130C f`or further 2 hours, after which the reaction produc-t was filtered, cooled down to 80C and then washed at 80C with n-heptane up to the disappearance of the chlorine .
; ll ions in the filtrate. ~Tbe so.lid, isolated by drying under 'I :'"

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vac~um, contained: Ti - 3.43~ by weight Ethylbenzoate ~ 9.50~ by weight. i :~
The results of t.he polymcrization test of propylene I :
under the conditlons of Example 1 are recorded in Table I.

S EXAMPI.E 8 1 !
14 g of MgCl2.1.9C2H50HØ8n-c4HgoH in the form of microspheres with a di.ameter below 50 micron, obtained by operating according to the process described in Example 1, were ' used fo.r the synthesis Gf a solid catalytic component foi].o~7ing :-:
the procedure of Example 7. The isolated solid sho~ed ~he following percent analysis by weight:
Ti = 2.93~
Ethylbenzoate = 9.27~. 1 ; ! .
~ ~ The results of the polymerization test of propylene ... 15 under the conditions of Example 1 are recorded in Table I.

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Claims (6)

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

1. Catalyst components for the polymerization of ole-fins, which comprise the reaction product of a Ti compound with a Mg halide, said catalysts components being in the form of spherical particles having an average diameter comprised within the range of from 1 to 100 micron, a surface area comprised between 300 and 500 m2/g and a porosity comprised between 0.3 and 0.4 cm3/g, and being capable of forming, by reaction with Al-alkyl compounds, catalysts which, when used in a standard test for the polymerization of propylene, yield polymers in the form of spherical particles having a flowability lower than 16 seconds, according to ASTM 1895-79 (A), and a bulk density higher than 0.4 g/cm3.

2. Catalyst components according to claim 1, in which the polymers in the form of spherical particles have a flowability of from 12 to 15 seconds.

3. Catalyst components according to claim l, containing in a combined form an electron-donor compounds in a molar ratio with the Ti compound of from 0.2 to 30

4. Catalyst components according to claim 1, obtained by reaction of TiCl4 with an adduct MgX2.nROH, wherein ROH is an alcohol, obtained by causing a homogeneous mixture of the adduct, in molten form, and of a liquid that is immiscible and does not react with the adduct, to pass through a predetermined path under conditions of turbulent motion and in quenching the emulsion at the outlets of said path.

5. Carriers for catalysts for the polymerization of olefins, comprising a Mg dihalide, in the form of spherical particles having an average diameter comprised between 1 and 100 micron, a surface area higher than 500 m2g and a porosity higher than 0.5 cc/g, the catalysts obtained from said carriers and from the catalyst components prepared by reacting TiCl4 with said carriers, being characterized in that, when used in a standard polymerization test, they yield polymers in the form of spherical particles having a flowability lower than 16 seconds, and a bulk.
density higher than 0.4 g/cm .

6. Carriers according to claim 5, the catalysts obtained from the catalyst components prepared by reacting TiCl4 with said carriers, being characterized in that, when used in a standard polymerization test, they yield polymers having a flowability comprised between 12 and 15 seconds