CA1142698A - PROCESS FOR PRODUCING .alpha.-OLEFIN POLYMERS - Google Patents

Abstract

Abstract of the Disclosure A process for producing .alpha.-olefin polymers is provided which comprises:
reacting an organoaluminum compound (0-A?1) with an electron donor (ED1) to obtain a reaction product (I);
reacting (I) with TiC?4 to obtain a solid product (II);
reacting (II) with an electron donor (ED2) and an electron acceptor to obtain a solid product (III);
combining (III) with an organoaluminum compound (0-A?2) and a reaction product (RP) of an organoaluminum (0-A?3) with an electron donor (ED3) ( (III), (0-A?2) and (RP) being referred to as catalyst components), and in this combination, subjecting a part or the whole of the catalyst components to polymerization treatment with an .alpha.-olefin at least in the presence-of (III) and said (0-A?2) to obtain a preliminarily activated catalyst; and polymerizing an .alpha.-olefin in the presence of the catalyst.
According to this process, even in the case of gas phase polymerization, the resulting polymer has a uniform particle size; the catalyst employed has not only a high stability but also a high activity whereby the advantages of gas phase polymerization can be fully exhibited; and further it is possible to easily control the stereoregularity of polymer.

Description

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SPECI~IC~T~ON
TITLE OF THE INVENTION
PROCESS YOR PRODUCING u-OLEFIN POLYMERS
BACKGROUND OF THE INVENTION
Field of the Invention:
This invention relates to a process. for producing ~-olefin polymers by the use of a novel catalyst which is suitable for ~-olefin polymerization, particularly gas phase polymerization, and further, as a modification of ~as phase polymerization, a combination of slurry or bulk polymerization with gas phase polymerization.
Description of the Prior Art:
It is well known that ~-olefins are polymerized by the use of so~called Ziegler-Natta catalysts comprising a compound of transition metals of IV ~ VI Groups of the Periodic Table and an organometallic compound of metals of I ~ III Groups of the Tablel including modified catalysts obtained by further adding an electron donor, etc~ theretoO
Among the catalysts~ those comprising titanium trichIoride as the component of transition metal compound have been most widely employed for obtaining highly crystalline polymers of e.g. propylene, hutene-l, etc. Such titanium trichloride is classified into the following three kinds according to its preparation:
(1) A material obtained by reducing TiCQ4 with hydrogen, followed by milling with ball mill for activation, which material has been referred to as titanium trichloride (~A).

(2) A material obtained by .reducing TiCQ4 with metallic aluminum, followed by milling with ball mill for activation, ..,~f ~j~ pc~

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which material is expre~sed by ~he yener~l formula TiCQ3 /3A~CQ3 and has been referred -to a~ titanium trichloride (AA) (3) A material obtained by reducing TiCQ~ with an organoaluminum compound, followed by heat treatment.
However, since any of these titanium trichlorides have not been satisfactory enough, various improvements have been attempted and proposed. Among them, a process has been proposed wherein a titanium trichloride obtained by reducing TiCQ4 with an organoaluminum compound is treated with an electron donor and TiCQ4 whereby the catalyst activity is enhanced and the amount of amorphous. polymer byproduced is reduced (e.g. Japanese patent application laid-open No.
34478/1972). Ho~ever, the catalysts obtained according to these processes haYe a drawback in that they are deficient in the heat stability.
Furth.er, a process has been proposed wherein TiCQ4 and an organoaluminum compound are separately mixed with a definite amount of a complex-forming agent (electron donors being a kind thereof), to obtain two mixture liquids which are then mixed toyether and reacted to prepare a solid catalyst component (.Japanese patent application laid-open No. 9296/1978).
However, this process, too, has a drawback in that the catalyst is deficient in the heat stability, as in the case o~ the above Japanese patent application laid-open No.
34478/1972.
Still further, a process wherein a uniform liquid material consistiny of an organoaluminum compound and an ether is added to TiCQ4 or TiCQ4 is added to the form~r liquid pc,6~ ' to prepare a li~uid material containing titanium trichloride ~Japanese patent application laid-open No. 115797/1977), as well as a process wherein -the above-mentioned liquid material is heated to a temperature of 150C or lower to precipitate a finely particulate titanium trichloride (Japanese patent application laid-open No. 47594/1977, e~c.) have been proposed.
However, these processes, too, have a drawback in that the catalysts are deficient in the heat stability.
On the other hand, as for processes for polymerizing ~-olefins ~herein Ziegler-Natta catalysts are employed but the phase of ~-olefins is varied, slurry polymerization carried out in a solvent such as n-hexane, etc. (e.g. Japanese patent publication No. 10596/1957), bulk polymerization carried out in a liquefied ~-olefin monomer such as liquefied propylene (e.g. Japanese patent publication Nos. 6686/1961, 14041/1963), and gas phase polymerization carried out in a gaseous monomer such as gaseous propylene (e.g. Japanese patent publication Nos. 14812/1964, 17487/1967), have been well known. Further, a process of bulk polymerization followed by gas phase polymerization has been also known (e.g. Japanese patent publication Nos. 14862/1974, Japanese patent application laid-open No. 135987/1976). Among these polymerization processes, gas phase one is advantageous in that recovery and reuse of solvent employed in polymerization as in the case of slurry polymerization process are unnecessary; recovery and reuse of liquefied monomer such as liquefied propylene as in the case of bulk polymexization process are unnecessary; hence the C05t of solvent or monomer recovery is small to simplify the equipments for producing ~-olefin polymers; etc. These gas ~pc/~f~"' phase polymerization processes, however, have had such disadvantages -that since the monomer inside the polymerization vessel is present in vapor phase, the monomer concentra-tion is relatively low as compared with those in slurry or bulk polymerization process, resulting i~ a lower reaction rate;
thus, in order to increase the polymer yield per unit weight of catalyst, it has been necessary to extend the retention time and hence make the capacity of the reactor larger, and also, in order to enhance the catalyst activity, trialkylaluminums have been modi.fied and used, resulting in reduction of the stereore~ularity of polymer~

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In the case of g~s pnase polyrnerization process, however, uneven catalyst part.icles are liable to result in uneven polymer particles. This is, in turn, liable to cause cohesion of polymer particles and clogging of polymer-discharqing port of polymer`ization vessel or transportation line, ~o make ifficult its long time, stabili~ed, continuous op~ration _ and also make the ~uality dispersion of polymers larger.
The present inventors have previously invented a polymerization process free of the above-mentioned draw~acks . even in the case of gas phase polymerization, that is, a process for producing ~-olefin polymers using a catalyst prepared by reacting a reaction product of an electron donor with an or~anoaluminum compound, with TiCQ~, in the presence of an aromatic compound to form a solid product, or reacting this solid product further with an electron donor to form a solid product;
and combining the solid product thus obtained, with an organo-aluminum compound.
~- The inventors have further made studies, and as a result, have invented a process comprising reacting an organoaluminum compound with an elec.tron.donor to obtàin a reaction product;
reacting thiS reaction product with TiC~4 to obtain a solid product; reacting this solid product with an electron donor and an electron acceptor to obtain another solid product;
combining this solid product wi.th an organoaluminum compound to obtain a caealyst; and.polymerizing.an ~-olefin in the .

;,638 Ljresence of thi~ ca-talyst (this process will be hereinafter referred to as prior invention). According to this polymeri-zation process, par-ticularly in the case of gas phase polymeri~
zation in the presence of a catalyst obtained by subjecting the catalyst of the above-mentioned process to a preliminary activation with an ~-olefin, a long time stabilized operation without forming any polymer lump has become possible even in the case of gas phase polymerization/ but the polymer yield per g of the solid catalyst component was 5,000 to 6,000 g, i.e.
the activity of the catalyst could not have been regarded as sufficient. Thus, the amount of catalyst employed could not have been reduced. If the amounts of alcohol, alkylene oxide, steam, etc. employed for killing of catalyst after production of ~-olefin polymers or for purification of polymer are reduced too much, then corrosive subs-tances remaining in polymer have often been not made unharmless, resulting in rusting of mold at the time of molding of polymer or harming the physical properties of polymerO
The present inventors have further continued studies for improvement, and as a result have found that if an unknown catalyst component is combined with the catalyst employed in the prior invention, and in this combination, the resulting catalyst components are subjected to polymerization treatment with an ~-olefin and employed for polymerization, then, even in the case of gas phase polymerization, no polymer lump is not only formed, but also the polymer yield can be sufficiently increased ~ pc~', 3~3 ., .
, and poly~er purification can be easily carried ou-t; it is possible to produce polymer, particularly polypropylene, under control of its stereoregularity; and the rate of atactic polymer formed is low, and have attained the present invention.

SUMMARY OF Tll:E: INVENTION
The Object of the preseht invention is to provide a process for producing ~-olefin polymers wherein, even in the case of gas phase polymeri~ation, the resulting polymer has a uniform particle size; ~he catalyst employed has not only a high stability but also a high activity whereby the advantages of gas phase polymerizaticn can be fully exhibited; and further it is possible to easily control the stereoregularity of polymer.
The present invention resides briefly in:
a process for produclng ~-olefin polymers which -- - comprises:
reacting an organoaluminum compound (O-A~l) with an electron donor (~1) to obtain a reactlon product (I);
reacting this reaction product (I) with TiCR4 to obtain a solid product (II);
react.ing this solid product (II) with an electron donor (ED2) and an electron acceptor (EA) to obtain a solid product ~III), .

combining this solid product (III) with an oryano-~luminum compound (O-AQ2) and a reactiorl product (RP) of an organoaluminum (O-~3) with an electron d~nor (ED3) (these three substances to be combined together wi.ll be hereinafter referred to as catalyst components), and in this combination, subjecting a part or the whole of the catalyst components to polymerization treatment with an ~-olefin at least in I the presence of said reaction product (III) and said j aluminum compound (O-AQ2) to obtain a prelimlnarily activated ¦ 10 catalyst; and polymerizing an ~-olefin or ~-olefins in the presence of this preliminarily activated catalyst.
The terms "polymerization treatment" referred to above means that a small amount of ~-olefin is brought into contact with catalyst components under polymerizable conditions and said ~-olefin is polymerized. By this poly-merization treatment, the catalyst components are brought to a state coated with polymer.
DETAILED DESCRIPTION OE' THE INVENTION
The process for preparing the catalyst employed in the present invention will be described below.

The preparation of the solid product (III) is carried out as follows:
An organoaluminum compound is first reacted with an , electron donor to obtain a reaction product (I), which is t then reacted with TiC~4 to obtain a solid product (II), which is then further reacted with an electron donor and an e~ectron acceptor to obtain a solid product (III).
T'he reaction of an organoaluminum compound (O-~Q) with an electron donor (~'Dl) is carried out in a solvent (SV), at a temperature of -20 to 200C, preferably -10 to 100C and for'a time of 30 seconds to 5 hours. The addition order of ¦ (0-AQ)', (EDl) and (SV) has'no'limitation, and the proportion of the amounts thereof employed is suitably 0.1 to 8 mols, preferably 1 to 4 mols, of an electron donor and O.S to 5Q, ¦ - preferably 0.5 -to 2Q, of a solvent, per mol of an organoaluminum.
Aliphatlc hydrocarbons are preferable as the solvent. Thus a reaction product (I) is obtained. The reaction product ~I) may be subjected to the subsequent reaction, in a state of ` liquid after completion of the reaction (which liquid will be hereinafter referred to as reaction liquid (I)), as it is, without separating the solid product (I).
The reaction of the reaction product (I) with TiCQ4 is carried out at a temperature of 0 to 200C, preferably 10 to 90C, for 5 minutes to 8 hours. ~lthough it is preferable to employ no solvent, aliphatic or aromatic hydrocarbons may be employed ' ., .

as solvent. Addition of (~), TiCQ~ and solvent may be carried ou-t in any order, and mixing of the total amount is preferably completed within 5 hours. As for the amounts of them employed for the reaction, the amount of solvent is 0 to 3,000 mQ per mol of TiCQ4, and the ratio (AQ/Ti) of the number of AQ atoms in (I) to that of Ti atoms in TiCQ~ is 0.05 to 10, preferably 0.06 to 0.2. After completion of the reaction, a liquid portion is separated and removed by filtration or decantation, followed by repeated washings with solvent to obtain a solid product (II), which may be employed in the next step in a state where it is suspended in solvent, as it is, or mav be further dried to employ the resulting solid product in the next step.
The solid product (II) is then reacted with an electron donor (ED2) and an electron acceptor (EA). Although this reaction may be carried out without employing any solvent, employment of aliphatic hydrocarbons yields preferable results. As for the amounts of them employed, 10 to 1,000 g~ preferably 50 to 200 g of (ED2), 10 to 1,000 gt preferably 20 to 500 g of (EA) and 0 to 3,000 mQ, preferably 100 to 1,000 mQ of solvent, each based on 100 g of the solid product (II) are employed.
It is preferable to admix these 3 or 4 substances at a temperature of -10 to 40C for a time of 30 seconds to 60 minutes and react them at a temperature of 40 to 200C, preferably~50 to 100C
for a time of 30 seconds to 5 hours. The order of ms/.l~\r .

addition of the solid product (II), (ED2), (EA) and solvent has no particular limitation. (ED2) and (EA~ may be reacted together in advance of mixing them with the solid product (II).
The reaction of (ED2) with (EA) is carri.ed out at a tempera-ture of 10 to 100C for a time of 30 minutes to 2 hours, and the resulting product is cooled down to 40C or lower and employed.
After completion of the reaction of the reaction product (II), (ED2) and (EA), a liquid portion is separated and removed by filtration or decantation, followed by repeated washings to obtain a solid product (III), which is employed in the next step after dried and taken out as solid matter, or in a state where it is suspended in a solvent, as it is.
The solid product (III) thus prepared is in the form of spherical particles having diameters of 2 to 100 microns, preferably 10 to 70 microns, and these particles have a narrow particle size distribution in the vicinity of the average values of -the above sizesO When the solid product (III) is observed with a microscope, it is seen that canals are present. The specific surface area of the solid product (III) is in the range of 125 to 200 m /g. On the other hand, the specific surface area of the solid product (II) is in the range of 100.to 120 m2/g. Thus, the above higher specific surface area of the solid product (III) has been brought about by reacting an electron donor (B2) and an election acceptor (E) with the solid product (II). According to the X ray diffraction spectra of the solid product (III), broad and strong diffraction.is observed in the vicinity of a lattice distance d of 4O85 A, but diffraction ms/l,~
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corresponding to the surface of d=5.~5A is not observed.
According to the surface infrared spectra measurement of the solid product (III), no absorpotion brought by hydroxyl group in the vicinity of 3,450 cm 1 is observed. The solid product (III) has a specific feature that it is thermally stable and even when it is stored at a high temperature of 30 to 50C, the performance of the resulting catalyst is not lowered, as described later, and such a high thermal stability is based on the above-mentioned structure of the solid product (III), which structure is formed under the production conditions according to the present invention.
The solid product (III) obtained above is combined with an organoaluminum compound (O-AQ2), a reaction product (RP) of an organoaluminum compound (O-AQ3) with an electron donor (ED3) and an ~-olefin (~-O) to effect a preliminary activation of catalystr and at the same time, the reaction product (RP) is adequately selected to obtain a polymer having its stereoregularity controlled.
The organoaluminum compounds employed in the present invention are expressed by the general forumal AQRnR'nX3 (n+n') wherein R and R' eaah represent a hydrocarbon group such as alkyl group, aryl group, alkaryl group, cycloalkyl group, etc.
or alkoxy group; X represents a halogen such as fluorine, chlorine, bromine or iodine; and n and n' each represent an optional number of 0 < n+n' < 3, and as concrete examples, trialkylaluminums such as trimethylaluminum, triethylaluminum, ms/¦jt~

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tri-n-propylaluminum~ tri-n-butylaluminum, tri~ utylaluminum, tri-n-hexylaiuminum, tri-i-hexylaluminum, tri-2-rne~hyl-pentylaluminum, tri-n-oc~ylaluminum, tri-n-decylaluminum, etc., dial~ylaluminum monohalides such as diethylaluminum monochloride, di-n-propylaluminum monochloride, di-i-butylaluminum monochloride, diethylaluminum monofluoride, diethylaluminum monobromide, diethylaluminum monoiodide, etc.; alkylaluminum hydrides such as diethylaluminum hydride; and alkylaluminum halides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, ethylaluminum dichlorlde, i-butylaluminum dichloride, etc.
are mentioned. Besides, alkoxyalkylaluminums such as mono-ethoxydiethylaluminum, diethoxymonoethylaluminum, etc.
! may be also employed. These organoaluminums may be employed in admixture of two or more kinds. The organoaluminum compounds I (O-AQl), (O-AQ2) and (O-AQ3) may be the same or different.
¦ As for the electron donors employed in the present invention, ! various kinds ar~ illustrated below, but it is preferable for (E~1) ,` and ~2) that electron donors composed singly or mainly (more than ~ 50~ by mol based on the total mols thereof) of ethers be employed and those other than ethers be employed together with ethers.
- ..
As for the electron donors employed, organic compounds containing at least one atom of oxygen, nitrogen, sulfur and phosphorus, .~ .
such as ethers, alcohols, esters, aldehydes, fatty acids, aromatic acids, ketones, nitriles, amines, amides, urea, thiourea, isocy~nates, azo compounds, ` - 13 -.
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phosphines, phosphites, phosphinites, t~ioethers, thioalcohols, etc. are mentioned. ~s for concrete examples, ethers 5uch ' as diethyl ether, di-n-propyl ether, di-n-butyl ether, f diisoamyl ether, di-n-pentyl ether, di-n-hexyl ether, di-i-hexyl ether, di-n-octyl ether, di-i-octyl ether, di-n-dodecyl .; ether, diphenyl ether, ethylene glycol monomethyl ether, ¦ diethylene glycol'di.methyl ether, tetrahydrofuran; alcohol~
such a~ methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, phenol, cresol, xylenol, ethylphenol, naphthol;
10 esters such as methyl methacrylate, ethyl acetate, bu'tyl formate, amyl acetate, vinyl lactate, vinyl acetate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, 2-ethylhexyl I benzoate, methyl toluylate, ethyl toluylate, 2-ethylhexyl i toluylate, me~hyl anisate, ethyl anisate, propyl anisate, ethyl ! cinnamate, methyl naphthoate, ethyl naphthoate, propyl naphthoate, butyl naphthoate, 2-ethylhexyl naphthoate, ethyl phenylacetate;
aldehydes such as acetaldehyde, benzaldehyde; fatty acids such as formic acid, acetic acid, propionic acid, lactic acid, ' oxalic acid, succinic acid, acrylic acid, maleic acid; aromatic 20 acids such as.b.enzoic acid; ketones such as methyl ethyl ketone methyl isobutyl ketone, benzophenone; nitriles such as acetonitrile; amines such as methylamine, diethylamine, tributylamine, triethanolamine, ~(N,N-dimethylamino) ethanol, ~yr~idine, quinoline, a-picoline, N,N,N',N'-tetramethyl-hexaethylenediamine, aniline, dimethylaniline; amides such as .

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formamide, hexamethyl phosphoric acid triamide, N,N,N' ,N' ,N"-pentamethyl-N~ dimethylaminoethyl phosphoric acid triamide, octamethylpyrophosphoroamide; ureas such as N,N,N',N'-tetramethylurea; isocyanates such as phenylisocyanate, toluylisoc~anate; aæo compounds such as azobenzene; phosphines such as ethylphosphine, triethylphospl~ine, tri-n-butylphosphine, ¦ tri-n-octylphosphine, triphenylphosphine, triphenylphosphine oxide; phosphites such as dimethylphosphite, di-n-octylph-~ osphite, triethylphosphite, tri-n-butylphosphite, ¦ 10 triphenylphosphite; phosphinites such as ethyldiethylphosphinite.
¦ ~thyldibutylphosphinite, phenyldip~lenylpl~osphinite; thioethers such as diethyl thioether, diphenyl thioether, methyl phenyl I thioether, ethylene sulfide, propylene sulfide; and thioalcohols i - such as ethyl thioalcohol, n-propyl thioalcohol, thiophenol, are mentioned. These electron donors may be employed in admixture. The electron donor (~) for obtainin~ the reaction product (I), (E~) to be reacted with the solid product (II) and (~) for obtaining the solid product (RP) may be the same or different, t respectively, The electron acceptors (EA) employed in the present invention are represented by halides.of elements of III Group to VI Group I of the Periodic Table. As concrete examples, anhydrous I AQCQ3, SiCQ4, SnCQ2, SnCQ4, TiCQ4, ZrCQ4, PCQ3, PCQ5, VCQq~
SbCQ5, etc. are mentioned. They may be employed in admixture.
TiCQ4 is most preferable.

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' As for the solvent, the following ones are employed:
As aliphatic hydrocarbons, n-heptane, n-octane, i-octane, etc. are mentioned. Further, in place of the aliphatic hydrocarbons or together therewith, halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloroethylene, trichloroethylene, tetrachloroethylene, etc. may be also employed. As for aromatic compounds, aromatic hydrocarbons such as naphthalene, and as their derivatives, alkyl substitutes such as mesitylene, durene, ethylbenzene, isopropylbenzene, 2-ethylnaphthalene, l-phenylnaphthalene, etc., and halides such as monochloroben2ene, o-dichlorobenzene, etc are mentioned.
Next, the process of preliminary activation by employing a combination of the solld product (III) with an organoaluminum compound (O-AQ2), a reaction product (RP) of an organoaLuminum compound (O-AQ3) with an electron acceptor (ED3), and an ~-olefin (~-O) will be mentioned beIow in detall~
The organoaluminum compounds (O-AQll, (O~A~2) and (O-AQ3) may be the same or different. The most perferable (O-AQl), (O-AQ2) and (O-AQ3~ are dialkylaluminum halides, dialkylaluminum halides and trialkylaluminums~ respectiveIy~
As for the ~-olefine (~~O) employed for the preliminary activation, straight chain monoolefins such as ethylene, ~ 16 ~
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propylene, butene-l, hexene-l, heptene-l and branched chain monoolefins such as 4-methyl-pentene-1, 2-methyl-pentene-1, 3-methyl-butene-1, and styrene, etc. are rnentioned. These olefins may be the same as or different from ~-olefins I employed for polymerization, and may be employed in admixture.
I . The electron donor (ED3) employed for preparing the reaction j product (PP) is as a whole, the same as those described in-the reaction for obtaining the solid product (III), but is not necess-ary to be indivisually the same as those employed for obtalning the solid product (III). The reaction product tRP) is usually obtained by reacting 1 mol of an organoaluminum ¦ compound with 0.01 to 5 mols of an electron donor in the ¦ presence of a solvent such as n-hexane, n-heptane, in I - an amount of 10 to 5,000 mQ based on 1 g of the organo-¦ aluminum and based on 1 g of the electron donor, at -30 to 100C
¦ for 10 minutes to 3 hours. Usually, the reaction is carried ! ` out by dropwise adding the electron d~nor diluted with the solvent to the organoaluminum compound diluted with the ` solvent.
~0 The preliminary activation may be carried out in f~ ` a hydrocarbon solvent such as propane, butane, n-pentane, ~n-hexane, n-heptane, benzene, toluene, or in a liquefied ~-ole~in such as liquefied propylene, liquefied butene-l, or in an ~-olefin gas such as ethylene yas, propylene gas.
Further, hydrogen may be made coexistent in the preliminary . activation.

:

, The preliminary activation may be carried out by subjecting a part or the whole of -the catalyst components of 1 g of the solid product (III), 0.1 to 500 g, preferably 0.5 to 50 g of an organoaluminum compound and 0.05 to 10 g of the reaction product (RP), to polymerization treatment at least in the presence of the solid product (III) and the organoaluminum compound, with 0.01 to 5,000 g, preferably 0.05 to 3,000 g of an ~-olefin. As for the conditions of the polymerization treatment, it is preferable that the temperature be in the range of 0 to 100C, preferably 10 to 70C, the time be in the range of one minute to 20 hours, and the ~-olefin be polymerized in an amount of 0.01 to 2,000 g, preferably 0.05 to 200 g per g of the solid product (III). In the polymerization treatment, 10 Q or less of hydrogen may be made present. In the preliminary activation, 50 Q or less of a solvent may be employed.
In advance of the preliminary activation, polymer particles obtained by slurry, bulk or gas phase polymerization may be made coexistent. Such polymer may be the same as or different from ~-olefin polymers as the object of polymerization. The amount of such polymer capable of being made coexistant may be in the range of 0 to 5,000 g per g of the solid product (III).
The solvent or ~-olefin employed in the preliminary activation may be removed by distilling off, filtration or ms/`^i .~ . , , ~ - ~ . . .

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the like means, midway during the preliminary activation or after completion of the activation. Further, for suspending ! the solid product in a solvent of 80 R or less per g of I the solid product, the sol.vent may be added.
¦ For the preliminary activation, there are various methods. As for the main embodiments therefox, the following are illustrated:
(1) a me~hod wherein solid product ~III) is combined ¦ with organoaluminum cosnpound (-~-Q2)' and ~-olefin (a-0) is added 1 10 to carry out polymerization treatment, followed by adding ~.
reaction product (RP);
(2) a method wherein solid product (III) is combined I with (0-AQ2) in the presence of (a-0) to carry out polymerization ! treatment with (~-O) followed by adding (RP);
! ~3~ a method wherein solid product (III) is combined j with (0-AQ2), and (RP) is added, followed by polymerization j treatment with (a-0); and ` (4) a method wherein, after ~he procedure of the above 1~ ~3), (RP) is further added.
With xegard to the methods (1) and (2) of preliminary activation, the following concrete methods are further ` ~illustra~ed:
(1-1) a method wherein solid pxoduct (III) is combined with tO-AQ2) and the resulting combination is subjected to polymerization treatment with (~-0) in vapor phase or in .. , .. ... . ~ .. , ...... .. . .. ...... , .. , . . .. , ~ ... . . . ..

liquefied a-olefin or in a solven-t, fol].owed by removing unreacted (~-O) or unreacted (~-O) and solven-t and thereafter adding (P.P);
(1-2) a method w~lerein (~P) is added without removing unreacted (a-O) or unreacted (~-O) and solvent~ in (1-1);
(1-3) a method wherein (RP) is added and thereafter unreacted (~-O) or unreacted (~-o) and solvent are removed, in (1-2);
tl-~) a method according to (1-1) ~ (1-3) wherein 10 ~-olefin polymer obtained in advance is added;
(1-5) a method according to (1-1) (1-4) wherein after preliminary activation, solvent or unreacted (~-O) and solvent are removed to obtain a catalyst in the form of powder;
(2-1) a method wherein (O-AQ2) is combined with solid . ¦
product (III) in the presence of propylene dissolved in a solvent or liquefied ~-olefin or ~-olefin gas, to carry out polymerization treatment with ~-olefin, followed by adding (RP);
(2-2) a method wherein (2-1) is carried out in the presence of ~-olefin polymer obtained in advance; and t2-3) a method wherein after preliminary acti~ation, unreacted (a-O) and solvent are removed under reduced pressure to obtain a catalyst in the form of powder.

. ` - 2 In the methods (1~ and (2), it 1s possible that a compo-nent obtained by subjecting a combination of solid product I (III) with (O-AQ2) to polymerization txeatment with (~-o) is not i mixed with (RP) at the time of catalyst preparation, but they are mixed together just before polymerization. Further, in the methods (1) - (4), it is possible to employ hydrogen ¦~ together with (~-O). Whether the catalyst is prepared in ! the form of slurry or in the form of powder affords no ~ essential difference.
¦ 10 The preliminarily activated catalyst prepared as ! mentioned above is employed for producing ~-olefin polymers.
¦ The polymerization may be carried out either by slurry ¦ polymerization in a hydrocarbon solvent or by bulk polymeri-¦ zation in liquefied ~-olè~in monomer, but, in the present ¦ invention, since the catalyst has a high activity, gas phase ¦ polymerization of ~-olefins exhibits a particularly notable ~ effectiveness, and slurry or bulk pol~merization followed ` by gas phase polymerization as a modiflcation of gas phase polymerization also exhibits a desirable effectiveness.
i 20 The gas phase polymerization of ~-olefins may be carried ` out not onl~ in the absence of solvent such as n-hexane, n-heptane, but also in a state where 0 to 500 g of solvent perKg of ~-olefin polymer is contained. Further it may be carried out either by continuous polymerization or batch polymerization. Furthermore, it may be carried out in - .

fluidized bed manner, or in f]uidized manner by way of ayitating elemen-ts, or in stirring manner hy way of vertical or horizontal type paddle.
As for the method of slurry or bulk polymerization followed by gas phase polymerization, of ~-olefins, the following are illustrated: for example, in the case of batch polymerization, a method wherein ~-olefin is poly-merized in a solvent or liquefied ~-olefin monomer, and thereafter the solvent or ~-olefin monomer is removed so that it is contained in an amount of 500 g or less per Kg of polymer particles, followed by polymerizing a-olefin in vapor phase, and a method wherein polymerization of ~-olefin is continued without removing the solvent or liquefied a-olefin, and moves into gas phase polymerization without adding any operation since the solvent or liquefied a-olefin is absorbed in the resulting polymer. A plural step polymeri-zation consisting of a combination of slurry or bulk poIymeri-zation with gas phase polymerization exhibits a desirable ~esult particularly in the case of continuous polyrnerization.
This plural step polymerization may be carried out as follows:
In the first step, slurry or bulk polymerization is carried out wherein the polymerization is continued so as to give a slurry concentration [(polymer (Kg))/(polymer (Rg) +solvent or liquefied ~-olefin (Kg))X 100~] of 70~ or higher, or the polymerization is carried out until a slurry concentration ... ~

, ~8 reaches 30 to 50~, and thereafter solvent or liquefied ~-olefin is removed so as to give a slurry concentration of 70~ or higher; and in the second step, ~-olefin is subjected i to vapor phase polymerization. In this method, the catalyst ! is added at the time of slurry or bulk polymerization of I the first step, and in the gas phase polymerization succes-¦ sively carried out, the ca~alyst of the first step may be suffic-¦ iently employed as it is, but a fresh catalyst may be also added in the second step. As for the proportion of the weight of polymer formed by slurry or bulk polymerization and that of polymer formed by gas phase polymerization, it is prefer-able that the proportion be in the range of 0.1 to 100 parts j by-weight of polymer of gas phase polymerization based on ¦ one part of polymer of slurry or bulk polymerization.
; The stereoregularity of polymer is controlled by varying the molar ratio of electron donor (ED3) to organoaluminum (O-A~3)~aS
- raw materials of reaction product (RP)(which will be hereinafter ~- referred to as molar ratio of raw materials of (RP)).
The molar ratio is varied in the range of 0.01 to 5. Lower molar ratio results in lower stereoregularity, while higher molar ratio results in higher stereoregularity.

~ - 23 ~

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As for the polymerization conditions of ~-olefins, any o~ slurry polymerization, bulk polymerization and gas phase polymerization may be carried out at a polymerization temperature of room temperature (20C) to 200C, under a polymerization pressure of the atmospheric pressure ¦ (0 kg/cm2G) to 50 kg/cm2G and usually for S minutes to 10 hours. In the polymerization, addition of a suitable amount ¦ of hydrogçn for adjustment of molecular wei~ht, and the like ¦ means are carried out as in conventional manner.
¦ 10 As for the ~~olefins employed in the polymerization ! of the present invention, straight chain monoolefins such as ethylene, propylene, butene-l, hexene-l, octene-l, etc., ! . branched chain monoolefins such as 4-methyl-pentene-1, 1 2-methyl-pentene-1, 3-methyl-butene-1, etc., diolefins such ¦ as butadiene! isoprene, chloroprene, etc., styrene, etc.
I . are mentioned. These olefins may be homopolymerized or ¦ copolymerized in combinatio~ with each other, for example, in combination of propylene with ethylene; butene with i ethylene; and;propylene wi.th butene-l. In thls case, they ' 20 may be polymerized in admixture of monomers or in a plurality .
`of steps where different ~-olefins may be employed in the first step slurry or bulk polymerization and the second step gas phase polymerization.

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The main effectiveness of the present invention consists in that even in the case of gas phase polymerization process where the monomer concentration is relatively low, a highly ~ crystalline polymer having a good form of powder can be ¦ obtained with a high polymer yield! and also the stereo-¦ regularity o~ polymer can be optionally controlled.
The effectiveness of the present invention will be further described in more detail.
The first effectiveness of the present invention is that the activity of the catalyst obtained is so high that a high polymer yield is, of course, obtained not only in the case of slurry or bulk polymerization, but also even in the case I of gas phase polymerization where the monomer concentration ¦ is relatively low, that is, the polymer yield per g of solid product (III) in the case of gas phase polymerization amounts to 7,000 to 12,000 g (polymer)~
~ `~ The second effectiveness of the present invention is '~ that since the polymer is obtained with a high yield, even if the amounts of alcohol, alkylene oxide, steam, etc. employed ' ~0 for killing the catalyst after production of ~-olefin polymers ¦ ~ or purifying the polymer are further reduced, polymer is not colored and has a yellowness index (YI) as low as O to 2.0;
further, evolution of corrosive gas having a bad effect such as degradation of physical propertiés of polymer or rusting of mold at the time of moldlng of polymer does not occur:

for example, even in tlle case where polymer is heat~d at 200C, evolution of acidic gas changing the color of a testing paper of Congo Red is not observed. - j The third effectiveness of the presen-t inven-tion is that the percentage of amorphous polymer formed at the time of produc-tion of ~-olefin polymers, is reduced, and also such effectiveness is great particularly at the time of production of copolymer. For example, in the production of propylene polymer, the amount of isotactic polypropylene as n-hexane-insoluble (20C) reaches 98 to 99.8~ in terms o isotactic index, and that of atactic polypropylene as n-hexane-soluble is only ~ ~
002 to 2~ in terms of atactic index. Thus, even when atactic polymer is not removed, disadvantages such as degradation of physical properties of polymer such as rigidity, heat stability, etc. are overcome, whereby removing step of atactic polymer can be omitted, resulting in simplification of production process of polymer.
The fourth effectiveness of the present invention is that it is possible to control the stereoregularity of polymer without increasing the amount of atactic polymer as n-hexane-soluble. ~or example, in the case of poly-propylene, it is possible to optionally control the stereoregularity of homopolymer in the range of 0.88 to 0.96 2 in terms of absorbancy ra-tio of those at 995 cm 1 to those at 974 cm , measured by infrared absorption method (which ratio wilI be hereinafter expressed by IR-I), and also the stereoregularity of copolymer in the range of 0~83 to 0.95, without increas~ in the amount of atactic polymer.
Beretofore, when the stereoregularity of homopolymer has been reduced, or wherl copolymers have been produced, for improving the physical properties of molded product of polymer such as rigidity, impact strength, heat seal temperature, etc., the amount of atactic polymer has increased. ~hereas according to the present invention, it has become possible to omit the removing step of atactic polymer and yet optionally control the stereoregularity of polymer depending on the application fields of polymer, in the production of polymer.
The fifth effectiveness of the present invention is that it is possible to optionally control the physical properties, particularly rigidity, of polymer in the range of 0.90 to 1~4X104 Kg/cm2 in terms of bending modulus. Thus it is possible to easily provide polymers suitable for various application fields ` 20 The sixth effectiveness of the present invention is that polymer particles having a good form are obtained and also the average particle size is small, tha. is, 90 to 99~ of poly.mer is in a proportion of 32 to 60 meshes pass.
The form of particles is close-to sphere; the amounts of large particles and fine particles are reduced; and .
- 2~7 -1, . . .

`:

the particle size distiribution is narrow. Further, the bulk I density (sD) of polymer is in the range of 0.45 to 0.52 and i a small area of storage tank per unit weight of polymer rnay I be sufficient; hence it is possible to make compact the plant for producing polymer; neither clogging trouble brought by I cohesion of polymer particles nor transporti~g trouble brought about by fine particles occurs; hence even in the case-of gas phase polymerization, it is possible to carry out a long time, stabilized operation.
The seventh effectiveness of the present invention is that storing stability and heat stability of catalyst are ¦ . both high. Although this effectiveness has already been observed in the above-mentioned prior invention, the effec-tiveness is maintained as it is, in the prPsent invention.
For example, even when the solid product (III) is allowed to stand at a high temperature of about 30C for about 4 months, no large reduction in the polymerization activity ¦ ` occurs; hence no particular storing equipment such as that ` for storing solid product (III~ while cooling it at abou~ 0C
is necessary, and even when the solid product (III) after combined with an organoaluminum, is allowed to stand in ~ a hlgh concentration of the solid product of 1.0% or higher, ! ~at 30C or higher, for about one week till polymerization is -- initiated, fine pulverization brought about by agitation in the catalyst tank hardly occurs, the form of polymer particles ., .
.~ , ' -is not degrad~d, and no reduction in the polymeriza-tion activity is observed. This effectiveness is remarkably enhanced by preliminary activation with a-olefin. As -a result, even when the catalyst is stored in the form of powder, reduction in the polymerization activity is small, the form of a-~olefin polymers obtained by employing ~his catalyst is good; hence the merit of gas phase polymerization is exhibited.
Example l ~l) Preparation of solid product ~III) n-Hexane (60 mQ), diethylaluminum monochloride (DEAC) (0.05 mol) and diisoamyl ether (0.12 mol) were mixed together at 25C for one minute and then reacted at the same temper-ature for 5 minutes, to obtain a reaction liquid (I) (molar ratio of diisoamyl ether/DEAC:2.4). TiCQ~ (0.4 mol) was introduced into a reactor purged wi~h nitroqen gas and heated to 35C, and thereto was dropwise added the total amount of the above~mentioned reaction liquid tI) for 30 minutes, followed ~y maintaining the resulting material at the same temperature for 30 minutes, elevating the ~emperature to 75~C, ;further reaction for one hour, cooling down to room temperature, j ~removing the supernatant li~uid, 4 times repeating a procedure of adding 400 mQ of n~hexane and removing the supernatant liquid by decantation, to obtain a solid product (II) (l9 g). The total amount oE this (II) was suspended in 300 mQ of n-hexane, .

;

and to the'resulting suspension were diisoamyl ether (16 g) and TiCQ4 (35 g) at 20C for about one minute, followed by reaction at 65C for o,ne hour. After completion of the reaction, the resulting material was cooled dow~ to room I temperature (20C) and the supernatant liquid was removed by decantation, followed by 5 tirnes repeating a procedure of adding 400 mQ of n-hexane, stirring for 10 minutes, still standing and removing the supernatant liquid, and drying under reduced pressure, to obtain a solid product (III).
~ 10 (2) Preparation of preliminarily activated cata~
t A 2 Q capacity stainless steel reactor equipped with ' slant blades was purged by nitrogen gas, and into this `, reactor were added n-hexane (20 mQ), diethylaluminum ..
monochloride (420 mg) and the solid product (III) t30 mg) ' at room temperature. Thereafter 150 mQ of hydrogen was ' introduced, and polymerization treatment was carried out by reacting them under a partial pressure of propylene of S Xg/cm G for 5 minutes (which polymerization treatment will be hereinafter abbreviated to r,eaction') (reacted propylene per g of solid product ~III): 80.0 g), followed by removing unreacted propylene, hydrogen and n-hexane under reduced ,~pressure, and thereafter adding a reaction product obtained by react,ion in n-hexane (20 mQ), triethylaluminum (85 mg) and hexamethylphosphoric'acid triamide ('llO mg) at 35C for 30 minutes, to obtain a preliminarily activated catalyst.
r ~ 30 ~

(3) Polymerizatlon of pro~ylen~_ Into the reactor containing the catalyst after completion -of the preliminary activation was introduced 150 mQ of hydrogen, and gas phase polymerization was carried out under a partial pxessure of propylene of 22 Kg/cm2G, at a polymerization temperature of 70C for 2 hours. After completion of the reaction, 3 g of methanol was i.ntroduced and killing reaction was carried out at 70C for 10 minutes, followed by cooling down to room temperature (20C) and drying the resulting polymer, to obtain 303 y of polymer. The polymer yield per y of solid product (III) was 10,100 g, the isotactic index (n-hexane-insoluble at 20C (~)), 99.0, BD of polymer, 0.48, and the polymer particles were uniform and no lump was.observed. I
No coloration of polymer was observed and yellowness index (YI) was 0.~. Further, in order to observe the extent of corrosiveness of polymer brought about by the ex-tent of heat stability of catalyst after killing, polymer was heated to a definite temperature and whether acidic gas is easily or . I, -difficultly evolved was observed through the presence or absence of color change of Congo Red (according to JIS K-6723).
As a result, no color change was observed.
Com~arative exa~le 1 Example 1 was repeated except that, in the preliminary activation of Example 1, after diethyl.aluminum monochloride-was combined with solid product (III), hydrogen was added, followed only.~y reaction of propylene, and no reaction product of triethylaluminum with hexamethylphosphoric acid triamide was added. (Catalyst preparation which is different only in no addition of reaction product (RP) of an organo-aluminum compound with an electron donor in the preliminary activation, and polymerizatlon-by the use of the thus prepared catalyst, as in the case of Comparative example 1 as compared with Example 1, will be hereinafter referred to as "Polymerization in the case of no addition of reaction product (RP) in the cor~esponding Example" in the following Comparative examples.) The resulting polymerization activity was low.
~ Comparative example 2 , Example 1 was repeated excèpt that, in the preliminary ac~ivation o~ Example 1, after diethylaluminum monochloride and solid product (III) were added, reaction product of triethylaluminum with hexamethylphosphoric acid triamide was added without reacting propylene. As a result, polymer lump formed and the polymer yield did not incrçase.
Comparative example 3 Example 1 was repeated except that, in the preliminary activation of Example 1, triethylaluminum was not reacted with hexamethylphosphoric acid triamide, but they were separately added. As a result, the polymerization activity was low and the isotactic index WdS also low.

, `:

Comparative ~
Example 1 was repeated except that, in the forrnation reaction of the reaction product (I) of ~xample 1, no diethylaluminum monochloride was employed.
Compara~ive example 5 Example 1 ~as repeated except that 0.12 mol (19 g) of - diisoamyl ether to be employed in the formatio~ reaction of-solid product (I) of Example 1 was not employed, bu-t it was instead added to 16 g of diisoamyl ether to be employed in the reaction with solid product (II).
Com~_ative example 6 Example 1 was repeated except that, in the formation reaction of solid produc-t (III) of Examyle 1, diisoamyl ether was not reacted.
Comparative example 7 Example 1 was repeated except that a reaction material obtained by adding 0.05 mol of diethylaluminum monochloride to a solution consisting of 0.4 mol of TiCQ4 and 0.12 mol of diisoamyl ether and reacting them together, was employed in place of reaction product (II) of Example 1.
Comparative example 8 Example 1 was repeated except that solid product (II) of Example 1 was employed in place of solid product (III).
Comparative example 9 Example 1 was repeated except that, in the ~ormation ~ 33 -.

reaction of solid product (III) of Example 1, TiC~4 was not f employed in the reaction with solid product tII).
. .
Exam~le 2 ;

f n-~leptane ~80 mQ), di-n-butylaluminum monochloride ¦ (0.10 mol) and di-n-butyl ether (0.30 mol) were mixed together at 30C for 3 minutes, followed by reaction for 20 minutes to obtain a reaction liquid (I). The total amount of this reaction..lif~uid (I) was dropwise added over 60 minutes to a solution consisting of toluene (50 mQ) and TiCQ4 (O . 64 ml?, ¦ 10 maintained aL 45C. The temperature of ~he resulting mixture J was elevated to 85C and reaction was further carried out for 2 hours, followed by cooling down to room temperature, removing the sup~rnatant liquid and twice repeating a procedure of adding 300 mQ of n-heptane and removing the supernatant liquid by decant-ation to obtain 49 g of solid product (II). The'total amount of ¦ this (II) was suspended in 300 mQ of n-heptane, and to the l~ ~ resulting suspension were added di-n-butyl ether (20 g) and TiCQ~ (150 g) at room temperature for about 2 minutes, followed by reaction at 90C for 2 hours, cooling, decantation, washing with n-heptane and drying to obtain a solid product ~III). Thereafter, preliminary activation of catalyst and polymerization of propylene were carried out as in Example 1, ~ (2) ànd (3).
f _mparative example 10 : Polymerization in the case oE no addition of reaction ~ -- 34 -.

~ j , , .
.
... . , .~.. . ... . - - - .. - -- - -.

prod~lct(RP) in the correspondincJ Example 2 was carried ou-t.

Com~arative example 11 -Example 2 was repeated except -that solid product (II) of Example 2 was employed in place of solid product (III) Example 3 Example 1 was repeated except that the formation reaction of solid product (II) was carried out by dropwise adding reaction liquid (I) to TiCQ4 maintained at 12C, at 12C for 45 minutes, and thereaf-ter maintaining the resulting mixture at 35C for 60 minutes. The resulting solid product (III) had a brown color.
Comparative example 12 Polymerization in the case of no addition of reaction product (RP) in the corresponding Example 3, was carried out.
Exam~e 4 Example 1 was repeated except that, in the formation reaction of solid product (II) of Example 1, the elevated temperature 75C after dropwise addition of reaction liquid tI) to TiCQ4, was changed to 65C. The resulting solid product (III~ had a brown color.
Comparative example 13 Polymerization in the case of no addition of reaction procluct (~) in the corresponding Example 4 was carried out.

Example 5 Diethylaluminum monochloride (0.057 mol) and d:iisoamyl -ether (0.15 mol) were dropwise aclded to n-hexane (40 mQ) at 18C for 5 minutes, and reaction was carried out at 35C
for 30 minutes. The resulting reaction liquid ~as dropwise added to TiCQ4 ~0.5 mol) at 35C for 180 minutes, followed by further maintaining the resulting mixture at 35C for 60 minutes, elevating the temperature to 75C! heating for 60 minutes, cooling down to room temperature ~20C), removing the supernatant liauid, and twice repeating a procedure of adding 400 mQ of n-hexane and removing the supernatant .liauid by decant-ation to obtain 24 g of a solid product (II). The total amount of this product was suspended in 100 m~ of n-hexane, and to the resulting suspension was added 12 g of diisoamyl ether, followed by reaction at 35C, for one hour, adding diisoamyl ether (12 g) and TiCQ4 (72 g) at 35C for 2 minutes, elevating the temperature to 65C, reaction for one hour, cooling down to room temperature (20C), decantation, washing with n-hexane and drying to o~tain a solid product (III). Thereafter, preliminary activation and propylene polymerization were carried out as in Example 1.
Comparative~example 14 Polymerization in the case of no addition of reaction product (RP) in the corresponding Example 5, was carried out~
Example 6 Example 5 was repeated except that, in the formatlon reaction of solid product ~I), diisopropylaluminum .
- - - 3~ -~4~
monochloride (0.06 mol) was reacted with di-n-octyl ether (0.14 mol).

Comparative example 15 . .
Polymerization in the case of no addition of reaction product ~RP) in the corresponding Example 6, was carried out.

Example 7 Example 5 was repeated except that, in the formation reaction of solid product (II) of Example 5, the amount o~
TiCQ4 employed to be reacted with reaction product (I) was made 0.12 mol.

Comparative example 16 Polymerization in the case of no addition of reaction product (G) in the corresponding Example 7, was carried out.

Example 8 Solid product (II) (2~ g) obtained as in Example 5 was suspended in 200 mQ of toluene, ana to the resulting suspension were added TiCQ4 (10 g) and di-n-butyl ether (26 g), followed by reaction at ~0C for 180 minutes, cooling down to room temperature (20C), decantation, washing with n-hexane and drying to obtain solid product (III). Subsequent preparation of preliminary activated catalyst and propylene polymerization were carried out as in Example 1.

_mparative example 17 Polymerization in the case of no addition of reaction product (RP) in the corresponding Example 8, was carried out.

ms/'~~~

_am~le 9 Triisobu-tylaluminum (0.03 mol) and di-n-dodecyl ether (0.07 mol) were reacted together in n-hexane (100 m~) at 20C for 30 minutes. The resulting reaction liquid was dropwise added to TiC~4 (0.15 mol) at 20C for 120 ~inutes, followed by maintaining the resulting mixture at 30C for 30 minutes, elevatin~ the temperature to 50C, reac-tion for 60 minutes, decantation of the supernatant li~uid, washing with n-hexane and drying to o~tain a solid product (II) (23 g), which was then suspended in 50 mQ of n-heptane. To the resulting suspension were added di-n-butyl ether (21 g) and TiCQ4 (40 g), followed by reaction at 50C for 140 minutes, cooling, decantation of the supern~tant li~uid, washing with n-hexane and drying to obtaln a solid product (III). The subseauent preparation of preliminarily activated catalyst and propylene polymerization were carried out as in Example 1.
Comparative example 18 Polymerization in the case of no addition of reaction product (~P) in the corresponding Example 9, was carried out.
The results of Examples 1 to 9 and Comparative Examples 1 to 18 are shown in Table 1.
. The terms "solid catalyst component" in this Table refer collectively to solid product (III), and solid product corresponding to solid product (III) as well as solid product (II) combined with organoaluminum, etc. and :

9~

employed for polymerization in Comparative example~. This definition also applies eo the succeeding Tables.

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l, Example 10 n-Pentane (~ m~), diethylaluminum monochloride (160 mg), solid product (III) (32 mg) obtained in ~xample l and polypropylene powder (5 g) were introduced and mixed together, follo~ed by removing n-pentane under reduced pressure. While the resulting ma-terial was fluidized in a 20Q capacity stainless steel reactor ha~ing an inner diameter of 20 cm and an inner height of 50 cm, with prop~lene gas under a partial pressu~e of propylene of 0.8 Kg/cm?G, at 30~C for 20 minutes, propylene was reacted in gas phase (reacted propylene per g of solid product (III):
1.8 g), ~ollowed by purging unreacted propylene, and adding a reaction product (RP) ob~ained by reacting triethylalurninum (30 mg) with ethyl benzoate (41 mg) in n-pentane (lO m~) at 20C for lO minutes to ob-tain a preliminarily activated catalyst, Thereafter gas phase polymerization of propylene was carried out as in Example l, (3).
Comparative example l9 Polymerization in the case of no addition of reaction product(RP) in the corresponding Example lO was carried out.
Example ll ~ .
Di~n-butylaluminum monochloride (120 mg) and solid pro:duct (III) (25 mg) obtained in ~xample 2 were introduced at 20C
into propylene (30 g), follo~ed by reaction under 9.8 Kg/cm G
- for lO minutes (reacted propylene per g of solid product (III~:
120 g). After purging unreacted propylene, a reaction product(RP) obtained by re~ctlng triisobut~laluminum (54 mg) ,' .

.

with ethyl benzo~te (30 m~) in n-^hexcnrle (1.~ mQ) at 30C
for 30 minutes was added to obt.a:irl a pre:l.iminarl].y activated ca-talyst. Thereafter ~as phase polymerization of propylene was carried out as in Example 1, (3).
C examp_e 20 Polymerization in the case of no adclition of reaction product (RP) in the corresponding F.xamp:le 11 WAS carried out.
Example 12 Diethylaluminum monochloride ~280 mg~ and solid product (III) (25 mg) obtained in E,xample 2 were introduced into n-pentane (20 m~) in the same reactor as that employed in Example 1 (2). Thereafter, while the partial pressure of propylene was elevated up to 5 Kg/cm2G at 15~C
(rate of pressure elevation: 1 Kg/cm G/min.), propylene was reacted (reacted propylene per g of solid product (III):
3~2 g). After purging unreacted propylene, a reaction product (RP) obtained by reacting trlethylaluminum (23 mg) with methyl p-toluylate (18 mg) in n-pentane (20 nQ) at 15C
for 30 minutes was added to obtain a preliminarily activated catalyst. Thereafter gas phase polymerization of propylene was carried out as in Example 1, (3).
Comparative ex ~
Polymerization in the case of no addi~ion of reaction produc-t (RP) in the corresponding Example 12 was carried out.
Examp].e 13 ~ 15 Example 12 was rep~ated except that, in -the preliminary .. ~3 ; activatior of catalyst of Example 12, the following reaction products (RPl were employed in place of reaction product of triethylaluminum with methyl p-toluylate:
Example 13: Reaction product of triisobutylaluminum (84 mg) 1 with N,N,N',N'-tetxamethylhexaethylenedi-I amine (90 mg) Example 14: Reaction product of diethylaluminum monochloride ! (24 mg), triethylaluminum (40 mg) and ethyl ¦ p-anisate (36 mg) Example 15: Reaction product of ethylaluminum dichloride - (25 mg), triethylaluminum (75 mg) and ¦ N,N,NI,N' tetramethylurea (28 mg) j Example 16 .
Example 12 was repeated except that, in the preparation . of reaction product (RP), diphenyl ether (34 mg) was employed ! in place of methyl p-toluylate. ,' - Example 17 n-Hexane (10 mQ), diethylaluminum monochloride (210 mg) and solid product (III) (28 mg) obtained in Exa~ple l'were intro duced,and further a reaction product (~P) obtained by reacting triethylaluminum (11 mg) with ethyl benzoate (15 mg) in n-hexane' (20 m'Q) at 28C for 30 minutes w'as added, follo~ed by removing ' ' n-hexane under reduced pressure. While the resulting material was fluidized with propylene under a partial pressure of propylene of 2 Kg/cm2G at 30C for 10 minutes, - ~4 -.

reactiOn was carried ou~. in ~as phase to obtain a preliminarily activated catalyst, followed by carrying out gas phase polymerization of propylene as in Example 1, (3).
Comparative example 22 Polymerization in the case of no addition of reac~lon product (RP) in the corresponding Example 17 was carried out.
Example 18 Propylene was in advance dissolved in n-hexane (100 m~) contained in the same reactor as tha-t employed in Example 1 (2), under a partial pressure of propylene of 2 Kg/cm G at 50C, and into the resulting solution were added diethylaluminum monochloride (180 mg), solid product (III) (20 mg) obtained in Example 1 and a reaction product (~) obtained by reacting triisobutylaluminum (18 mg) with methyl p-toluylate (24 mg) in n-hexane (10 mQ) at 20C for one hour, followed by maintaining the partial pressure of propylene for 7 minutes so as to give ~0 g-of reacted propylene per g of solid proauct (III), p~!rging unreacted propyler.e and.'removing n-hexane under reduced pressure. The.reafter gas phase polymerization of propylene was carried out as in Example 1, (3).
Comparative example_23 Polymerization in the case of no addition of reaction product (RP) in the corresponding Example 18 was carried out.
Exam~le 19 Example 1 was repeated except tha~, in the preparati~n .

of preliminarily activated catalyst of Example 1, ethylene was reacted in place of propylene, under 1 Kg~cm2G, at 35C
for 10 minutes (reacted ethylene per g of solid product 2.~ g).
Exam~le 20 ~ Example 1 was repeated except that, in the preparation j of preliminarily activated catalyst of Example 1, butene-1 was reacted in place of propylene, under 0.5 Kg/cm G at 35C
¦ for 10 minutes (reacted butene-l per g of solid product (III):
lQ 0.3 g).

Example 21 , I Example 1 was repeated except that diisopropylaluminum monochloride (380 mg) was employed in place of diethyl-aluminum monochloride, in Example 1, (2).
The results of Examples 10 ~ 21 and Comparative examples 19 _ 23 a.re shown in Table 2~

- ~6 -- . . . .

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N
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. ~ , ..

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P~ ~ O O O O OO O O O O O O U~ O O O O
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r l ~1 P~ .1 . ~~ ~-- N ~ ~r~l NCO N r-l N N

rl )-I aJ r-l1.l (11 r~lh ~) r~ .4 (11 . I ~ C~l r~l z O ~ ~ ) P~ P~ ~rJ P~
Z ~ O rl ScO ~rl ~O rl ~ O rl X O rl ~ z hl c ~ W
_ _ 3 Example 22 After a preliminarily activated catalyst was obtained as in Example 12, 300 mQ of hydrogen and then 600 g of propylene were introduced into the reactor holding the catalyst, and bulk polymerization was carried out at 70C under a partial pressure of propylene of 31 Kg/cm2G, for 2 hours. After completion o the reaction, unreacted propylene was purged and post-treatment was carried out as in Example 1 to obtain a polymer.
Example 23 ~ After a preliminarily activated catalyst was obtained as in Example 12, 300 mQ of hydrogen and then 200 g of propylene were introduced into the reactor holding the catalyst, and bulk polymerization was .. . . . ..
- carried out at 60C, under a partial pressure of propylene of 26 Kg/cm2G for 30 minutes to polymerize 35 g o~ propylene.
Thereafter, while the resulting slurry.containing unreacted propylene was flushed into a fluidized bed reactor having a diameter of 20 cm and a volume of 20 Q and equipped with agltating elements, and propylene was circulated at a flow rate of S cm/sec. at a reaction temperature of 70C under a partial pressur~
o~ propylene of 21 Kg/cm G, to fluidize polymer, gas phase polymerization was carried out for 2 hours. The subsequent ~-post-treatment was carried out as in Example 1.
Example 24 Bulk polymerization was carried out under 26 Kg/cm2G, at 60C for 30 minutes as in Example 23. Thereafter, unreacted liquefied propylene was transferred to a separate feed tank connected to the reac~or, and the temperature of the reactor was elevated to 72C. While propylene was fed from the feed tank to the reactor so as to give a polymeri-zation pressure of 26 Kg/çm2G, gas phase polymeri~2tion was carried out for 2.hours. ~ e subsequent post-treatment was i carried out as itl Example 1.
Example 25 ¦ Bulk polymeriza~ion was carried out under 26 Kg/cm G
at 60C for 30 minutes as in Example 23. Thereafter, when the polymerization temperature was elevated to 70C, the polymerization pressure became 31 Kg/cm2G. When ~he poly-merization was continued as it was, the pressure lowered down to 26 Kg/cm2G during 40 minutes; thus bulk polymerization ` moved continuously to gas phase polymerization. While propylene was fed so as to maintain the pressure,at~26K~/cm G, ~as phase polymerization was carried out for additional 60 minutes. The subsequent post-treatment was carried out as in Example 1 to obtain a po~ymer.
Example 26 , n-Hexane ~1,000 m~), diethylaluminum monochloride (206 mg) and solid product tIII) (18 mg) obtained in Example 2 we~e introduced into a reactor, and propylene was reacted under a partial pressure of propylene of 1.2 Kg/cm G, at 20~C, for 10 minutes (reacted propylene per g Oe solid product (III):

.

~, , .

.. . . , ~ , . . . . .

0.6 g). Thereafter, unreacted propylene was purged, ~nd a reaction product (~P) obtained by reacting triethylaluminum (23 mg) with methyl p-toluylate (24 mg) in n-hexane (20 mQ), at 20C for 30 minutes, was added to obtain a' preli~inarily ~ activated catalyst. Thereinto was 150 mQ of hydrogen, and slurry polymerization was carried out under a partial pressure of propylene of 13 ~g/cm2G at 70C for 3 hours, followed by removi'ng n-hexane by steam stripping to obtain a polymer.
Comparative exam ~
Polymerization in the case of no addition of reaction product (~P) in Example 26 was carried ou..
Example 27 A preliminarily activated catalyst was obtained as in Example 26 except that 80 mQ of n-hexane was employed in place of l~OO mQ thereof. Thereafter hydrogen (200 mQ) was introduced into the reactor holding the catalyst, and slurry .... . ... . . . ... . . ..
polymerization was carried o~t under a partial pressure of propylene of 10 Kg/cm G, at 70~C for 60 minutes to polymerize 60 g of propylene (polymerized propylene per g of solid product ~III): 3,300 g). The resulting slurry containing solvent and unreacted propylene was introduced into a ,fluidized bed equipped with agitating elements to carry ~' out gas phas,e polymerization as in ~xample 23.
Example 28 , n Hexane (200 mQ), diethylaluminum monochloride (1.8 g) .

and solid product (III) ~0.3 g) obtained in Example 2 were put in a fluidized bed reactor eauipped wlth agitating elements, used in Exa-mples 23, and propylene was reacted under a partial pressure of propylene of 1.5 Kg/cm2G, at 25C for lO minutes (reacted propylene per g of solid product (III): l.l g). Further, a reaction product (RP) obtained by reacting t~iethylaluminum (0.45 g) with methyl p-toluylate (0.36 g) in n-hexane (80 m~) at 20C for 5 hours was added to obtain a preliminarily activated catalyst. Hydrogen (3,000 mQ) was put in the reactor holding the catalyst, and propylene was reacted under a partial pressure of propylene of 21 Xg/cm G at 70C under its circulation at a rate of 5 cm/sec. Initially slurry polymerization was carried out, but after one hour (polymerized propylene per g of solid product (III): 5,200 g), polymer began to cause fluidization, and gas phase polymerization was carried out for addi.tional one hour. After polymerization, post~treatment was carried out as in Example l to obtain a pol~mer.
Compaxative example 25 -- ~ .
Polymerization in the case of no addition of reaction product(RP) in Example 28 was carried out.
~xample 29 --Solid product (III) obtained as in ~xample 1 was stored at 3~C for 4 months. Thereafter, propylene was polymerized as in Example l (2) and (3).

~ 51 -.

Example 30 ~ preliminarily activated ca~alyst obtained as in Example 12 was allowed to stand wit~1 stirriny at 30C for one week, collowed by polymerizing propylene as in Example 12.
Comparative exa~ple 26 Catalyst preparation was carried out as in Example 12 except that after diethylaluminum monochloride and solid product (III) were introduced into n-pentane, propylene was not reacted. Thereafter the catalyst was allowed to stand with stirring at 30C for one week, followed by polymerizing propylene as in Example 12. ~olymerization activity was notably reduced; also polymer BD was reduced;
and polymer lump formed.
The results of Examples 22 ~ 30 and Comparative examples 24 ~ 26 are shown in Table 3~

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-- 53 _ Exam~le 31 Employiny the catalyst ob-tained in Example ~, ethylene polymerization was carried out under a partial pressure of hydro~ene of 12 Ky/cm2G and a partial pressure of ethylene of 12 Kg/cm G, at 85~C.
Example 32 ~ polymer (propylene-ethylene ~loc]; copolymer) was obtain~
ed as in Example 27 except that the slurry polymerization of the first step was carried out with propylene, and the gas phase polymerization of the second step was carried out with ethylene uncler a partial pressure of hydrogen of 8 Kg/cm and a partial pressure of ethylene of 12 Kg/cm2G at 70C
for 2 hours, Examp e 33 A polymer (propylene-ethylene copolymer) was obtained as in Example 23 except that an olefin mixture of 200 g of propylene with 20 g of ethylene was employed in place of 200 g of propylene.
Example 34 A polymer (propylene-butene-l copolymer) was obtained as in Example 33 except that 30 g of butene-l was employed in place of 20 g of ethylene.
Example 35 Employing a prel.iminarily activated catalys-t obtained as in Example 1, (1) and (2) except that 320 mg of 3~

triethylaluminum was employed in place`of diethylaluminum monochloride in Example 1 (2), ethylene polymeri~ation was carried out as in Example 31.
Example 3 6 Diethylaluminum mor.ocl~]oride (941 mg), solid product (III) 480 mg) obtained in ~xample 1 and a reaction p~roduct (RP) ~132 mg) (molar ratio: 0.30) obtained by reacting triethyl-aluminu~ (95 m~)~(0.83 ~,mol) with methyl p-toluylate (37 mg) I (0.25 m~ol) in n~}lexane (300 ml) at 28C for o~e hour, were ¦ 10 added to n-hexane (500 mQ), ancl propylene was ! reacted under a partial pressure of propylene of 2 Kg/cm2G
at 35C for 10 minutes (reacted propylene per g o~ solid product (III): 17 g), followed by purging unreacted propylene to obtain a preliminarily activated catalyst. Successively, 3,900 m~ of hydrogen was introduced, and while ethylene was ! fed at a rate of 1.6 g/min. under a partial pressure of propylene o~ 22 Kg/cm2G, propylene-ethyle~e copolymerization was carried out at 60C for 120 minutes. Ethylene content in the polymer was 3.4%.
Comparative example 27 Polymerization in the case of no addition of reaction .~product(RP) in Example 36 was carried out`
Comparative exam~les 28 ~ 30 Example 36 was repeated except that, in the preliminary - activation of Example 36, triethylaluminum ~95 mg) (0.83 mmol) .. .. ..... v, .. ,., .. ,, ~".. .. .. . . . . . . . ........ .. . . . . .

3~3 (Comparative example 28) or metllyl p-toluylate (37 mg) (0.25 mmol) (Comparative example 29) was employed in place of reaction produc-t (~P), or triethylaluminum (95 mg~ was not reacted wi-th methyl p-toluylate (37 mg), but they were separately and at the same time added (Comparative example 30). In any of these cases, atactic polymer increased.
Comparative example 31 Example 36 was repeated except that, in the preparation of the preliminarily activated catalyst, no propylene was reacted. Polymer lump formed and polymer yield did not increase. I
Example 37 Example 36 was repeated except that ethylene was fed at a rate of 2.3 g/min. Ethylene con-tent in polymer was 5.1~.
The results of Examples 36 and 37 and Comparative examples 27 _ 31 are shown in Table 4.

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- - _ 57 _ .

Example 38 Triethylaluminum (0.07 mol) was mixed ~Jlth di-n-propyl ether ~0.15 mol) in n-octane (~5 mQ) at 20C for 2 minutes and then they were reacted tocJether at the same temperature for 30 minutes to obtain a solid product (I), which was then dropwise added to TiCQ4 (0.6 mol) at 32C over 4 hours, - followed by maintaining the temperature at 35C for one hour, - further elevating the temperature to 78C, reacting for 2 hours, cooling down to room temperature (20C), removing the sUpernatar~t liguid, 5 times repeating a procedure of adding 400 mQ of n-hexane and removing the~supernatant liquid by decantation, confirming that TiC~ was not detected in the decanted liquid, filtration and drying to obtain 23 g of a solid product (II).
Di-n-pentyl ether (47 mQ) and anhydrous AQCQ3 (5 g~ were added to n-heptane (300 mQ) and they were reacted together at 80C for 2 hours to dissolve anhydrous AQCQ3, followed .
by cooling down to 30C, adding the above-mentioned solid product (II) (23 g), reaction at 80C, for 2 hours, cooling down to room temperature, removing the supernatant liquid by decantation, 3 times repeating a procedure of adding 300 m~ ¦
of n-hexane and removing the supernatantliquid by decantation `filtration and drying to obtain a solid product (III).
The subsequent preliminary activation of catalyst and propylene polymerization were carried out as in Example l, l~
(2) and (3).

- 5~ -Example 39 In place of the reaction of reaction product (II) with . - diisoamyl ether and TiCQ~ in ~xample 1, diisoamyl ether ~38 g), SiCQ4 (12 g) and TiCQ~ (17 g) were added to n-hexane . (200 mQ) at room temperature (20C) for about one minute, followed by adding solid product ~II) (19 g), reaction at ¦ 75C for 2 hours, washing with n-hexane and drying to obtain ¦ a solid product (III). The subsequent preliminary activation of catalyst and propylene polymerization were carried out as ¦ 10 in Example 1, (2) and.(3).
t Comparative example 31 I Example 1 was repeated except that, in the preparation of solid product ~III), after the reaction of TiCQ4 with reaction product (I), the supernatant liquid was not removed, but il . n-hexane was added so as to give 300 mQ, and the resulting liquid was employed in place of the suspension of solid - product ~ , for the subsequent reaction with diisoamyl ether and TiCQ4.
Comparative example 32 Example 1 was repeated except that, in the preparation of solid product(III)of Example 1, n-hexane (60 mQ) and .~diethylaluminum monochloride (0.05 mol) were added to a solution consisting of TiCQ~ (0.4 mol) and diisoamyl ethe~ (0 12 mol), at 35C for 30 minutes, followed by maintaining the temperature at the same one ~or 30 minutes, .

. ~ .. .. . . . . ... . . .
i' elevatinc3 the -temperature to 75C, reaction Eor adclitional one hour, cooling down to room temperature, and washinc; with n-hexane, to obtain 19 c3 of a solid product, which was employecl in place of solid product (~
The results of ~xamples 38 and 39 and Comparative - exaMples 31 a~d 32 are shown in Table 5.

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o`- o o ~i i~ a o ~: .__ _._ t ~t ~ O O C~ O
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:

Example 40 Into a stainless steel reactor equipped with slant blades, were introduced n-hexane (800 mQ), die~hylaluminum monochloride (2,880 mg) and solid product (III) (540 mg) obtained in Example 1, at 20C and propylene was reacted under a partial pressure of propylene of 1.5 Kg/cm G at 20C
for 7 minutes (reacted propylene per g of solid product (III):
14 g), following by purging unreacted propylene, and adding reaction product (RP) (419 mg), obtained by reacting triethylaluminum (181 mg) (1.59 mmol) with methyl p-toluylate (238 mg) (1.59 mmol) (molar ratio: 1.0) in n-hexane (200 mQ) at 20C for 3 hours, to obtain a preliminarily activated catalyst. Successiv~ly, hydrogen (7,200 mQ) was introduced, and gas phase polymerization was carried out under a partial pressure of propylene of 22 Kg/cm G, at a polymerization temperature of 70C for 2 hours9 followed by adding 49 g of methanol, killing reaction at 70C for one hour, cooling down to room temperature (20C) and drying to obtain a polymerO
This polymer was pressed at 200C under 10 Kg/cm G for 3 minutes to obtain a film, which was then water-cooled, annealed at 135C for 120 minutes and subjected to measurement of IR-I accordiny to Luongo's method (see J.P. Luongo, J.
Appl. Polymer Sci., 3, 302 (1960)) and also to measurement of bending modulus according to JIS K-72030 Further, other m~asurement values were obtained as in Example 1.

ms/`J~

.

' Examples 41 _ 44 Example 40 was repeated except that the amount of methyl p-toluylate employed was varied as follows:
Example 41 -- 477 mg (3.18 mmol) (moiar ratio of raw naterials of ~ (RP-): 2.0, amount of (RP): 658 mg) Example 42 -- 119 mg (0.79 mmol) (molar ratio of raw naterials of (-RP): 0.50, amount of ~RP): 300 mg) Examp]e 43 -- 60 mg (0.4 mmol) (molar ratio of raw materials of (RP): 0.25, amount of (RP): 241 mg) Example 44 -- 36 mg (0.24 ~nol) (molar ratio of raw materials of (RP): 0.15, amount of (~P): 217 mg) Comparative example 33 Example 40 was repeated except that no reaction produc~ (RP) was added in the catalyst preparation.
Comparative example 34 Example 40 was repeated except that triethylaluminum (181 mg) (1.59mmo~ was employed in place of reaction product(~) , in the catalyst preparation. Atactic polymer increased.
-- Comparative examples 35 _ 39 .
Example 40 was repeated except that, in the catalyst preparation, the following various amounts of mçthyl p-toluylate were employed in place of reaction product(~) :
Comparative ex. 35 -- 477 mg (3.18 mmol) " ~ " 36 -- 238 mg (1.59 mmol) " " 37 -- 119 mg (0.79 mmol) " " 38 -- 60 mg (0.4 mmol) " 39 -~ 36 mg (0.24 mmol) IR-~s and-bending moduli were unchanged.

~ 63 -.

. The results of Examples ~0 ~ 4~ and Comparative examples 33 ~ 39 are shown in Tab].e 6.
Figures 1 and Z show the infrared spectrum of the products of example 45 and comparative example 40, respectively~

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Example 45 and Comparative example ~0 Example 45 The solid product (III) obtained in Examples 1, 2, 5 and 8 were subjected to measurements of specific surface area and surface infrared spectra, X ray diffraction, analyses of AQ, Ti, CQ and diisoamyl ether and observation with an optical microscope. The results are shown in l'able 7 and Infrared spectra Fig. 1.

(1) Measurement of specific surface area:
Specific surface area was measured at the temperature of liquid nitrogen, according to one point sET method, employing Micromeritics specific surface area-automatic measurement apparatus 2200.

(2) Measurement of surface infrared spectra The diffuse reflection spectra of samples sandwiched between two KRS-S plates were measured employing Fourier transform spectrophotometer (JIR-400) manufactured by Nihon Denshi Kabushiki Kaisha (3) X ray diffraction- .
X ray diffraction was carried out according to powder method empLoying a goniometer (PMG-S2) manufactured by Rigaku Denki Kabushiki Kaisha and also employing Cu Ka line (~ = 1.54~) and Ni as filter, at ~0 KV and 20 mAO

(4) Analysi.s of composition:
Weighed samples were decomposed with water, folLowed ~ 66 -ms~

by analyzing A~ and Ti according to atom absorption method.
EIe^tron donors were extracted with n-hexane, ollowed by measuxement according to gas chromatography. The content was calculated from the calibration curve.

(5) Obser~ation with optical microscope:
Samples sandwiched between glass plates were observed by an optical microscope tmanufactured by Olympus Kogaku Co.).
Com~arative example 40 ~ or comparison, a catalyst complex prepared according to Example 1 described in the specification of Japanese ~atent application laid-open No.Sho 47-34478/1972 (USP ~,210,738) was measured. The results are shown in Tab}e 7 and Infrared spectra Fig. 2.

- In Figs. 1 and 2, measurement was carried out under the following conditions: sampling rate: 1,00, resolution:
4 00 ard tlmes: 300.

~' '' .

, .
~ 67 -.

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. Substituting the .catalyst complex obtained in Comparative example 20, for the solid produck (III), propylene polymerizati.on was carried out as in Example 1.
The polymer yield per g of the catalyst complex was g,700 g. . .
Example 46 and Comparative example 42 The solid product ~III) obtained in Example 1 and the catalyst compiex obtained in Comparative example 40 were heated in nitrogen gas atmosphere at 55C for 4,days, followed by cooling and then propylene.
polymerization as in Bxample 1. The solid product (III) obtained in ~xample 1 was superior in the thermal stability and the reduction in the polymer yield was 5 ~, Gr less, whereas, in the case of the catalyst complex obtained in Comparative example 40, the reduction in the polymer yield was as high as 75~. The results are in Tab].- 8,.

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... .

Claims (18)

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

1. A process for producing .alpha.-olefin polymers which comprises:
reacting one mol of an organoaluminum compound (O-A?1) with 0.1 to 8 mols of an electron donor (ED1) in a solvent at a temperature of -20° to 200°C, to obtain a solid product (I);
reacting this solid product (I) with TiC?4 in a ratio (A?/Ti) of the number of atoms of aluminum to that of Ti in TiC?4, of 0.05 to 10, at a temperature of 0° to 200°C, and thereafter removing the resulting liquid portion and TiC?4 freed by washing, to obtain a solid product (II);
reacting 100 g of this solid product (II) with 10 to 1,000 g of an electron donor (ED2) and 10 to 1,000 g of an electron acceptor at a temperature of 40° to 200°C, to obtain a solid product (III);
combining 1 g of this solid product (III) with 0.1 to 500 g of an organoaluminum compound (O-A?2) and 0.05 to 10 g of a reaction product (RP) obtained by reacting 1 mol of an organoaluminum compound (O-A?3) with 0.01 to 5 mols of an electron donor (ED3) at a temperature of -30° to 100°C, (the substances employed in this combination being hereinafter referred to as catalyst components), and in this combination, subjecting a part or the total of the catalyst components to polymerization treatment with 0.01 to 5,000 g of an .alpha.-olefin, at least in the presence of said solid product (III) and said organoaluminum compound (O-A?2), to obtain a preliminarily activated catalyst; and polymerizing an .alpha.-olefin or .alpha.-olefins in the presence of this preliminarily activated catalyst.

2. A process according to Claim 1 wherein said polymerization is carried out by gas phase polymerization.

3. A process according to Claim 1 wherein said polymerization is carried out by slurry polymerization followed by gas phase polymerization.

4. A process according to Claim 1 wherein said polymerization is carried out by bulk polymerization followed by gas phase polymerization.

5. A process according to Claim 1 wherein said organoaluminum compounds (O-A?1), (O-A?2) and (O-A?3) may be the same or different and are expressed by the general formula:
A?RnR'n'x3-(n+n') wherein R and R' each represent an alkyl, aryl, alkaryl, cycloalkyl or alkoxy group; X represents fluorine, chlorine, bromine or iodine; and n and n' each represent an optional number of O < n+n' ? 3.

6. A process according to Claim 1 wherein said electron donors (ED1), (ED2) and (ED3) may be the same or different and each are one or more members selected from the group consisting of ethers, alcohols, esters, aldehydes, fatty acids, aromatic acids, ketones, nitriles, amines, amides, urea, thiourea, isocyanates, azo compounds, phosphines, phosphites, phosphinites, thioethers and thioalcohols.

7. A process according to Claim 1 or Claim 6 wherein (B1) and (B2) are each composed mainly of ethers,and electron donors other than ethers are employed together with ethers.

8. A process according to Claim 1 wherein said electron acceptor is one or more members selected from the group consisting of anhydrous A?C?3, SiC?4, SnC?2, SnC?4, TiC?4, ZrC?4, PC?3, PC?5, VC?4 and SbC?5.

9. A process according to Claim 1 wherein said solvent is an aliphatic hydrocarbon.

10. A process according to Claim 1 wherein said reaction of said reaction product (II) with said electron donor (B2) and said electron acceptor is carried out in an aliphatic hydrocarbon.

11. A process according to Claim 1 wherein said reaction of said reaction product (II) with said electron donor (B2) and said electron acceptor is carried out by reacting, in advance, said electron donor (B2) with said electron acceptor at a temperature of 10° to 100°C for 30 minutes to 2 hours, cooling the resulting reaction product down to 40°C or lower and reacting this reaction product with said reaction product (II).

12. A process according to Claim 1 wherein said preparation of preliminarily activated catalyst is carried out by combining said solid product (III) with said organoaluminum compound (A2), subjecting the resulting combination to polymerization treatment with an .alpha.-olefin and thereafter adding said reaction product (G).

13. A process according to Claim 1 wherein said preparation of preliminarily activated catalyst is carried out by combining said solid product (III) with said organoaluminum compound (A2) in,the presenee of an .alpha.-olefin to thereby subject the former both to polymerization treatment with said .alpha.-olefin, and thereafter adding said reaction product (G).

14. A process according to Claim 12 or Claim 13 wherein the material obtained by said polymerization treatment and consisting of said solid product (III), said organoaluminum compound (A2) and a polymer of said .alpha.-olefin, and said solid product (G) are separately stored and mixed together just before said polymerization and employed as the catalyst therefor.

15. A process according to Claim 1 wherein said preparation of preliminarily activated catalyst is carried out by combining said solid product (III) with said organoaluminum compound (A2), adding the resulting combination to said solid product (G), and thereafter subjecting the mixture to polymerization treatment with an .alpha.-olefin.

16. A process according to claim 1 wherein said preparation of preliminarily activated catalyst is carried out by combining said solid product (III) with said organoaluminum compound (A2), adding the resulting combination to said solid product (G), subjecting the resulting mixture to polymerization treatment with an .alpha.-olefin and thereafter further adding said reaction product (G) to the thus treated material.

17. A process according to claim 1 wherein said polymeri-zation treatment is carried out so that the polymerized amount of said .alpha.-olefin can be 0.01 to 2,000 g per g of said solid product (III).

18. A process for producing .alpha.-olefin polymers which comprises:
reacting one mol of an organoaluminum compound (Al) with 1 to 4 mols of an electron donor (B1) in 0.5 to 5? of an aliphatic hydrocarbon solvent at a temperature of -10°
to 100°C, to obtain a solid product (I);
reacting this solid product (I) with TiC?4 in a ratio (A?/Ti) of the number of atoms of aluminum to that of Ti in TiC?4, of 0.06 to 0.2, at a temperature of 10° to 90°C, and thereafter removing the resulting liquid portion and TiC?4 freed by washing, to obtain a solid product (II);
reacting 100 g of this solid product (II) with 50 to 200 g of an electron donor (B2) and 20 to 500 g of an electron acceptor in 0.1 to 1? of an aliphatic hydrocarbon at a temperature of 53° to 100°C to obtain a solid product (III);
combining 1 g of this solid product (III) with 0.5 to 50 g of an organoaluminum compound (A2) and 0.05 to 10 g of a reaction product (G) obtained by reacting 1 mol of an organo-aluminum compound (A3) with 0.01 to 5 mols of an electron donor (B3) at a temperature of -30°C to 100°C, (the substances employed in this combination being hereinafter referred to a catalyst components), and in this combination, subjecting a part or the total of the catalyst components to polymeri-zation treatment with 0.05 to 3,000 g of an .alpha.-olefin, at least in the presence of said solid product (III) and said organoaluminum compound (A2), to obtain a preliminarily activated catalyst; and polymerizing an .alpha.-olefin or .alpha.-olefins in the presence of this preliminarily activated catalyst.