CA1115447A

CA1115447A - Process for preparing olefin polymers or copolymers

Info

Publication number: CA1115447A
Application number: CA285,572A
Authority: CA
Inventors: Syuji Minami; Akinori Toyota; Norio Kashiwa
Original assignee: Mitsui Petrochemical Industries Ltd
Current assignee: Mitsui Chemicals Inc
Priority date: 1976-08-27
Filing date: 1977-08-26
Publication date: 1981-12-29
Also published as: NO152753B; AT350258B; PH15738A; DE2738627C2; IT1084731B; NO152753C; JPS5327677A; NL177831C; BR7705674A; ZA775067B; ES462114A1; JPS5812888B2; PT66956A; FR2362868A1; NO772897L; ATA613677A; PT66956B; SE7709631L; FR2362868B1; NL7709399A

Abstract

Abstract of the Disclosure The invention is a process for obtaining highly stereoregular poly or or copolymers. The process comprises polymerizing or copolymerizing olefins in the presence of a catalyst comprising: a solid complex titanium component at least containing magnesium, titanium and halogon, an organometal-lic compound of a metal of Groups I to III of the periodic table, and an organic acid anhydride.

Description

l~iS~7 This invention relates to a process which can afford highly stereoregular polymers or copolymers in high yields when applied to the polymerization or copolymerizaLion of ~-olefins, especially those having at least 3 carbon atoms.
Many prior suggestions have been known for the preparation of highly stereoregular polymers or copolymers by using a solid complex titanium component at least containing magnesium, titanium and halogen, preferably treated with an electron donor, as a titanium catalyst component which constitutes a catalyst for the polymerization or copolymerization of ~-olefins containing at least 3 carbon atoms (for example, German Laid-Open Patent Publication Nos. 2,153,520, 2,230,672 and 2,553,104).
These prior suggestions teach combinations of specific catalyst-forming components, and combinations of catalyst-forming procedures and the catalyst-forming components as essential conditions. As is well known, the characteristics of catalysts containing a solid complex titanium component of this type vary greatly according to differences in the combination of the above catalyst-forming components, the combinations of the catalyst-forming procedures, and the combinations of these conditions. When catalyst- ;
forming components and/or catalyst-forming procedures which are essential in a given combination of conditions are used in a different combination of conditions, it is quite impossible to anticipate whether similar results will be obtainable. Frequently, the result is a catalyst having quite poor properties.
The aforesaid solid complex titanium component at least containing magnesium, titanium and halogen is no exception. If in the polymerization or copolymerization of ~-olefins containing at least 3 carbon atoms in the presence of hydrogen using a catalyst composed of the aforesaid titanium component and an organometallic compound of a metal of Groups I to IV of the periodic table, a catalyst composed of a titanium trichloride component obtained by reducing titanium tetrachloride with metallic aluminum, hydro-'X - 1 -S'~`7 gen, or an organoaluminum compound is used together with a donor known to have an effect of inhibiting the formation of an amorphous polymer, the effect varies unanticipatably according to the donor used.
The present inventors have made efforts for many years in order to provide a process which can produce highly stereoregular polymers in high yields while advantageously overcoming the trouble of forming an amor-phous polymer in the presence of a catalyst composed of ~a) a solid complex titanium component at least containing magnesium, titanium and halogen, and (b) an organometallic compound of a metal of groups I to III of the periodic table.
It has now been found that an organic acid anhydride, preferably a carboxylic acid anhydride including an aromatic carboxylic acid anhydride, used together with ~a) and (b) can afford a catalyst which can overcome the above trouble and has high activity and superior reproducibility of its properties.
Accordingly, it is an object of this invention to provide an im-proved process for preparing highly stereoregular olefin polymers in high yields by overcoming the trouble of forming an amorphous polymer.
The present invention provides a process for preparing olefin polymers or copolymers which comprises polymerizing or copolymerizing olefins in the presence of a catalyst comprising (a) a solid complex titanium com-ponent at least containing magnesium, titanium and halogen and an electron donor, (b) an organometallic compound of a metal of Groups I to III of the Mendelejeff's periodic table, and ~c) an organic carboxylic acid anhydride.
The present invention also provides a catalyst composition for polymerization or copolymerization of olefins, said composition comprising (a) a solid complex titanium component at least containing magnesium, tita-nium and halogen obtained by reacting a magnesium compound with an electron donor, and then reacting the reaction mixture with a titanium compound by suspending the mixture in a liquid tetravalent titanium compound with or without using an inert solvent, (b) an organometallic compound of a metal S~7 of Groups I to III of the Mendelejeff's periodic table, and ~c) an organic carboxylic anhydride.
The solid complex titanium component (a) is a solid complex which has a halogen/titanium molar ratio of more than about 4, and does not substantially permit the liberation of a titanium compound by washing with hexane at room temperature. The chemical structure of this solid complex is not known, but presumably, the magnesium atom and the titanium atom are bonded firmly by, for example, having the halogen in common. The solid complex may, depending upon the method of preparation, contain other metal atoms such as aluminum, silicon, tin, boron, germanium, calcium and zinc, electron donors, or organic groups ascribable thereto. It may further con-tain an organic or inorganic inert diluent, suchas LiCl, CaC03, BaC12, NaC03,

2 2 3 2 4' 2 3' Si2' Ti2' NaB407, Ca3(P04)2, CaS04, Al (S0 ) CaC12, ZnC12, polyethylene, polypropylene, and polystyrene. Preferably, the solid complex is the one treated with an electron donor. In preferred examples of the solid complex titanium component (a), the halogen/titanium molar ratio is above about 4, preferably at least about 5, more preferably at least about 8, and the magnesium/titanium molar ratio is at least about

3, preferably about 5 to about 50, and the electron donor/titanium molar ratio of about 0.2 to about 6, preferably about 0.4 to about 3, more prefe-rably about 0.8 to about 2. Furthermore, the specific surface area of the solid is at least 3 m2/g, preferably at least about 40 m2/g, and more pre-ferably at least about 100 m2/g. It is also desirable that the X-ray spec-trum of the solid complex ~a) should show amorphous character irrespective of the starting magnesium compound, or it is in a more amorphous state than ordinary commercially available grades of magnesium dihalide.
The solid complex titanium component (a) can be formed by various means, and most commonly, a magnesium compound and a titanium compound are contacted while at least one of them contains halogen, and if desired, the product is treated with an electron donor. Various suggestions have been known for the preparation of such component ~a), and can be used in this inven1:ion. Some of such suggestions are disclosed in German Laid-Open Patent Publications Nos. 2,230,672, 2,504,036, 2,553,104 and 2,605,922 and Japanese Laid-Open Patent Publications Nos. 28189/76, 127185/76, 136625/76 and 87486/77.
Typical methods disclosed in these documents involve the reaction of at least a magnesium compound (or metallic magnesium), an electron donor and a titanium compound.
Examples of the electron donor are oxygen-containing electron donors such as water, alcohols, phenols, ketonesJ aldehydes, carboxylic acids, esters, ethers and acid amides, and nitrogen~containing electron donors such as ammonia, amines, nitriles and isocyanates.
Specific examples of such electron donors include alcohols contain-ing 1 to 18 carbon atoms such as methanol, ethanol, propanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, and isopropyl benzyl alcohol; phenols containing 6 to 15 carbon atoms which may contain a lower alkyl group, such as phenol, cresol, xylenol, ethyl phenol, propyl phenol, cumyl phenyl, and naphthol;
ketones containing 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone and benzophenone; aldehydes containing 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octyl aldehyde, benzaldehyde, tolualdehyde and naphthoaldehyde; organic acid esters con-taining 2 to 18 carbon atoms such as methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethylbenzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, y-butyrolactone, ~-valerolactone, coumarine, phthalide and ethylene carbonate; acid halides containing 2 to 15 carbon atoms such as acetyl chloride, benzyl chloride,

- 4 -toluic acid chloride, and anisic acid chloride; ethers containing 2 to 20 carbon atoms such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, and diphenyl ether; acid amides such as acetamide, benzamide and toluamide; amines such as methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline and tetramethylethylene diamine; nitriles such as acetonitrile, benzonitrile and tolunitrile; and compounds of aluminum, silicon, tin etc. which contain the aforesaid functional groups in the molecule. These electron donors can be used as a mixture of two or more.
Suitable magnesium compounds used for the formation of the solid complex titanium compound (a) are those containing halogen and/or organic groups. Specific examples of such magnesium compounds include magnesium dihalides, magnesium alkoxyhalides, magnesium aryloxyhalides, magnesium hydroxyhalides, magnesium dialkoxides, magnesium diaryloxides, magnesium alkoxyaryloxides, magnesium acryloxyhalides, magnesium alkylhalides, magnesium arylhalides, magnesium dialkyl compounds, magnesium diaryl com-pounds, and magnesium alkylalkoxides. They may be present in the form of adducts with the aforesaid electron donors. Or they may be double compounds containing other metals such as aluminum, tin, silicon, germanium, zinc or boron. For example, they may be double compounds of halides, alkyl com-pounds, alkoxyhalides, aryloxyhalides, alkoxides and aryloxides of metals such as aluminum, and the above-exemplified magnesium compounds. Or they may be double compounds in which phosphorus or boron is bonded to magnesium metal through oxygen. These magnesium compounds may be a mixture of two or more. Usually, the above-exemplified compounds can be expressed by simple chemical formulae, but sometimes, according to the method of prepara-tion of the magnesium compounds, they ~annot be expressed by simple formu-lae. They are usually regarded as mixtures of the aforesaid compounds.
For example, compounds obtained by a method which comprises reacting magne-sium metal with an alcohol or phenol in the presence of a halosilane, phos-phorus oxychloride, or thionyl chloride, and a method which comprises pyro-~ 5 ~

lyzing Grignard reagents, or decomposing them with compounds having a hydro-xyl group, a carbonyl group, an ester linkage, an ether linkage, or the like are considered to be mixtures of various compounds according to the amounts of the reagents or the degree of reaction. These compounds can of course be used in this invention.
Various methods for producing the magnesium compounds exemplified hereinabove are known, and products of any of these methods can be used in this invention. Also, prior to use, the magnesium compound may be treated, for example, by a method which comprises dissolving it singly or together with another metal compound in ether or ace~one, and then evaporating the solvent or putting the solution into an inert solvent thereby to separate the solid. A method can also be employed which involves pre-pulverizing mechanically at least one magnesium compound with or without another metal compound.
Preferred among these magnesium compounds are magnesium dihalides, aryloxyhalides and aryloxides, and double compounds of these with aluminum, silicon, etc. More specifically, they are MgC12, MgBr2, MgI2, MgF2, MgCl-~OC6H5), Mg~OC6115)2, MgCl~OC6H4-2-CH3), Mg~OC6H4-2-CH3)2, ~MgC12)X~Al(OR)n C13 ~ y, and ~MgC12)x~Si(OR)mCl4 ~ y. In these formulae, R is a hydrocarbon group such as an alkyl or aryl group, m or n R groups are the same or dif-ferent, O_ n _3, O-m _4, and x and y are positive numbers. MgC12 and its complexes or double compounds are especially preferred.
Suitable titanium compounds used for the formation of the solid complex titanium compound (a) are tetravalent titanium compounds of the formula Ti~OR)gX4 g wherein R is a hydrocarbon group, preferably an alkyl group containing 1 to 6 carbon atoms, X is a halogen atom, and 0_g _4.
Examples of the titanium compounds are titanium tetrahalides such as TiC14, TiBr4 or TiI4; alkoxytitanium trihalides such as Ti~OCH3)C13, Ti(OC2H5)C13, Ti(0 n-C4Hg) C13, Ti(OC2H5)Br3, and Ti(O iso-C4Hg)Br3; alkoxytitanium dihalides such as Ti(OCH3)2C12, Ti(OC2H5)2C12, T ( 4 9 2 2 Ti(OC2H5)2Br2; trialkoxytitanium monohalides such as Ti~OCH3)3Cl, Ti~OC2H5)3 X

~.5~7 Cl, ri(O n-C4Hg)3CI and Ti~OC2H5)3 Br; and tetraalkoxytitanium such as Ti(OCH3)4, Ti (OCH3)4, Ti(OC2H5)4, and Ti(O n-C4Hg)4. Of these, the tita-nium tetrahalides are preferred, and especially preferred is titanium tetra-chloride.
Preferably, the solid complex titanium compound (a) is pre-treated with an electron donor. Examples of the electron donor are esters, ethers, ketones, tertiary amines, acid halides, and acid anhydrides, which do not contain active hydrogen. Organic acid esters and ethers are especially preferred, and most preferred are aromatic carboxylic acid esters and alkyl-containing ethers, Typical examples of suitable aromatic carboxylic acid esters include lower alkyl esters such as lower alkyl esters of benzoic acid, and lower alkyl esters of alkoxy benzoic acid. The term "lower"
means the possession of 1 to 4 carbon atoms. Those having 1 or 2 carbon atoms are especially preferred. Suitable alkyl-containing ethers are those containing 4 to 20 carbon atoms such as diisoamyl ether and dibutyl ether.
There are various examples of reacting the magnesium compound (or metallic magnesium), the electron donor and the titanium compound, and ty-pical ones are described below.
~I~ Method involving reacting the magnesium compound with the electron donor and then reacting the reaction mixture with the titanium compound:-~I-a) Method ~I~ with the copulverization of the magnesium com-pound and the electron donor:-The electron donor added at the time of copulverization needs not to be in the free state, and may be present in the form of an adduct with the magnesium compound. At the time of copulverization~ additional ingredients, which may be included in the complex titanium component (a), for example, the aforesaid organic or inorganic inert diluent, a halogena-ting agent such as a halogen compound of silicon, a silicon compound such as polysiloxane, and a compound of aluminum, germanium or tin, or a part of the titanium compound may be present together. Or the electron donor may ~~`
be present in the form of an adduct (complex compound) with such a compound.

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The amount of the electron donor used is preferably about 0.005 to about 10 moles, more preferably about 0.01 to about 1 mole, per mole of the mag-nesium compound.
The copulverization may be carried out by using ordinary devices such as a rotary ball mill, a vibratory ball mill, and an impact mill. If the rotary ball mill is used, and 100 stainless steel ~SUS 32) balls having a diameter of 15 mm are accomodated in a ball mill cylinder having an inner capacity of 800 ml and an inside diameter of 100 mm and made of stainless steel ~SUS 32) and 20 to 40 g of the materials to be treated are put into it, it is advisable to perform the pulverization for at least 24 hours, preferably at least 48 hours at a rotating speed of 125 rpm. The tempera-ture of the pulverization treatment is usually room temperature to about 100C.
The copulverized product can also be reacted with the titanium compound by copulverizing means. However, it is preferred to suspend the copulverized product in at least about 0.05 mole, preferably about 0.1 to about 50 moles, per mole of the magnesium compound, of a liquid titanium compound with or without using an inert solvent. The reaction temperature is from room temperature to about 200C, and the reaction time is from 5 minutes to about 5 houTs. The reaction can of course be performed under conditions outside these specified ranges. After the reaction, the reaction mixture is hot-filtered at a high temperature of, say, about 60 to 150C
to isolate the product which is then well washed with an inert solvent before use in polymerization.
~I-b) Method ~I) without the copulverization of the magnesium compound and the electron donor:-Usually, the magnesium compound is reacted with the electron donor in an inert solvent, or the magnesium compound is dissolved or suspended in the liquid electron donor for reaction. It is possible to employ an embodi-ment in which magnesium metal is used as a starting material, and reacted with the electron donor while forming a magnesium compound.

~5~

The amount of the electron donor used is preferably about 0.01 to about 10 moles, more preferably about 0.05 to about 6 moles, per mole of the magnesium compound. The reaction proceeds sufficiently at a reaction temperature of from room temperature to about 200C for 5 minutes to about

5 hours. After the reaction, the reaction mixture was filtered or evapora-ted, and washed with an inert solvent to isolate the product. The reaction of the reaction product with the titanium compound can be performed in the same way as described in (I-a).
(I-c) Method which comprises reacting the reaction product bet-ween the magnesium compound and the electron donor with a compound selected from organoaluminum compounds, silicon compounds and tin compounds, and then reacting the resulting product further with the titanium compound:-This method is a special embodiment of the method (I-b~. General-ly, complexes obtained by the method (I-a) have superior properties, but some of complexes obtained by the method (I-b) have inferior properties to those obtained by method (I-a). The properties of such complexes can be very effectively improved by the performance of method (I-c) in which the organoaluminum compound, silicon compound or tin compound is reacted prior to the reaction with the titanium compound.
Examples of the organoaluminum compounds that can be used in this method are trialkyl aluminums, dialkyl aluminum hydrides, dialkyl aluminum halides, alkyl aluminum sesquihalides, alkyl aluminum dihalides, dialkyl aluminum alkoxides or phenoxides, alkyl aluminum alkoxy halides or pheno-xyhalides, and mixtures of these. Of these, the dialkyl aluminum halides, alkyl aluminum sesquihalides, alkyl aluminum dihalides, and mixtures of these are preferred. Specific examples of these include triethyl aluminum, trii- ;
sobutyl aluminum, diethyl aluminum hydride, dibutyl aluminum hydride, diethyl aluminum chloride, diisobutyl aluminum bromide, ethyl aluminum ses-quichloride, diethyl aluminum ethoxide, ethyl aluminum ethoxy chloride, ethyl aluminum dichloride, and butyl aluminum dichloride.
The silicon or tin compounds, for example silicon or tin halogen X - g _ ~ . . . : : .

compounds or organic compounds, are compounds containing at least one halo-gen or hydrocarbon group directly bonded to silicon or tin, and may further contain hydrogen, an alkoxy group, a phenoxy group, or the like. Specific examples include, silicon tetrahalides, tetraalkyl silicons, silicon alkyl halides, silicon alkylhydrides, tin tetrahalides, tin dihalides, tin alkyl-halides, and tin hydride halides. Of these, silicon tetrachloride and tin tetrachloride are preferred.
The reaction between the magnesium compound and the electron donor can be performed by the method (I-b). The reaction of the resulting reaction product between the magnesium compound and the electron donor with the organoaluminum compound, silicon compound or tin compound may be carried out in an inert solvent. Such a compound is used in an amount of preferably about 0.1 to about 20 moles, more preferably about 0.5 to about 10 moles, per mole of the magnesium compound. The reaction is carried out preferably at a temperature of from room temperature to about 100C for 5 minutes to 5 hours. After the reaction, the reaction mixture is preferably well washed with an inert solvent, and then reacted with the titanium compound. The reaction of this reaction product with the titanium compound can be perfor-med in accordance with the method described in (I-a).
~ ~ Method which comprises simultaneously reacting the magnesium com-pound, the electron donor and the titanium compound.
~I~ Method which comprises reacting the reaction product between the titanium compound and the electron donor with the magnesium compound.
The reactions in the methods CI~ and ~I~ are preferably perfor-med by copulverization. The pulverization conditions and the proportions of the raw materials are the same as set forth under method CI~. In these methods, however, it is not preferred to use a large quantity of the tita-nium compound. The amount of the titanium compound is preferably about 0.01 to about 1 mole per mole of the magnesium compound.
The above methods are typical methods, and many modifications are possible as shown below.

J ~L15L.~

(1) Method CI~ in which the electron donor is caused to be present when reacting the titanium compound.
(2) ~ method in which the organic or inorganic inert diluent and the silicon, aluminum, germanium or tin compound are caused to be present during the reaction; a method in which these compounds are caused to act before the reaction; a method in which these compounds are caused to act between the reactions; a method in which these compounds are caused to act after the reaction. A typical example of methods is the method (I-c).
These reagents can be used at desired points in the above methods.
For example, (2-a) Method in which a halogenating agent sucl- as SiC14 is caused to act on the compound obtained by methods CI~ CI~ and ~
(3) Method in which the titanium compound is caused to act two or more times:-(3-a) The method in which the titanium compound and the electron donor are reacted with the reaction product obtained by any of the methods CI~ to ~
13-b) The method in which the titanium compound, the organoalu-minum compound and the electron donor are reacted with the reaction product of any one of these methods CI~ to ~
A number of other modifications can be made by changing the order of addition of reaction agents, or by carrying out a plurality of reactions, or by using additional reaction agents. In any of such methods, it is desirable that the halogen, titanium and magnesium in the complex (a), the proportion of the electron donor, the surface area of the complex (a) and the X-ray spectrum of the catalyst be within the above ranges or in the above-mentioned conditions.
In the present invention, polymerization or copolymerization is carried out in the presence of a catalyst composed of the solid complex titanium component (a) at least containing magnesium, titanium and halogen and preferably being treated with an electron donor, (b) an organometallic , .

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compound of a metal of Groups I to III of the periodic table, and ~c) an organic acid anhydride.
The organometallic compound (b) has a hydrocarbon group directly bonded to the metal, and includes, for example, alkyl aluminum compounds, alkyl aluminum alkoxides, alkyl aluminum hydrides, alkyl aluminum halides, dialkyl zincs, and dialkyl magnesiums. Preferred among them are the organo-aluminum compounds. Specific examples of the organoaluminum compounds are trialkyl or trialkenyl aluminums such as Al~C2H5)3, Al~CH3)3, Al~C3H7)3, Al~C4Hg)3 and Al~C12H25)3; alkyl aluminum compounds having such a structure that many aluminum atoms are connected through oxygen or nitrogen atoms, 2 5 2 ~ 2H5)2, (C4Hg)2AlOAl(C4H9)2, and (C2H )2AlNAl(C H ) ;

dialkyl aluminum hydrides such as (C2H5)2AlH or (C4Hg)2AlH; dialkyl aluminum halides such as (C2H5)2AlCl, (C2H5)2AlI or (C4Hg)2AlCl; and dialkyl aluminum alkoxides or phenoxides such as (C2H5)2Al(OC2H5) and (C2H5)2Al(OC6H5). Of these, the trialkyl aluminums are most preferred.
Examples of the organic acid anhydride (c) include aliphatic mono-carboxylic acid anhydrides containing 2 to 18 carbon atoms such as acetic anhydride, propionic anhydride, n-butyric anhydride, iso-butyric anhydride, monochloroacetic anhydride, trifluoroacetic anhydride, caproic anhydride, lauric anhydride and stearic anhydride; aliphatic polycarboxylic acid anhydrides containing 4 to 22 carbon atoms such as succinic anhydride, maleic anhydride, glutaric anhydride, citraconic anhydride, itaconic anhy-dride, methylsuccinic anhydride, dimethylsuccinic anhydride, ethylsuccinic anhydride, butylsuccinic anhydride, octylsuccinic anhydride, stearylsuccinic anhydride, and methylglutaric anhydride; alicyclic carboxylic acid anhydri-des containing 8 to 1~ carbon atoms such as bicyclo ~.2 ~ heptene-2,3-dicarboxylic anhydride or methylbicyclo ~.2.~ heptene-2,3-dicarboxylic anhydride; and anhydrides of aromatic carboxylic acids containing 9 to 15 carbon atoms such as acetobenzoic anhydride, acetotoluic anhydride, benzoic anhydride, toluic anhydride, phthalic anhydride, and trimellitic anhydride.

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Of these, the aromatic carboxylic acid anhydrides are preferred.
The aliphatic monocarboxylic acid anhydrides are next preferred although they tend to give somewhat low polymerization ~ctivity. These acid anhydri-des can also be used as electron donors in the preparation of the solid com-plex titanium component (a).
These acid anhydrides may be used as addition reaction products or substitution reaction products with organometallic compound (b). The pre-ferred method of using the acid anhydrides is to purge the polymerization system with an olefin monomer, add the acid anhydride and the organometallic compound ~b), and then add the titanium catalyst component (complex) (a).
It is possible to contact the acid anhydride with the organometallic compound outside the pol~merization system, and then feed them into the polymerization system.
According to the process of this invention, olefins such as ethy-lene, propylene, l-butene or 4-methyl-1-pentene can be advantageously car-ried out. The process can especially advantageously be applied to the poly-merization of ~-olefins containing at least 3 carbon atoms, copolymerization (random copolymerization, and block copolymerization) of these with each other, copolymerization of these with not more than 10 mole% of ethylene, ;~
and copolymerization of these with polyunsaturated compounds such as conju-gated dienes.
The polymerization can be carried out either in the liquid or vapor phase. When it is performed in the liquid phase~ an inert solvent such as hexane, heptane or kerosene may be used as a reaction medium, but the olefin itself may serve as the reaction medium. In the case of the liquid-phase polymerization, the preferred concentration of the solid complex titanium component (a) in the polymerization system is about 0.001 to about 5 millimoles, preferably about 0.001 to about 0.5 millimole as titanium atom per liter of the solvent, and the preferred concentration of the organometal-lic compound is about 0.1 to about 50 millimoles as metal atom per liter of the solvent. In the case of the vapor phase polymerization, the solid tita-5'~7 nium catalyst component (A) is used in an amount of about 0.001 to about 5 millimoles, preferably about 0.001 to about 1.0 millimole per liter of polymerization zone, more preferably about 0.01 to about 0.5 millimole per liter of polymerization zone, calculated as titanium atom. The organo-metallic compound ~B) is used preferably in an amount of about 0.01 to about 50 millimoles per liter of polymerization zone calculated as metal atom.
The ratio of the organometallic component ~b) to the solid complex titanium component ~a) may be such that the ratio of the metallic atom in component ~b) to the titanium atom in component (a) is preferably 1/1 to lO00/1, preferably 1/1 to 200/1. The amount of the acid anhydride component (c) is preferably about 0.001 to about 1 mole, more preferably about 0.01 to about 1 mole, per metal atom of the organometallic compound (b).
Polymerization reactions of olefins in the presence of the cata-lyst of this invention can be performed in the same way as in the polymeri-zation of olefins with ordinary Ziegler-type catalysts. Specifically, the reaction is performed in the substantial absence of oxygen and water.
When a suitable inert solvent such as an aliphatic hydrocarbon (e~g., hexane, heptane or kerosene) is used, the catalyst and an olefin and option-ally a diolefin are charged into a reactor, and the polymerization is car-ried out. The polymerization temperature is usually about 20 to 200C, preferably about 50 to about 150C. Preferably, the polymerization is car-ried out at elevated pressures, that is, from normal atmospheric pressure to about 50 kg/cm2, especially about 2 to about 20 kg/cm2. The molecular weight of the polymer can be adjusted to some extent by changing the poly-merization conditions such as the polymerization temperature, and the molar proportion of the catalyst, but the addition of hydrogen to the polymeri-zation system is most effective.

The process of this invention can aford highly stereoreg~lar polymers having a large melt index in high yields.
The following examples illustrate the invention in more detail.

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~L15~7 Exam~L_ Anhydrous magnesium chloride (20 g), 6.0 ml of ethyl benzoate and 3.0 m:L of methyl polysiloxane (viscosity 20 centistokes at 20C) were charged into a stainless steel (SUS-32) ball mill having an inner capacity of 800 ml and an inside diameter of 100 mm and containing 2 8 kg of a stain-less steel (SUS-32) balls having a diameter of 15 mm in an atmosphere of nitrogen. These materials were contacted with one another for 24 hours at an impact acceleration of 7G. Ten grams of the resulting solid product was suspended in 100 ml of titanium tetrachloride, and contacted with stirring at 80C for 2 hours. The solid was collected by filtration, and sufficient-ly washed with purified hexane until no free titanium tetrachloride was detected in the wash liquid. The washed solid was dried to afford a solid complex titanium component (a) which contained 3.0% by weight of titanium atom, 58.2% by weight of chlorine atom, 18.0% by weight of magnesium, and 15.5% by weight of ethyl benzoate, and had a specific surface area of 180 m /g.
A 2-liter autoclave was purged with propylene, and then 750 ml of hexane which had been fully deprived of oxygen and moisture, 4.5 millimoles of triethyl aluminum, 1.5 millimoles of phthalic anhydride, and 0.03 milli-mole, calculated as titanium atom, of the component (a) were charged into the autoclave. The autoclave was sealed, and then, 250 ml of hydrogen was charged, and the temperature was raised. When the temperature of the poly-~erization system rose to 60C, propylene was introduced into the autoclave and its polymerization was started at a total pressure of 8 kg/cm2. The polymerization was performed at 60C for 6 hours. Then, the introduction of propylene was stopped, and the contents of the autoclave were cooled to room temperature. The resulting solid was collected by filtration, and dried to afford 335.7 g of polypropylene as a white powder. The polymer had a boiling n-hepcane extraction residue of 94.9%, an apparent density of 0.31 g/mlJ and a melt index of 2.7. Concentrating the liquid layer afforded 13.4 g of a solvent-soluble polymer.

.XI

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Example 2 Commercially available anhydrous magnesium chloride (9.5 g; 0.1 mole) was suspended in 0.3 liter of kerosene, and at room temperature, 23.3 ml ~0.4 mole) of ethanol and 14.3 ml (0.1 mole) of ethyl benzoate were added. The mixture was stirred for 1 hour. Then, 24.2 ml (0.2 mole) of diethyl aluminum chloride was added dropwise at room temperature, and stirred for 1 hour. The solid portion of the reaction product was collect-ed, washed fully with kerosene, and suspended in 0.3 liter of kerosene con~aining 30 ml of titanium tetrachloride. The reaction was performed at 80C for 2 hours. After the reaction, the supernatant liquid was removed by decantation. The solid portion was fully washed with fresh kerosene to afford a solid complex titanium component (a) which contained 3.5% by weight of titanium atom, 59.3% by weight of chlorine atom, 19.3% by weight of magnesium atom, and 14.7% by weight of ethyl benzoate, and had a speci-fic surface area of 175 m2/g.
Propylene was polymerized in the same way as in Example 1 except that 0.05 millimole, as titanium atom, of the component (a) was used. Poly-propylene was obtained in an amount of 327.4 g as a white powder. The polymer has a boiling n-heptane extraction residue of 95.0% by weight, an apparent density of 0.32 g/ml and a melt index of 3.6.
Concentrating the liquid layer afforded 11.7 g of a solvent-soluble polymer.
Examples 3 to 8 Propylene was polymerized in the same way as in Example 1 except that each of the acid anhydrides shown in Table 1 was used instead of the phthalic anhydride. The results are shown in Table 1.

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,~1 - 1 7 Example 9 Commercially available Mg(OCH3~2 (8.6 g; 0.1 mole) was suspended in 0.3 liter of kerosene, and 10.6 ml (0.1 mole) of o-cresol was added. The reacl;ion was performed for 1 hour at 80C. At the same temperature, 7.2 ml (0.05 mole) of ethyl benzoate was added, and the reaction was further car-ried out for 1 hour. The reaction mixture was cooled to 60C, and 2.9 ml (0.025 mole) of SiC14 was added dropwise over the course of 30 minutes, and the reaction was performed at 60C for 1 hour. After cooling, the solid portion of the product was collected. It was fully washed with kero-sene, and suspended in 300 ml of titanium tetrachloride and reacted at 130C for 2 hours. After the reaction, the supernatant liquid was removed by decantation. The solid portion was fully washed with fresh kerosene to afford a solid complex titanium component (a) which contained 4.1% by weight of titanium atom, 54% by weight of chlorine atom, 16.7% by weight of magnesium atom, and 11.3% by weight of ethyl benzoate.
Propylene was polymerized in the same way as in Example 1. There was obtained 296.2 g of polypropylene as a white powder. The polymer had a boiling n-heptane extraction residue of 95.1%, an apparent density of 0.30 g/ml and a melt index of 3.6.
Concentrating the liquid layer afforded 12.0 g of a solvent-soluble polymer.
Example 10 Ball milling was performed in the same way as in Example 1 except that 6.5 ml of isoamyl ether were used instead of ethyl benzoate. The pulverized product was contacted with titanium tetrachloride in the same way as in Example 1 to afford a component (a) which contained 2.1% by weight of titanium atom and 69% by weight of chlorine atom.
Propylene was polymerized in the same way as in Example 1. There was obtained 325.3 g of polypropylene as a white powder which had a boiling n-heptane extraction residue of 93.3%, an apparent density of 0.35 g/ml, and a melt index of 4Ø

~r - 18 -5~ 7 Concentrating the liquid layer afforded 9.9 g of a solvent-soluble polymer.
Example 11 A reactor equipped with a reflux condenser was charged with 200 ml of Grignard reagent ~ethyl ether solution, 2 moles/liter), and 0.4 mole of p-cresol was added dropwise at room temperature. After the reaction, the ethyl ether was removed by distillation. The resulting white powder was suspended in 200 ml of purified kerosene. Ethyl benzoate ~0.1 mole) was added to the suspension, and the reaction was performed at 80C for 2 hours. After the reaction, the reaction mixture was cooled to room tempera-ture. The resulting solid was collected by filtration, washed with puri-fied hexane, and dried at reduced pressure.
The reaction product was suspended in 300 ml of titanium ~etrachlo-ride, and with stirring, reacted at 80~C for 2 hours. After the reaction, the product was hot-filtered, and sufficiently washed with purified hexane.
Drying under reduced pressure afforded a solid complex titanium component (a) which contained 3.3% by weight of titanium atom, 56% by weight of chlo-rine atom, 18.7% by weight of magnesium atom, 8.7% by weight of ethyl ben-zoate, and has a specific surface area of 170 m2/g.
Propylene was polymerized in the same way as in Example 1. There was obtained 264.2 g polypropylene as a white powder. The polymer had a boiling n-heptane extraction residue of 93.7%, an apparent density of 0.32 g/ml, and a melt index of 3.2.
Concentrating the liquid layer afforded 9.7 g of a solvent-soluble polymer.
Example 12 Anhydrous magnesium chloride (20 g) and 1.2 ml of titanium tetra-chloride were placed in a stainless steel (SUS-32) ball mill cylinder having an inner capacity of 800 ml and an inside diameter of 100 mm and having accomodated therein 100 stainless steel (SUS-32) balls having a diameter of 15 mm, and contacted with each other for 30 hours at a speed of 125 rpm.

~ ~5~7 Ten grams of the solid powder obtained was suspended in 100 ml of kerosene and at 60C, 15 ml of ethyl p-toluate was added dropwise over the course of 30 minutes. The reaction was performed at 70C for 1 hour. The pro-duct was collected by filtration, washed with hexane, dried. Ten grams of the resulting solid product was suspended in 100 ml of titanium tetra-chloride, and reacted at 100C for 2 hours. The product was filtered, sufficiently washed with hexane, and dried. The resulting solid complex titanium component (a) contained 2.0% by weight of titanium atom and 56.0%
by weight of chlorine atom.
Propylene was polymerized in the same way as in Example 1. There was obtained 265.4 g of polypropylene as a white powder. The polymer had a boiling n-heptane extraction residue of 93.7%, an apparent density of 0.32 g/ml and a melt index of 6.2.
Concentrating the liquid layer afforded 10.3 g of a solvent-soluble polymer.
Example 13 Ten grams of the solid complex titanium com~ound (a) obtained in the same way as in Example 1 was suspended in 200 ml of purified kero-sene, and 6.3 millimoles of titanium tetrachloride was added at room temperature. The reaction was performed for 1 hour. Further, 6.3 milli-moles of ethyl benzoate was added, and the reaction was performed for 1 hour. The reaction product was filtered, washed with hexane, and dried to afford a solid complex titanium component (a) which contained 3.5% by weight of titanium atom.
Propylene was polymerized in the same way as in Example 1.
There was obtained 276.2 g of polypropylene as a white powder. The poly-mer had a boiling n-heptane extraction residue of 93.7~, an apparent den-sity of 0.34 g/ml and a melt index of 4.8.

Concentrating the liquid layer afforded 10.2 g of a solvent-soluble polymer.

~ - 20 -~5~7 Examples 14 to 18 Solid complex titanium components ~a) were prepared in the same way as in Example 1 except that ethyl benzoate was changed to electron donors as shown in Table 2, and propylene was polymerized. The results are shown in Table 2.

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Examples 19 to 23 Solid titanium complexes were prepared in the same way as in Example 2 except that the alcohol, ester and organoaluminum compound (or tin or silicon compound) were changed as shown in Table 3, and propylene was polymerized in the same way as in Example 1. The results are shown in Table 3.

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~ - 25 -

Claims

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

1. A process for preparing olefin polymers or co-polymers which com-prises polymerizing or co-polymerizing olefins in the presence of a catalyst comprising (a) a solid complex titanium component at least containing mag-nesium, titanium, halogen and an electron donor, (b) an organometallic compound of a metal of Groups I to III of the Mendelejeff's periodic table, and (c) an organic carboxylic acid anhydride.

2. The process of claim 1 wherein the solid complex titanium component (a) is treated with an electron donor.

3. The process of claim 2 wherein the electron donor is a compound selected from the group consisting of organic acid esters and ethers.

4. The process of claim 1 wherein the organometallic compound (b) is an organoaluminum compound.

5. The process of claim 1 wherein the acid anhydride (c) is a compound selected from the group consisting of aliphatic monocarboxylic acid anhydrides containing 2 to 18 carbon atoms, aliphatic polycarboxylic acid anhydrides containing 4 to 22 carbon atoms, alicyclic carboxylic acid anhydrides con-taining 8 to 10 carbon atoms and aromatic carboxylic acid anhydrides contain-ing 9 to 15 carbon atoms.

6. The process of claim 1 wherein the halogen/titanium molar ratio in the solid complex titanium component (a) exceeds about 4, and the magnes-ium/titanium molar ratio is at least about 3.

7. The process of claim 1 wherein the amount of the solid complex titanium component (a) is about 0.001 to about 5 millimoles as titanium atom per liter of solvent in the case of a liquid-phase reaction in a reaction solvent, and about 0.001 to about 5 millimoles as titanium atom per liter of polymerization zone in the case of a vapor-phase reaction.

8. The method of claim 1 wherein the amount of the organometallic compound (b) is about 0.1 to about 50 millimoles as the metal atom per liter of solvent in the case of a liquid phase reaction in a reaction solvent, and is about 0.1 to about 50 millimoles as the metal atom per liter of poly-merization zone in the case of a vapor phase reaction.

9. The process of claim 1 wherein the amount of the acid anhydride (c) is about 0.001 to about 1 mole per metal atom of the organometallic compound (b).

10. The process of claim 1 wherein the olefin is an .alpha.-olefin con-taining at least 3 carbon atoms.