DD206384A5 - METHOD FOR PRODUCING OLEFIN POLYMERS OR COPOLYMERS - Google Patents

Abstract

The invention relates to purification processes for the preparation of olefin polymers or copolymers characterized by the fact that it comprises the polymerisation of olefins or the copolymerization of olefins with each other or with services in the presence of a catalyst system, consisting of the following components (A), (B) AND (C): (A) a solid titanium catalyst component containing magnesium, titanium, halogen and an ester of polycarboxylic acids and ESTERS of polyhydroxy compounds, wherein the catalyst component obtained by contacting a solution in liquid HYDROCARBONS FROM (I) a magnesium compound with (II ) A TITANIUM CONNECTION IN THE INFLUENCESS CONSTITUTION TO FORM A SOLID PRODUCT OR FIRST PREPARATION OF A SOLUTION IN LIQUID HYDROCARBONOUND OF THE MAGNESIUM COMPOUND (I) AND TITANIUM COMPOUND (II), AND SUBSEQUENT EDUCATION OF THE SOLID PRODUCT THEREOF, WHERE THE RESPONSE OF THE FORMATION OF THE SOLID PRODUCT IS CARRIED OUT IN THE PRESENCE OF (D) AT LEAST ONE E LEKTRON ENDONATOR AND, DURING OR AFTER THE FORMATION OF THE SOLID PRODUCT, CONTACTING THE SOLID PRODUCT WITH (E) AN ESTER SELECTED UNDER ESTERS OF POLYCARBONIC ACIDS AND ESTERS OF POLY-HYDROXY COMPOUNDS, (B) AN ORGANOMETALLIC COMPOUND OF A METAL SELECTED UNDER METALS OF GROUP I TO III OF THE PERIOD SYSTEM , AND (C) AN ORGANOSILICIUM COMPOUND WITH AN SI-OC BINDING OR SI-NC BINDING.THE FURTHER OBJECT OF THE INVENTION IS THE SOLIDITANATE CATALYST COMPONENT (A) AS SUCH AS IN CONNECTION WITH COMPONENTS (B) AND (C).

Description

The invention relates to a process for the preparation of olefin polymers (sometimes called both homopolymers and copolymers of olefins) by polymerization (both homopolymerization and copolymerization are sometimes referred to herein) of olefins. In particular, it relates to a process for the preparation of olefin polymers with high stereospecificity in large quantities by polymerization of α-olefins having at least 3 carbon atoms.

Characteristic of the known technical solutions

Many techniques have heretofore been recommended with regard to the formation of a solid catalyst component consisting essentially of magnesium, titanium, halogen and an ion donor, and it is known that the use of this solid catalyst component highly stereospecific polymers with high catalytic activity in the polymerization of ^ -olefins of at least 3 carbon atoms, however, it was desirable to "improve many of these earlier techniques in terms of the activity of the catalyst components and the stereospecificity of the polymer."

For example, in order to obtain a high quality olefin polymer without the need for

2 7. JUfi. 19 3 3 * C ^ i? 3V G

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To obtain ζα tion, the proportion of formed stereospecific Polymerem be very high, and the yield of polymer per unit of the transition metal should be sufficiently high. From this point of view, the earlier techniques can be quite high for certain types of polymers. however, few are entirely satisfactory in view of the residual halogen content of the polymer which causes corrosion of molding machines. In addition, many of the ICA tyrosate orcomponents prepared according to previous techniques have the deficiency to reduce yield and stereospecificity to a significant degree.

JP-OS Ir, 34590/1373 (published 26, July 1979) discloses a process for the polymerization of olefins using / a catalyst system containing a compound which overlaps with the component (G) of the catalyst system used in the invention However, this document has no disclosure of the component (A) given in the present application. Japanese Unexamined Patent Publication No. 36203/1980 (published Mar. 13, 1380) also discloses a process of polymerization of olefins using a catalyst system containing a compound which is capable of reacting with the component used in the present invention ( C), but it lacks the disclosure of the catalyst component e (A) »

3 ^ - 23.6.1983

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The JP-OS Hr. No. 811/1981, published Jan. 7, 1981 (corresponding to US Pat. No. 4,330,649), to the invention of which the present inventors were involved, discloses a process for the derivation of Qlefin polymers or copolymers having good I ¹ ability, a uniform particle size and a uniform particle size distribution which is particularly suitable for the polymerization of α-olefins having at least 3 carbon atoms. However, this patent does not suggest any use of a polycarboxylic acid ester and / or an ester of a polyhydroxy compound as a sorbron donor in the formation of a solid titanium catalyst component. Furthermore, it lacks any reference to the combined use of such an ester and the aforementioned electron donor (D) and the combined use thereof with the organic silicon compound (G),

The present inventors made extensive investigations to provide yet another improved process for the polymerization of olefins. Tightening efforts have led to the finding that, using a novel catalyst system type, consisting of the titanium catalyst component (A) prepared by using both the electron donor (D) and the ester (E) selected from esters of the polycarboxylic acids and esters of polyhydroxy compounds, and the above components (3) and (G), polymers having excellent quality in terms of particle size, particle size distribution Particle shape and bulk density with high catalytic performance and a very low decrease in activity over the course of

244747 3 * «e.

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It has also been found that the method according to the invention reduces the deficiency of the state of the art in that an attempt to obtain a high melt-in-one polymer by carrying out the invention has been made. Polymerization in the presence of a molecular weight control agent, such as hydrogen, resulted in a not insignificant decrease in stereospecificity. It has further been found that the use of a small amount of Wasserstaff makes it possible to adjust the melt index of the polymer. The present invention also provides the unexpected advantage that the use of a molecular weight controlling agent such as hydrogen tends to increase the activity of the catalyst.

Aim of the invention; ,

The aim of the invention is therefore to provide an improved process for the polymerization of olefins.

Explanation of the essence of the invention

The invention has for its object to find a novel catalyst system for the production of Ole.finpolymeren or -copolyseren.

More particularly, the invention relates to a process for the preparation of olefin polymers or copolymers which comprises the polymerization of olefins or the copolymerization of olefins and dienes in the presence of a catalyst system: 3 consisting of the following components (A) ₅ (B) and (G) consists: '

47 A7 3 - ^ 23.6.1933

AP C 08 Ρ / 244 74 7/3 61 615/11

(a) a solid toluene catalyst component containing magnesium, halide, halogen and an eater selected from the esters of polycarboxylic acids and the esters of polyhydroxy compounds, the catalyst component being obtained by contacting a liquid hydrocarbon solution of (i) a magnesium compound having (ix) a titanium compound in the liquid state to form a solid product or first preparing a liquid hydrocarbon solution of the magnesium compound (i) and the iitanium compound (ii), and then forming a solid product thereof, wherein the reaction to form the solid product is at least carried out in the presence of (D) an electron donor selected from Monocarbonsäureestern aliphatic Garbonsäuren, ^ arbonsäureanhydriden, ketones, aliphatic ethers, aliphatic carbonates, alkoxy group-containing alcohols, aryloxy groups containing alcohols, orga ^~:;. African Silici compounds having a Si-O-G bond and organic phosphorous compounds having a PGC bond, and during or after the formation of the solid product contacting the solid product with (S) an ester selected from the esters of polycarboxylic acids and esters of polyhydroxy compounds,

(3) an organometallic compound of a metal selected from the metals of Groups I to III of the Periodic Table, and

(G) an organic silicon compound having a Si-O-C bond or Si-I-C bond »

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The invention also relates to the above solid titanium catalyst component.

In the polymerization of QC olefins having at least 3 carbon atoms by the process of the present invention, the resulting polymer shows little or little reduction in stereospecificity even when the melt index is changed by using a molecular weight controlling agent such as hydrogen. Further, by carrying out the process of the present invention by the slurry polymerization method or the gas phase polymerization method, a granular or spherical polymer having a good flowability, a high bulk density and the like can be obtained. has a narrow particle size distribution, most of the particles having a moderate particle size. The process according to the invention also has the advantage that the decrease in the activity of the catalyst during the polymerization time is extremely low.

The magnesium compound (i) used in the preparation of the solid titanium catalyst component (A) in the invention is preferably a magnesium compound having no ability to reduce, d. H. A magnesium compound free from a magnesium.silicon compound. carbon bond or a magnesium-hydrogen bond, "^ ine such magnesium compound may be derived from a magnesium compound, slide has an ability to fieduktion,

Examples of the magnesium compound having no induction capability are magnesium halides such as magnesium.

24 47 4 7 3 - ^ - 2 ₃ .6.

AP G 08 P / 244 747/3 61 615/11

Chloride, magnesioin bromide ,. Magnesium iodide and magnesium fluoride; Alkoxy magnesium halides, ζ * BC-GQ alkoxy magnesium halides such as methoxymagnesium chloride, aethoxymagnesium chloride, isoproporxymagnesiunichloride, butoxy-a-laeazaaciloride and octoxymagnesium chloride; Arylosymagnesium halides, e.g. 3. Phenomagnagna dialkylaluminum, which may optionally be substituted by lower alkyl groups, such as phenol magnesium chloride and methyl-1-phenosymagnesium chloride; ilkoxyiaagnesium compounds, e.g. B. GQ Q-Alkoxyaagneaiumverbindungen, such as Athoxymagnesium, Isopropoxymagnesium, Butoxymagnesium, n-Octosymagnesium and 2-ÄthylhexosymagnesiuH; Acryloxymagneaium compounds, e.g. B. Phenoxyaagnesiumverbindungen, which may be optionally substituted by lower alkyl groups; and magnesium salts of carboxylic acids, ζ » Β. Magnesium salts of. aliphatic carboxylic acids having 1 to 20 carbon atoms,? / ie magnesium laurate Lind ilagnesiumstearät ^ The magnesium compounds may be in the form

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of complexes or mixtures with other metals. The halogen-containing magnesium compounds, especially magnesium chloride, alkoxymagnesium chlorides and aryloxymagnesium chlorides, are preferred among these magnesium compounds.

In the preparation of the liquid-hydrocarbon solution of the magnesium compound (i), various hydrocarbon solvents can be used. Examples include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, tetradecane and kerosene; alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, cyclooctane and cyclohexene; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene and cymene; and halogenated hydrocarbons such as dichloroethane, dichloropropane, trichlorethylene, carbon tetrachloride and chlorobenzene.

The solution may be prepared by various methods selected according to the types of magnesia compound and solvent, for example by simply mixing the two, mixing the two and heating the mixture, or mixing the magnesium compound with the hydrocarbon solvent in the presence of or after treatment with an electron donor capable of solubilizing the magnesium compound, such as an alcohol, an aldehyde, a carboxylic acid, an ether or a mixture thereof, or a mixture thereof with another electron donor and, if necessary, heating the mixture.

For example, in the case of dissolving a halogen-containing magnesium compound (i) in the hydrocarbon solvent with the aid of an alcohol, the alcohol may be in an amount of at least 1 mole, preferably at least about 1.5 mole, more preferably more than 2 mole, per mole The halogen-containing magnesium compound may be used, although the molar ratio thereof may be suitably varied depending on the type and amount of the hydrocarbon solvent and the type of magnesium compound. It is

There is no particular upper limit to the amount of alcohol, but from an economic point of view, it is desirable to use it in not too large an amount. For example, the amount of the alcohol is up to about 40 moles, preferably up to about 20 moles, more preferably up to about 10 moles per mole of the magnesium compound (i). When an aliphatic or alicyclic hydrocarbon is used as the hydrocarbon solvent, alcohols in the above-mentioned proportion are used, and among them, alcohols having at least 6 carbon atoms in an amount of at least about 1 mole, preferably at least about 1.5 moles, per mole of the Halogen containing magnesium compound used. This is preferable because the halogen-containing magnesium compound can be solubilized by using alcohols in a small total amount and a catalyst component having high activity can be produced. In this case, when only alcohols having not more than 5 carbon atoms are used, their amount should be at least about 15 moles per mole of the halogen-containing magnesium compound, and the resulting catalyst component has a lower catalytic activity than those obtained as described above. On the other hand, when an aromatic hydrocarbon is used as the hydrocarbon solvent, the halogen-containing magnesium compound can be solubilized using alcohols in the above amounts regardless of the types of the alcohols. Furthermore, when e.g. a tetraalkoxytitanium simultaneously as the titanium compound (ii) in the solubilization of the halogen-containing magnesium compound, the use of a small amount of alcohols to solubilize the halogen-containing magnesium compound.

Preferably, the contacting of the halogen-containing magnesium compound with the alcohols in a hydrocarbon medium usually at room temperature .. or carried out a higher temperature and depending on the types of these compounds in excess of about 55 ⁰ C, preferably from about SO ⁰ C to about 30O ⁰ C ₇ bei'etwa particular 100 to 200 ⁰ C. The con-

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Clock duration can also be selected appropriately. For example, it is about 15 minutes to about 5 hours, preferably about 30 minutes to about 2 hours. Examples of suitable alcohols having at least β carbon atoms are C _fi -C "aliphatic alcohols, such as 3-methyl pentanol, 2-Äthylbutanol, n-heptanol, n-octanol, 2-ethylhexanol, decanol, dodecanol, tetradecyl alcohol, undecenol, oleyl alcohol and stearyl alcohol ; C ₁ -C 10 -alicyclic alcohols, such as cyclohexanol and methylcyclohexanol; C -C aromatic alcohols, such as benzyl alcohol, methylbenzene alcohol, isopropylbenzyl alcohol, α-methylbenzyl alcohol and α, α-dimethylbenzyl alcohol; and C _g -Cp aliphatic alcohols having an alkoxy group such as n-butyl cellosolve (= ethylene glycol mononobutyl ether) and 1-butoxy-2-propanol. Examples of other alcohols are alcohols having not more than 5 carbon atoms, such as methanol, ethanol, P. tropanol, butanol, ethylene glycol and methyl carbitol.

When the carboxylic acid is used as the electron donor, organic carboxylic acids having at least 7 carbon atoms are suitable. Examples include those having 7 to 20 carbon atoms, such as caprylic acid, 2-ethylhexanoic acid, undecylenic acid, undecanoic acid, nonylic acid and getanoic acid.

Suitable aldehydes for use as electron donors are ¹ those having at least 7 carbon atoms. Examples are those of 7 to 13 carbon atoms, such as capric aldehyde, 1-ethylhexyl aldehyde, capryl aldehyde and undecyl aldehyde.

Suitable amines are those having at least δ carbon atoms. Examples include amines having from 6 to 18 carbon atoms, such as hepytyl on the in, octyl on the amine, nonylamine, decylamine, laurylamine, undeciamine and 2-ethylhexylamine.

An example of ether as an electron donor is tetrahydrofuran.

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The preferred amounts of these carboxylic acids, aldehydes, amines and ethers and the preferred temperatures at which they are used are substantially the same as described above.

The hydrocarbon solution solution of the magnesium compound (i) can also be prepared by using metallic magnesium or other magnesium compound which can be converted into the magnesium compound (i) and dissolving in the hydrocarbon solvent to convert it into the magnesium compound (i ) are formed. For example, this can be achieved by reacting a magnesium compound having an alkyl, alkoxy, aryloxy, acyl, amino or hydroxyl group, magnesium oxide or metallic magnesium in a hydrocarbon solvent containing the alcohol, the amine, the aldehyde, contains, dissolves or suspends the carboxylic acid, the ether, etc., and forms a halogen-containing magnesium compound (i) having no reduction ability while containing a halogenating agent such as hydrogen halide, a halogen-containing silicon compound ¹ , halogen, a calogen Aluminum compound, a halogen-containing lithium compound or a halogen-containing sulfur compound halogenated. Alternatively, it is possible to use a Grignard reagent, a dialkylmagnesium, magnesium hydride or a complex of such a magnesium compound with another organometallic compound, for example a magnesium compound with reducing agent.

1 2 higung, represented by the formula M Mg R R X Y_, wherein

CC ij Ό O - ^ O

M is aluminum, zinc, boron or beryllium, R and R are a hydrocarbon group, X and Y are a group of the formulas OR, OSiR ⁴ R 1, R ⁰ , NR R or SR, R ³ , R ⁴ ,

C c η ο

R, R, R and R represent a hydrogen atom or a carbon monoxide

group, R is a hydrocarbon group, α and β are greater than 0, p, q, r and s are a number of at least 0, m is the atomic valency of M, ß / a = 0.5, ρ + q + r -fs = mcc + 2β and 0 4 (r + s) / (cc + Q) <1.0, with a compound capable of destroying the reducing ability, such as an alcohol, a ketone, an ester, a

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Ether, an acid halide, a silanol, a siloxane, oxygen, water, an acetal or an alkoxy or aryloxy compound of silicon or aluminum, and the resulting magnesium compound (i) having no reduction ability in the hydrocarbon solvent dissolve. In the above formulas, examples of hydrocarbon groups are C -C -Q-alkyl groups such as an ethyl group, propyl group, butyl group, amyl group, hexyl group, octyl group and dodecyl group, and Cg-C- aryl groups such as a phenyl group and ToIy!

As the titanium compound (ii), various titanium compounds can be used in the preparation of the titanium catalyst component (A). Preference is given to tetravalent titanium compounds of the formula

wherein R represents a hydrocarbon group, - X represents a halogen atom and g is a number represented by 0 = g = 4. In the above formula, examples of the hydrocarbon group are C 2 -C 4 alkyl groups and a phenyl group having a substituent such as a lower alkyl group, e.g. may have a C 1 -C 4 alkyl group, and a halogen atom.

Specific examples of titanium compound (ii) include titanium tetrahalides such as TiCl ₄ , Ti 3r _4, and TiJ ₄ ; Alkoxytitanium trihalides such as Ti (QCH ₃ ) Cl ₃ , Ti (OC ₂ H ₃ ) Cl ₃ , Ti (OnC ₄ H ₉ ) Cl ₃ , Ti (OC ₂ H ₅ ) Br ₃ and Ti (O-IsO) C ₄ H ₉ ) Br ₃ ; Alkoxytitanium dihalides such as Ti (OCH _{3) 2} C1 _2, Ti (OC ₂ H _{5) 2} ^C1 2 »Tito nC ^ Hg) 2 ^C1 2 ^{and Ti} (° ^C 2 ^H s) 2 ^{Br? Trialkox} Y- ^{: itan} - ^raono halides, such as Ti (OCH ₃ KCl, Ti (OC ₂ H ₅ ) 1 Cl, Ti (0-n C _d H _g ) ₃ Cl and Ti (OC-Hc), 3r; Tetra-alkoxy-titanium compounds such as Ti (OCH ₃ I ₄ , 'Ti (OC ₂ Hc) ₄ and Ti (0-nC ₄ H _g ) ₄ ; mixtures thereof and mixtures thereof with hydrogen halides, halogens, other metal compounds, Among these, the halogen-containing titanium compounds are preferable Titanium tetrahalides, especially titanium tetrachloride, are particularly preferred.

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The Ti'tan compound (ii) in the liquid state may be a single or a mixture of titanium compounds, which in turn are liquid, or it may be a solution of the titanium compound in a solvent such as hydrocarbons.

In the present invention, the solid catalyst component (A) containing magnesium, titanium, calcine and a compound selected from esters of the polycarboxylic acids and esters of the polyhydroxy compounds can be prepared in the following manner.

A liquid hydrocarbon solution of the magnesium compound (i) is contacted with the titanium compound (ii) in a liquid state to form a solid product. Or, a liquid-hydrocarbon solution of a mixture of the magnesium compound (i) and the titanium compound (ii) is first prepared, and then a solid product is formed therefrom. The reaction of forming the solid product is carried out in the presence of at least one electron donor (D) specified below, and the product is reacted with the ester (E) selected from esters of the polycarboxylic acids and esters of the polyhydroxy compounds during formation of the solid product [Embodiment (a)] or after the formation of the solid product [Embodiment (b)].

The electron donor (D) is selected from monocarboxylic acid esters, aliphatic carboxylic acids, carboxylic anhydrides, ketones, aliphatic ethers, aliphatic carbonates, alkoxy group-containing alcohols, aryloxy group-containing alcohols, Si-0-C3 organic silicon compounds, and organic phosphorus compounds POC bond. Examples of preferred electron donors include CC-monocarboxylic acid esters, CC "_-, preferably C ₁ -C _r -aliphatic carboxylic acids, C _d -C _n ^ carboxylic anhydrides, C ₃ -C ₉ ketones, C _n -C ₁ ,. aliphatic ethers, C 1 -C ₁ -aliphatic carbonates, alcohols containing C 1 -C 6 -alkoxy groups,

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C 1 -C 18 aryloxy group-containing alcohols, organic silicon compounds having a Si-O-C bond wherein the organic group has 1 to 10 carbon atoms, and organic phosphorus compounds having a P-O-C bond wherein the organic group has 1 to 10 carbon atoms.

Specific examples of monocarboxylic acid esters are methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, isobutyl acetate, tert-butyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerianate, ethyl pyruvate, ethyl pivalate, methyl chloroacetate, ethyldichloroacetate, methyl methacrylate, ethyl crotonate, methylcyclohexanecarboxylate, methyl benzoate, ethyl benzoate, Propyl benzoate, 3-butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, ethyl anisate, and ethyl ethoxybenzoate.

Specific examples of aliphatic carboxylic acids are formic acid, acetic acid, propionic acid, butyric acid and valeric acid.

Specific examples of carboxylic acid anhydrides are acetic anhydride, maleic anhydride, benzoic anhydride, phthalic anhydride, trimellitic anhydride and tetrahydrophthalic anhydride.

Specific examples of ketones are acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl n-butyl ketone, acetophenone, benzophenone, cyclohexanone and benzoquinone.

Specific examples of aliphatic ethers include methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, ethyl benzyl ether, ethylene glycol dibutyl ether and anisole.

Specific examples of Mkoxycnjppen-containing alcohols are butyl cellosolve (ethylene glycol monobutyl ether) and ethyl cellosolve (ethylene glycol monoethyi ether).

Specific examples of aliphatic carbonates are dimethyl, carbonate D-.iäthylcarbonat and ethylene carbonate.

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Specific examples of organic silicon compounds having a Si-O-C bond are methyl silicate, ethyl silicate and diphenyldimethoxysilane.

Specific examples of organic phosphorus compounds having a P-O-C bond are trimethyl phosphite and triethyl phosphite.

If desired, these electron donor compounds can be formed in situ during the formation of the catalyst component (A).

Examples of preferred polycarboxylic acid esters or esters of polyhydroxy compounds used in the preparation of the catalyst component (A) are those having a skeleton represented by the formulas

R ³ -C -COOR ¹

k '2 RC-COOR,

or

R ³ -C -OCOR ⁵ RC-OCOR

ι

worm R represents a substituted or unsubstituted hydrocarbon group; R ~, R and R ° represent a hydrogen atom or a substituted or unsubstituted hydrocarbon

3 4

R and R "represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group

3 4

and preferably one of R and R "is a substituted or unsubstituted hydrocarbon group,

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or R and R may be linked together; and the aforementioned substituted hydrocarbon group is a substituted hydrocarbon group having a hetero atom such as N, O and S, s.3. one that has a group like COC-. COOR, COOH, OH, SO ^ IVCNC- or MH ₉ contains is.

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Examples of the hydrocarbon group in the above formulas include C -C _Q alkyl groups such as a methyl, ethyl, propyl, butyl, amyl, hexyl or octyl group, Cg-Cg-aryl groups such as phenyl, tolyl, xylyl, benzyl or naphthyl group, C -C -Alkylidengruppen, such as a methylidene, ethylidene or propylidene, and CC ^ ₀ alkenyl groups such as vinyl, allyl or propenyl group.

3 * 4 Examples of the ring formed by the bonding of R and R are cyclohexane, benzene, naphthalene, norbornane and cyclopentane rings.

These hydrocarbon groups may contain substituents as illustrated above.

Among these electron donors (D), preferred are monocarboxylic acid esters, aliphatic carboxylic acids, carboxylic anhydrides, ketones, alkoxy group-containing alcohols and organic silicon compounds having a Si-O-C bond. The monocarboxylic acid esters and carboxylic acid anhydrides are particularly preferred.

Specific examples of preferred polycarboxylic acid esters (Ξ) include C - C_ aliphatic polycarboxylic esters, such Diäthylmethylsuccinat, diisobutyl a-methylglutarate, Diäthylmethylmalonat, Diäthyläthylmaionat, Diäthylisopropylmalonat, Diäthylbutylmalonat, Diäthylphenylmalonat, Diäfnyldiäthylmalonat, Diäthyldibutylmalonat, Monoisooctylmaleat, diisooctylmaleate, diisobutyl maleate, Diisobutylbutylmaleat, 'diisopropyl β-methylglutarate, diallyl ethyl succinate, di-2-ethylhexyl fumarate, diisooctyl citrate, and esters of long chain dicarboxylic acids (eg, diethyl diadipate, diisobutyl adipate, diisopropyl sebacate, di-n-butyl sebacate, di-n-octyl sebacate and di-2-ethylhexyl sebacate); C ₁₀ -C ₃ alicyclic polycarboxylic acid esters such as diethyl 1,2-cyclohexanecarboxylate and diisobutyl-1, Z-cyclohexanecarboxylate; C 1 -C 8 -aromatic polycarboxylic esters, such as monoethyiphthalate, dimetyl phthalate, methylethyl phthalate, monoisobutyl phthalate, diethyl phthalate, ethyl isobutyl phthalate, di-n-propyl phthalate, diisopropyl

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phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-n-heptyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, di-neopentyl phthalate, di-decyl phthalate, benzyl butyl phthalate, diphenyl phthalate, diethylnaphthalenedicarboxylate and dibutylnaphthalenedicarboxylate; and C ₃ -C ₃ heterocyclic polycarboxylic acid esters such as esters of 3,4-furan dicarboxylic acid.

Examples of preferred esters of polyhydroxy compounds (E) are esters formed between C _r to C, aromatic polyhydroxy compounds and C to C ₁₂ "", preferably C 1 to C aliphatic carboxylic acids such as 1,2-diacetoxybenzene , 1-methyl-2,3-diacetoxybenzene and 2,3-diacetoxynaphthalene.

In introducing the substance derived from the ester selected from esters of the polycarboxylic acids and esters of polyhydroxy compounds into the catalyst component (A), it is not always necessary to use such compound itself as a starting material. If desired, it is possible to use a compound capable of being converted into such a compound during the preparation of the titanium catalyst component (A) and converting it to the ester during the preparation of the catalyst component (A).

The amount of the electron donor (D) present during the formation of the solid product in the embodiment (a) or (b) is, for example, about 0.01 to about 1 mol, preferably about 0.05 to about 0.5 mol, per each Mol of the magnesium compound (i). By choosing such an amount, the particle size of the solid product can be adjusted.

When the amount of the electron donor (D) zv. is large, it can be deposited on the solid product to a great extent and possibly exert adverse effects, although the extent of the adverse effects varies according to the type of the electron donor (D). It is therefore preferable to select an appropriate amount within the above range.

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When the solid product is formed in the presence of the polycarboxylic acid ester and / or the ester of the phenylhydroxy compound, (E), according to the embodiment (a), the ester (E) is preferably used in an amount of about 0.01 to about 1 mole, especially from about 0.1 to about 0.5 mole, per mole of the magnesium compound (i) used. Preferably, the molar ratio of ester (E) deposited on the solid product to the electron donor (D) is adjusted to 1: about 0.01 to about 2, more preferably l: about 0.1 to about 1.

In order to form a magnesium and titanium-containing solid product of a hydrocarbon solution of the magnesium compound (i) and the titanium compound (ii) in a liquid state, it is preferred to use a method of reacting the two liquids by contacting them with each other a halogen-containing compound as titanium compound (ii). in an amount sufficient to form the solid product. The amount of titanium compound (ii) used may vary according to its type,

the contacting conditions and the amounts of the electron donor (D) and the other constituents vary. Preferably, their amount is at least 1 mole, usually about 2 to about 200 moles, more preferably about 3 to about 100 moles, per mole of the magnesium compound Ci).

When the solid product is difficult to form by merely contacting the liquid hydrocarbon solution of the magnesium compound (i) with the titanium compound (ii) in a liquid state, or the solid product is difficult to be simply left standing by the hydrocarbon solution of the compounds (i) and (ii) an additional amount of titanium compound (ii), preferably a halogen-containing titanium compound, (ii) 'may be added, or another precipitating agent may be added to form the solid product, examples of such Precipitants are halogenating agents. such as halogens, halocenated hydrocarbons, halogen-containing silicon compounds, halogen-containing aluminum compounds, halogen-containing

kl kl 3

Lithium compounds, halogen-containing sulfur compounds and halogen-containing antimony compounds. Specific examples are chlorine, bromine, hydrogen chloride, hydrochloric acid, phosphorus pentachloride, thionyl chloride, thionyl bromide, sulfuryl chloride, phosgene and nitrosyl chloride.

The solid product differs in shape or size depending on the conditions of its formation. In order to obtain a solid product having a uniform shape and a uniform particle size, it is preferred to avoid rapid formation. For example, when the solid product is to be formed by mixing the compounds Ci) and (ii) in the liquid state and reacting with each other, it is advisable to mix them at a sufficiently low temperature which does not cause rapid formation of a solid product and then - gradually increase the temperature. According to this method, a granular or spherical solid product having a large particle diameter and a narrow particle size distribution can be easily obtained. *

Will one. Slurry polymerization or gas phase polymerization is carried out by using the granular or spherical solid catalyst component having a good particle size distribution which can be obtained as above, the resulting polymer is granular or spherical and has a narrow particle size distribution, a high bulk density and a good flowability. The term "granular" as used herein refers to particles that look like an array of fine powders when examined with the aid of an enlarged photograph. Particles ranging from those having numerous non-planar portions to those approaching a true sphere may be obtained as a granular product depending on the preparation of the solid catalyst component.

44 74 7 3

Contacting the liquid hydrocarbon solution of the magnesium compound (i) with the titanium compound (ii) in a liquid state may be carried out for example at a temperature of about -70 ⁰ C to about +200 ⁰ C. The temperatures of the two liquids to be contacted may be different from each other. In general, it is often preferred to use a non-high temperature contact-dissolution method to obtain a solid catalyst component of desired granular or spherical shape and high performance. For example, temperatures of about -70 to about +50 C are preferred. If the contacting temperature is too low, precipitation of a solid product is sometimes not observed. In such a case, it is desirable to increase the temperature to about 50 to about 150 C, for example, or to continue contacting for a longer period of time until precipitation of the solid product occurs.

The solid product is preferably washed with an excess of liquid titanium compound or liquid halogenated hydrocarbon, preferably titanium tetrachloride, 1,2-dichloroethane, chlorobenzene, methyl chloride and kexachloroethane, at least once at a temperature of, for example, about 20 to about 150 ° C. Thereafter, the product is usually washed with a hydrocarbon and can be used in the polymerization. Examples of the hydrocarbon may be the same as those given above with respect to the formation of the liquid-hydrocarbon solution of the magnesium compound (i).

The method according to the embodiment (a) is excellent because its operation is simple and a high performance solid catalyst component (A) can be obtained.

In the embodiment (b), the following procedure can be used. '

244747 3

2 / - 22Τ -

A suspension of the solid product is formed after forming a hydrocarbon solution of the magnesium compound (i) and the titanium compound (ii) or by contacting the magnesium compound (i) in a liquid state and the titanium compound (ii) in a liquid state as in the embodiment ( a) ago. In general, a method can be used in which the polycarboxylic acid ester and / or the ester of the polyhydroxy compound are added to this suspension and reacted at a temperature of, for example, about 0 to about 150 ° C. The amount of the electron donor used is the same as in the embodiment (a). The resulting solid product may be washed at least once with a liquid titanium compound, preferably an excess of titanium tetrachloride.

Chloride at a temperature of about 20 to about 150 ° C.

If desired, embodiments (a) and (b) may be applied together in the present invention.

In the formation of the solid product in the present invention as described above, a porous inorganic and / or organic solid compound may be present such that the solid product is deposited on the surface of the porous solid compound. In this case, it is possible to previously contact the porous solid compound with the magnesium compound (i) in the liquid state, and then contact the porous solid compound containing the liquid magnesium compound with the liquid titanium compound (ii) ,

Examples of the porous solid compound are silica, alumina, polyolefins, and products obtained by treating these compounds with halogen-containing compounds such as chlorine, bromine, hydrogen chloride, 1,2-dichloroethane, and chlorobenzene.

The solid titanium catalyst component (A) used in the invention may be one obtained according to the

24 47 47

above embodiment (a) or (b) with or without further washing with a titanium compound, a hydrocarbon, etc.

Preferably, the solid titanium catalyst component (A) which can be obtained by any of the above-described embodiments is used for the polymerization after being well washed with a hydrocarbon. The obtained solid titanium catalyst component (A) preferably has such a composition that the magnesium / titanium atomic ratio, for example from about 2 to about 100, preferably from about 4 to about 50, more preferably from about 5 to about 30, the halogen / titanium atomic ratio is e.g. from about 4 to about 100, preferably from about 5 to about 90, more preferably from about 8 to about 50, and the electron donor / titanium molar ratio is e.g. from about 0.01 to about 100, preferably from about 0.2 to about 10, more preferably from about 0.4 to about 6. As stated above, the shape of the catalyst component (A) is granular or nearly spherical in many cases. Usually, it has a specific surface area of, for example, at least about

2 "2

10 m / g, preferably about 100 to about 1000 m / g.

The halogen in the solid titanium catalyst component (A) is chlorine, bromine, iodine, fluorine or two or more of them, preferably chlorine. The electron donor included in the catalyst component (A) contains at least the ester (E) selected from esters of polycarboxylic acids and esters of polyhydroxy compounds, and sometimes also contains the electron donor (D) '.

The ratio of the ester (E) to the other electron donor (D) varies depending on the type of the electron donor (D). The catalyst component (A) exhibits good performance even if it is not more than about 2 moles, preferably not more than about 1 mole, more preferably not more than 0.5 moles of the other slektronene donor (D) per mole of ester Contains (E).

244747 3 _ - £ -

In the present invention, olefins are polymerized by using a catalyst system consisting of the solid titanium catalyst component (A) prepared as above, the organometallic compound (3) of the metal of Groups I to III of the Periodic Table, and the organic silicon compound (C).

As examples of the organometallic compound (3), the following compounds may be mentioned.

(1) Organoaluminum compounds having at least one Al-C bond in the molecule, e.g. Organoaluminum compounds of the general formula

R ¹ Al (OR ² ) H x m η ρ q

Wherein R and R are the same or different and each having a hydrocarbon group, for example a hydrocarbon group with. 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, m is a number represented by 0 <m = .3, η is a number represented by 0 in <3, ρ is a number by 0 ip <3, q is a number represented by 01 q <3, and

(2) Complex alkylated products of aluminum and a metal of Group I represented by the general formula

M ¹ A1R ¹ ₄

1 1

wherein M is Li, Na and K and R is as defined above

(3) Dialkyl compounds of a metal of the group xi represented by the general formula

12 2

wherein R and R are as defined above and M is Mg, Zn

and Cd means. ·

244747

In the above formulas are examples of the carbon

12 hydrogen group of R and R alkyl groups and aryl groups.

Examples of organoaluminum compounds (1) are shown below.

12 1

Compounds of general formula R Al (OR) -, wherein R and R are as defined above, m is preferably a number represented by 1.5 i m i 3;

1 1

Compounds of the general formula R AlX-, wherein R is as

³ m J-m ⁷

X is halogen and m is preferably a number represented by 0 <m <3;

Compounds represented by the general formula 11

R AlH-, wherein R is as defined above and m before 3- nr

preferably a number represented by 2 ^ m <3, and

12 Ί

Compounds of the general formula R Al (OR) X. in which R "and R are as defined above, X is halogen, 0 <m i 3, 0 = η <. 3, Ot q <3 and m + n + q = 3.

Specific examples of the organoaluminum compounds of the formula (1) are trialkylaluminums such as triethylaluminum and tributene-1aluminum; Trialkenylaluminum compounds such as triisoprenylaluminum; partially alkoxylated alkylaluminum compounds, e.g. Dialkylaluminum alkoxides, such as. Diethylaluminum ethoxide and dibutylaluminum butoxide; Alkylaluminum sesquialkoxide, such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide; Compounds with an average composition expressed by

12 R - ^ - t-AKOR) _n , -; partially halogenated alkylaluminum compounds, eg, dialkylaluminum halides, such as diethylaluminum chloride, dibutylaluminum chloride, and diethylaluminum bromide; Alkylaluminum sesquihalides, such as ethylaluminum sesquichloride, butylaluminum sesquichloride and ethylaluminum sesquibromide; Alkylaluminum dihalides, such as ethylaluminum dichloride, propylaluminum dichloride and 3-butylaluminic acid dibromide; partially hydrogenated alkylaluminum compounds, z.3. Dialkylaluminum hydrides, such as diethy! Aluminum hydride and di-

244747 3

butylaluminum hydride, alkylaluminum dihydrides such as ethylaluminum dihydride and propylaluminum dihydride; and partially alcoholated and halogenated alkylaluminum compounds, e.g. Alkylaluminum alkoxyhalides such as ethylaluminum ethoxychloride, butylaluminum butoxychloride and ethylaluminum ethoxybromide.

Examples of compounds mentioned under (2) above are LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ J ₄ .

Examples of the compounds mentioned above under (3) are diethylzinc and diethylmagnesium. Alkylmagnesium halides, such as ethylmagnesium chloride, can also be used.

Organoaluminum compounds in which two or more aluminum atoms are bonded via an oxygen or nitrogen atom, analogously to the compounds (1), may also be used. Examples of such aluminum compounds are (C ₂ H ₅ ) ₂ AlOAl (C ₂ H ₅ ) ₂ , (C ₄ Kg) ₂ AlOAl (C ₄ K ₉ ) and (C ₂ K ₅ ) ₂ AlNAl (C ₂ H ₅ ) ₂ ,

Among the above organoaluminum compounds, trialkylaluminum compounds and alkylaluminum compounds in which two or more aluminum atoms are bonded are preferable.

Examples of the organosilicon compound (C) having a Si-O-C or Si-N-C bond are alkoxysilanes and aryloxysilanes. For example, may be mentioned organosilicon compounds represented by the following general formula

R Si (OR ¹ ). η 4-n

wherein R represents a hydrocarbon group such as an alkyl, cycloalkyl, aryl, alkenyl, keto-alkyl or aminoalkyl group, or halogen, R "represents a hydrocarbon group such as an alkyl, cycloalkyl, aryl, alkenyl or alkoxyalkyl

2447 47

group, and η is a number represented by O 4 η έ 3, preferably O ^ η 1 .2, and n_ R groups or (4-n_) OR groups may be the same or different.

In the above formula R is preferably a C ₁ -Cp - hydrocarbon group such as a C -C _Q alkyl group, a C ^ -Cp-cycloalkyl group, a C, -C_ aryl group, a C -C _1o alkenyl group, a C ₁ -C ₁ --Halogenalkylgruppe or a C -C. Aminoalkyl group, and a halogen atom such as a chlorine atom; and R is preferably a C.-C- hydrocarbon group, such as a C.-C alkyl group, a C ₅ -C ₂ - ^c Y ^c loalkylgruppe, a C_-C "-aryl group, a C" -C alkenyl group, or a C "-C alkoxyalkyl group.

Further examples of the catalyst component (C) include siloxanes having the group OR · and carboxylic acid silyl ester. Examples of-R are the same as those given above. Also, the reaction product of a compound having no Si-O-C bond with a compound having an O-C bond obtained either in advance or in situ may be used. For example, For example, the co-use of a halogen-containing silane compound containing no Si-OC bond, 'or a silicon hydride' with an alkoxy group-containing aluminum compound, an alkoxy group-containing magnesium compound, another metal alcoholate, an alcohol, a formate ester, ethylene oxide, etc. can be cited , The organosilicon compound may contain another metal such as aluminum and tin.

Examples of preferred organosilicon compounds as component (C) include trimethylmethoxysilane, Trimethylathoxysilan, dimethyldimethoxysilane, Dimethylciäthoxysilan, diphenyldimethoxysilane, Methylpnenylcimethoxysilan, Diphenyldiäthoxysilan, Äthyltrimethoxysilan, methyltrimethoxysilane, vinyl trimethoxy silane ', trimethoxysilane, phenyl, y'-Chlorpropy 1-trimethoxysilane, methyltriethoxysilane, Äthyltriäthoxysilan, vinyltriethoxysilane, Butyltriethoxysilane, phenyltriethoxysilane, γ -aminopropyltriethoxysilane, chloro-diethoxysilane,

244747 3

Ethyltriisopropoxysilane, vinyltributoxysilane, ethylsilicate, butylsilicate, trimethylphenoxysilane, methyltriallyloxysilane, vinyltris (β-methoxyethoxy) silane, vinyltriacetoxysilane, dimethyltetraethoxydisiloxane and phenyldiethoxydiethylaminosilane. Among them, methyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, vinyltributoxysilane, ethylsilicate, diphenyldimethoxysilane, diphenyldiethoxysilane and methylphenylraethoxysilane [the compounds of the

above formula R Si (OR) . ] especially before ³³ η 4-η

Trains t.

Component (C) may be used in the form of an adduct with other compounds.

According to the invention there is provided a process for the preparation of olefin polymers or copolymers comprising the polymerization or copolymerization of olefins or the copolymerization of at least one olefin with a minor proportion, e.g. up to 10 mol% of a diene in the presence of a catalyst system consisting of the solid titanium catalyst component · (A), the organometallic compound (B) and the organosilicon compound (C).

Examples of usable olefins are olefins having 2 to 10 carbon atoms, such as ethylene, propylene, 1-butene, · 4-methyl-1-pentene and 1-octene. They can be homopolymerized or random copolymerized or block copolymerized. The diene may be a polyunsaturated compound such as conjugated dienes or non-conjugated dienes. Specific examples include butadiene, isoprene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-kexadiene, ethylidene norbornene, vinyl norbornene, and 1,7-octadiene.

The catalyst system according to the invention can advantageously be used in the polymerization or copolymerization of α-olefins with at least 3 carbon atoms, in particular in the polymerization or copolymerization of α-olefins with 3 to

2447 47 3

10 carbon atoms, or in the copolymerization of at least one such a-01efin with bis. be used to 10 mol% of ethylene and / or a diene.

The catalyst system of the present invention exhibits the excellent property that when used for the polymerization of ethylene, it gives a high yield of polymer having a narrow particle size distribution, a high bulk density and a narrow molecular weight distribution.

The polymerization can be carried out either in liquid or in the gas phase. When the liquid-phase polymerization is carried out, inert solvents such as hexane, heptane and kerosene can be used as the reaction medium. If desired, the olefin itself can be used as the reaction medium. The amount of the catalyst can be appropriately selected. For example, 1 each reaction solvent in the case of liquid phase reaction or 1 per volume of reaction zone in the case of a gas phase reaction, component (A) in an amount of 'from 0.0001 to in a preferred ^embodiment: 1 mMol used as the titanium atom; the component (B) is used in such a proportion that the amount of the metal atom in the component (B) is 1 to 2,000 moles, preferably 5 to 500 moles, per mole of the titanium atom in the component (A): and the component (C) used in such a proportion that the amount of silicon atom in the component (C) is 0.001 to 10 mol, preferably 0.01 to 2 mol, more preferably 0.05. to 1 mole per mole of metal atom in component (B).

The catalyst components (A), (B) and (C) may be contacted with each other before or during the polymerization. If they are brought into contact before the polymerization, only two of them can be freely selected and brought into contact. Or, two or three components may be partially picked up and placed in contact with each other. The contacting of these components prior to polymerization may be carried out in an inert gas atmosphere or in an AtmosDhäre of an olefin.

244747 3

-ZS

The polymerization temperature is preferably about 20 to about 200 ° C, especially about 50 to about 180 ⁰ C. The

Pressure is from atmospheric to about 98 * 10 Pa

2 5

(100 kg / cm), preferably from about 2 x 10 6 Pa to about

5 2

49.10 Pa (about 2 to about 50 kg / cm). The polymerization may be carried out batchwise, semi-continuously or continuously, or the polymerization may also be carried out in two or more stages with different reaction conditions.

If the method of the invention is applied to the stereospecific polymerization of cc-olefins. having at least 3 carbon atoms, polymers having a high stereospecificity index with high catalytic activity can be formed. While an attempt to use a high melt index polymer through the use of hydrogen in the polymerization of an olefin using the heretofore recommended solid titanium containing catalyst components tends to result in a significant reduction in stereospecificity, the use of the catalyst system of this invention may have this tendency Reduce.

In view of the high activity of the catalyst, the yield of the polymer per unit weight of the solid titanium catalyst component (A) is greater than that in the prior art if polymers having the same stereospecificity index are to be obtained. Therefore, the catalyst residue, especially the halogen content, of the resulting polymer can be reduced. This not only enables the catalyst removal operation to be omitted, but also significantly inhibits the corrosion tendency of molds during molding.

When the process of the present invention is applied to slurry polymerization or gas phase polymerization, a granular or near-spherical polymer can be formed which looks as if it were the aggregate product of fine powders. In such a way

11 Ί 1 Ll \ ' ² ^ " 23.6.1983

£ «4 <4 / H / α ^ QO ₈ 57244 747/3

61 615/11

granular or spherical polymer has good flowability and can be used directly without pelletization in some applications. Another advantage is that the melt index of the polymer can be changed by using a lower amount of molecular weight controlling agent such as hydrogen than in the case of conventional catalyst systems and surprisingly by increasing the amount of the molecular weight control agent the activity of the catalyst in the Unlike conventional catalysts tends to increase. In conventional catalyst systems, increasing the amount of the molecular weight control agent in an attempt to obtain a polymer having a high melt index results in the decrease in the partial pressure of the quenfin monomer and, of course, in the decrease of the activity of the catalyst system no such problem, and its activity tends to increase as the amount of the molecular weight controlling agent increases.

While the conventional catalyst systems decrease in activity over the course of the polymerization, such a phenomenon is hardly observed in the catalyst system of the present invention. The present invention also has the advantage that even if the catalyst system is used in a multi-stage continuous polymerization process · The amount of polymeric product can be greatly increased,

Since the catalyst system according to the invention is very stable at high temperatures, a reduction of the stereos

/ »7 A 7 * 1" ²⁸ ^ ^- 23.6.1933

^ / ". · W A C 08/244 747/3

61 615/11

apezifität even hardly beobaciitet when propylene is polymerized at a temperature of, for example, about 90 _# C · ⁰

Ausftihrungsbeiapiel

The following examples illustrate the invention in more detail.

244747 3 - ^# -

Example 1 .

Preparation of a Solid Titanium Catalyst Component (A)

4.76 g (50 mmol) of anhydrous magnesium chloride, 25 ml of decah and 23.4 ml (150 mmol) of 2-ethylhexyl alcohol were reacted at 130 ° C. for 2 hours to form a uniform solution. To the solution was added 1.11 g (7.5 mmol) of phthalic anhydride, and the mixture was further stirred at 130 ° C for 1 hour to dissolve the phthalic anhydride in the uniform solution. The resulting uniform solution was cooled to room temperature and completely dropwise added with 200 ml (1.8 mol) of titanium tetrachloride kept at -20 ° C over one hour. After the addition, the mixture was heated to 110 ° C over 4 hours, and when the temperature reached 110 ° C, 2.68 ml (12.5 mmol) of diisobutyl phthalate was added. The mixture was then kept under stirring at this temperature for 2 hours. After the reaction, the reaction mixture became hot, filtered to collect the solid portion. The solid portion was resuspended in 200 ml of titanium tetrachloride and reacted at 110 ° C. for 2 hours. After the reaction, the solid portion was collected by hot filtration and washed with decane and hexane kept at 110 ° C until no free titanium compound was detected in the washings.

The solid titanium catalyst component (A), which had been synthesized by the above method, was stored in the form of a slurry in hexane. A portion of the slurry was dried to examine the composition of the catalyst. The obtained solid titanium catalyst component (A) was found to contain 3.1% by weight of titanium, 56.0% by weight of chlorine, 17.0% by weight of magnesium and 20.9% by weight of diisobutyl phthalate.

Polymerization:. '' .. ·

A 2 liter autoclave was charged with 750 ml of purified hexane and under propylene atmosphere at room temperature was passed 2.51 mmol of triethylaluminum, 0.125 mmol of phenyltriethylamine.

244747 3

- zer -

oxysilane and 0.015 mmol, calculated as titanium atom, of the catalyst component (A) prepared as described above in the autoclave. After introduction of 200 ml of hydrogen, the temperature was raised to 70 ° C. and propylene was polymerized for 2 hours. During the polymerization,

5 2

de the pressure at 6.9 · 1Ο Pa overpressure (7 kg / cm G) maintained.

After the polymerization, the slurry containing the obtained polymer was filtered to separate into a white powdery polymer and a liquid layer. After drying, the amount of white powdery polymer was 379.2 g. The polymer had an extraction residue in boiling n-heptane of 98.9%, a melt index (MI) of 7.5 and an apparent density of 0.44 g / ml. The particle size distribution of the white powdery polymer was as shown in Table I. Concentration of the liquid layer gave 1.9 g of a solvent-soluble polymer. As a result, the activity was 25,400 g .ppm / mmol Ti, and the total isotactic index (II) of the entire polymer was 98.4%.

Table I

> 1190 μ > 840 μ > 420 μ > 25O μ > 177μ > 105μ > 44μ 44 μ > 0 0 4 _; 1 95.7 0.2 0 0 0

Examples 2 to 6

The procedure of Example 1 was followed except that the amount of hydrogen used in the polymerization was changed into 100 ml, 400 ml, 800 ml, 10 ml and 2000 ml, respectively. The results are shown in Table II.

24 47 47

Table II

In game Quantity of hydrogen (ml) MI Activity (g PP / mmol Ti) II {%) of the white powdery polymer II (%) of the total polymer 2 100 2.7 20,000 98.9 98.4 1 200 ". 7.5 25,400 98.9 98.4 3 400 20 30,800 98.5 98.0 4 800 59 32 100 98.3 97.7 5 ' 1000 145 34,000 97.7 97.0 5 2000 280 29-600 97.4 96.5

Examples 7 and

The procedure was as in Example 1 except that the polymerization temperature was changed to ί results are given in Table III.

The temperature was changed to 80 C or 90 C. The

Table ± 11

at I polymer activity II (%) of the II (%) of the bulk MI game sations- (g PP / white overall density 'tempera mMöl. Ti) powder polymers (G / ml) door- shaped ( ⁰ C) / polymers 1 70 25,400 98.9 98.4 0.44 ⁷ y ⁴ 7th 80 25,300 '99, 2 98.5 0.43 10.1 8th 90 22,500 98.7 98.1 0.41 21.3

kl kl 3

Example 9

Charged to a 2 .1 autoclave with 500 g of propylene and brought at room temperature 0.25 mmol of triethylaluminum, 0.025 mmol diphenyldimethoxysilane and 0.005 mmol, calculated as titanium atom, the catalyst component described in Example 1 (A) in the autoclave. 750 ml of hydrogen were also introduced into the autoclave. The temperature was raised to 80 ° C and propylene polymerized for 1 hour. After drying, the amount of total polymer obtained was 192.3 g. The total polymer had an extraction residue in boiling heptane of 98.6%, a MI of 3.2 and an apparent density of 0.48 g / ml. The activity in this case was therefore 38,500 g PP / mmol Ti.

Examples 10 to 14

The procedure was as in Example 9, except that 0.375 mmol of triethylaluminum, 0.0188 mmol of phenyltriethoxysilane and 0.0025 mmol, calculated as the titanium atom, of the catalyst component (A) described in Example 1 were used in the polymerization and the polymerization time was 15 minutes, 30 minutes , 1 hour, 2 hours or 3 hours respectively, The results are in table. IV specified.

Table IV

examples Polvmerisa- A: <ti Vi-ca- II (%) of the bulk st> iel tion time (g PP / overall density (Minutes) mmol of Ti) polymers (G / ml) 10 15 10,400 97.0 0.47 11 30 25,200 98.2 0.48 12 50 32,800 98.3 0.49 13 120 72,400 97.9 0 _; 48 14 180 88 400 97.9 0.49 p

Example 15 .

750 ml of purified hexane were charged to a 2 liter autoclave and, under a propylene atmosphere at room temperature, 2.51 mmol of triethylaluminum, 0.125 mmol of diphenyldimethoxysilane and 0.015 mmol, calculated as titanium atom, of the catalyst component (A) described in Example 1 were introduced into the autoclave on. After introducing 200 ml of hydrogen, the temperature was raised to 70 ° C. and propylene was polymerized for 2 hours. During the polymerization, the pressure became

5 2

maintained at 6.9-10 Pa gauge (7 kg / cm G). The reaction mixture was worked up by the same method as in Example 1. The results are given in Table V.

Example 16

A 2 liter autoclave was charged with 750 ml of purified hexane and charged under a propylene atmosphere at room temperature with 2.51 mmol of triethylaluminum, 0.225 mmol of phenyltrimethoxysilane and 0.015 mmol of bromine, calculated as titanium atom, of the catalyst component (A) described in Example 1. , After introducing 200 ml of hydrogen, the temperature was raised to 70 ° C and propylene was polymerized for 2 hours. During the polymerization, the pressure became

5?

maintained at 6.9 * 10 Pa gauge (7 kg / cm.G). The reaction mixture was worked up in the same manner as in Example 1. The results are given in Table V.

Example 17

A 2 liter autoclave was charged with 750 ml of purified hexane, and under a propylene atmosphere at room temperature, passed 2.51 mmol of triethylaluminum, 0.30 mmol of vinyltrimethoxysilane and 0.015 mmol, calculated as titanium atom, of the catalyst component described in Example 1 (A ) in the autoclave. For 'introducing 200 -ml of hydrogen, the temperature was raised to 70 ⁰ C, and one polymerisiertePropylen 4 hours. During the polymerization, the pressure was maintained at 6.9 * 10 "Pa gauge (7 kg / cm G)." The reaction

244747 3

⁰ S 3?

The mixture was worked up in the same manner as in Example 1. The results are given in Table V.

Example 18 . _

A 2 liter autoclave was charged with 750 ml of purified hexane, and under a propylene atmosphere at room temperature, brought 2.51 mmol of triethylaluminum, 0.45 mmol of methyltrimethoxysilane and 0.015 mmol, calculated as titanium atom, of the catalyst component (A) described in Example 1 the autoclave. After introducing 200 ml of hydrogen, the temperature was raised to 70 ° C and propylene was polymerized for 2 hours. During the. Polymerization, the pressure was maintained at 6.9 * 10 Pa gauge (7 kg / cm G). The reaction mixture was worked up in the same manner as in Example 1. The results are given in Table Y.

Example 19

Charged to a 2 1 autoclave with 750 ml of purified hexane and under a propylene atmosphere at room temperature, 2.51 mmol Triathylaluminium, 0.30 mmol Tetraäthoxysilan and 0.015 mmol, calculated as titanate, the catalyst component described in Example 1 (A) the autoclave. After introducing 200 ml of hydrogen, the temperature was raised to 70 ° C. and propylene was polymerized for 4 hours. During the polymerization, the pressure was maintained at 6.9 x 10 Pa gauge (7 kg / cm G). The reaction mixture was worked up in the same manner as in Example 1. The results are given in Table V.

Example 20

A 2 liter autoclave was charged with 750 ml of purified hexane, and under a propylene atmosphere at room temperature, put 2.51 mmol of triethylaluminum, 0.225 mmol of ethyltriethoxysilane and 0.015 mmol, calculated as titanium atom, of the catalyst component (A) described in Example 1 into the autoclave on. After introducing 200 ml of hydrogen, the temperature was raised to 70 ° C, and polymerized

44747

Propylene 4 hours. During the polymerization, the pressure became

5 2

held at β, 9 "10 Pa gauge (7 kg / cm G). The reaction mixture was worked up in the same manner as in Example 1. The. Results are given in Table V.

Example 21

A 2 liter autoclave was charged with 750 ml of purified hexane and under a propylene atmosphere at room temperature, 2.51 mmol of triethylaluminum, 0.225 mmol of vinyltriethoxysilane and 0.015 mmol, calculated as titanium atom, of the catalyst component (A) described in Example 1 were obtained. in the autoclave. After introducing 200 ml of hydrogen, the temperature was raised to 70 ° C. and propylene was polymerized for 4 hours. The reaction mixture was worked up in the same manner as in Example 1. The results are given in Table V. , [

Example 22

A 2 liter autoclave was charged with 750 ml of purified hexane and under a propylene atmosphere at room temperature afforded 2.51 mmol of triethylaluminum, 0.225 mmol of methylphenyldimethoxysilane and 0-015 mmol, calculated as titanium atom, of the catalyst component described in Example 1 (A) in the autoclave. After introducing 200 ml of hydrogen, the temperature was raised to 70 ° C, and propylene was polymerized for 2 hours. During the polymerization was

5 ¹ '··' 2

the pressure is maintained at S, 9-10 Pa overpressure (7 kg / cm G).

The reaction mixture was worked up in the same manner as in Example Ί. The results are given in Table V.

Example 23 .

A 2 liter autoclave was charged with 75Ο ml of purified hexane and under a propylene atmosphere at room temperature brought 1.8 mmol of triethylaluminum, 0.45 mmol of monochlorodiethylaluminum, 0.12 mmol of phenyltriethoxysilane and 0.015 mmol, calculated as titanium atom, in Example 1 described cat

47 47 3

After introducing 200 ml of hydrogen, the temperature was raised to 70 ° C. and propylene was polymerized for 2 hours. During the polymerization, the pressure was maintained at 6, S * 10 Pa overpressure (7 kg / cm G. The reaction mixture was worked up in the same manner as in Example 1. The results are given in Table V.

Table V

Organic silicon compound (C) Activity (g PP / mmol Ti) 600 II (%) of the total polymer MI 3 Bulk density (g / ml) _; 45   In game diphenyldimethoxysilane 31 700 98.9 6 2 0 45 15 Phenyltrimethoxysilane 23 200 98.6 ' 5, 0 0 , 44 16 vinyltrimethoxysilane 19 300 97.6 25 4 0 / 44 17 Me thy11rime thoxys i1an 23 300 96.9 11 0 0 , 43 18 tetraethoxysilane 22 200 96.8 58 0 0 , 44 19 Äthyltri äthoxysilan. 22 700 98.0 24 0 0 , 43 20 vinyltriethoxysilane 18 700 98.0 27 2 0 45 21 Me thy1phe ny! Dime thoxy-si lan 29 100 98.6 4th 6 ⁰ 44 22 Phenyltriäthoxysilan · 23 97.6 T-. ⁰ 23 Example 24

Preparation of a Solid Titanium Catalyst Component (A)

4.76 g (50 mmol) of anhydrous magnesium chloride, 25 ml of decane and 23.4 ml (150 mmol) of 2-ethylhexylalcohol were reacted at 130 ° C. for 2 hours to form a uniform solution. 1.11 g (7.5 mmol) of phthalic anhydride were added to the reading. The mixture was stirred at 13O ° C for 1 hour to dissolve the phthalic anhydride. The obtained uniform solution was cooled to room temperature and completely poured

Dropwise to 200 ml (1.8 mmol) at -20 ° C held titanium tetrachloride for one hour. After the addition, the temperature of the mixed solution was raised to 110 ° C over 4 hours. When the temperature reached 110 ⁰ C, · were added 3.5 g (12.5 mmol) of di-n-butyl phthalate to, and the mixture was held for 2 hours at the same temperature. After 2 hours, the solid portion was collected by hot filtration from the reaction mixture. The solid portion was resuspended in 200 ml of titanium tetrachloride and again heated at 120 ° C. for 2 hours. After the reaction, the solid portion was collected by hot filtration and washed completely with decane and hexane kept at 120 ° C until no more free titanium compound was detected in the washings.

The obtained catalyst component (A) was stored in the form of a slurry in hexane. A part of the slurry was dried to examine the composition of the catalyst. It was found that the obtained catalyst component (A) contained 2.1% by weight of titanium.

The polymerization is carried out using propylene obtained using the solid titanium catalyst component obtained in the same manner as in Example 1. The results are shown in Table VI.

Example:'. 25 '

Preparation of a Solid Titanium Catalyst Component (A)

4.76 g (50 mmol) of anhydrous magnesium chloride, 25 ml of decane and 23.4 ml (150 mmol) of 2-ethylhexyl alcohol were reacted at 130 ° C. for 2 hours to form a uniform solution. 1.11 σ (7.5 mmol) of phthalic anhydride was added to the solution, and the mixture was stirred at 130 ° C for 1 hour to give the phthalic anhydride. to solve. The resulting uniform solution was cooled to room temperature and added dropwise to 200 ml (1.8 mol) of titanium tetrachloride kept at -20 ° C. in the course of one hour. After the addition, the mixture was heated to 110 ° C over 4 hours. ais

4 4 7 4 /

the temperature of 110 ⁰ C reached, was added to 2.6 ml (13.0 mmol) of diethyl phthalate. The mixture was kept at this temperature for 2 hours. After the reaction for 2 hours, the solid portion was collected from the reaction mixture by hot filtration. The solid portion was resuspended in 200 ml of titanium tetrachloride and again reacted at 120 ° C for 2 hours. After the reaction, the solid portion was again collected by hot filtration and washed with decane kept at 120 ° C and with hexane until no free titanium compound was detected in the washings.

The obtained solid titanium catalyst component (A) prepared as above was stored in the form of a slurry in hexane. A portion of the slurry was dried to examine the composition of the catalyst component. The obtained solid titanium catalyst component (A) was found to contain 4.0% by weight of titanium.

Using the obtained solid titanium catalyst component (A), propylene was polymerized in the same manner as in Example 1. The results are shown in Table VI. indicated.

Example 26

Preparation of a Solid Titanium Catalyst Component (A)

4.75 g (50 mmol) of anhydrous magnesium chloride, 25 ml of decane and 23.4 ml (150 mmol) of 2-ethylhexyl alcohol were reacted at 130 ° C. for 2 hours to form a uniform solution. 1.11 g (7.5 mmol) of phthalic anhydride was added to the solution, and the mixture was stirred at 1300C for 1 hour to dissolve the phthalic anhydride. The resulting uniform solution was cooled to room temperature and added dropwise to 200 ml (1.8 mol) of titanium tetrachloride kept at -20 ° C dropwise in the course of one hour. After the addition, the mixture was heated to 110 ° C over 4 hours heated. When the temperature reached 110 ⁰ C, was added 2.9 ml (12.5 mmol) of diisopropyl phthalate, and the mixture was at 2 hours

244 7 47 3

vz

- 28 -

kept at the same temperature. After 2 hours of reaction, the solid portion was collected from the reaction mixture by hot filtration. The solid portion was resuspended in 200 ml of titanium tetrachloroethane and again reacted at 120 ° C. for 2 hours. After the reaction, the solid portion was again collected by hot filtration and washed with decane kept at 120 ° C and with hexane until no more free titanium compound was detected in the washings.

The solid titanium catalyst component (A) prepared as above was stored in the form of a slurry in hexane. A portion of the slurry was dried to examine the composition of the catalyst. The obtained solid titanium catalyst component (A) was found to contain 2.9% by weight of titanium.

Using the obtained solid titanium catalyst component (A), propylene was polymerized in the same manner as in Example 1. The results are given in Table VI. '.

Table VI

   at Ester (E) activity II {%) of the MI. bulk game (g PP / aesamten density rrMol polymers Ti) (G / ml) 24 Dl-n-butyl-phthalate 23,000 97.6 l .2,9 0.42 25 , D ia thy I-ph thai at 18,300 97.5 11.1 0 _; 44 26 Diisopropy1-phthaiat 20 1-00 97.3 9.2 0.44

Example 27

Preparation of a catalyst component (A):

5.25 g of C ₉ K ₅ OMgCl, 23.2 ml of 2-ethylhexyl alcohol and 50 ml of decane were mixed at room temperature for about 1 hour. To the resulting uniform solution was added 1.11 g of phthalic anhydride and the reaction was carried out at 130 ^° C. for 1 hour.

244747

to dissolve the phthalic anhydride in the uniform solution. The solution was then cooled to room temperature. The thus obtained uniform solution was added dropwise with stirring for one hour to 200 ml of titanium tetrachloride kept at -20 ° C. The mixture was worked up in the same manner as in Example 1 to form a catalyst component (A).

polymerization:

Propylene was polymerized in the same manner as in Example 15 except that the catalyst component (A) prepared as above was used. The polymerization activity was 23,700 g PP / mmol Ti and the total polymer had a II of 96.0%. The apparent density of the polymer was 0.42 g / ml «

Example 28

Preparation of a catalyst component (A):

A decane solution (150 ml) containing - 50 mmol ethyl butylmaanesium and 17.0 ml ethylhexanol was reacted at 80 ° C for 2 hours to form a uniform solution. 1.11 g (7.5 mmol The uniform solution was added dropwise with stirring over one hour to 200 ml of titanium tetrachloride kept at -20 ° C. Thereafter, the same procedure as in Example 1 was followed to use the same To obtain catalyst component (A).

polymerization:

Propylene was polymerized in the same manner as in Example 15 using the obtained catalyst component (A). The results are given in Table VII.

Example 29

Preparation of a catalyst component (A):

A uniform solution was added 4.76 g (50 mmol) of anhydrous magnesium chloride, 25 ml of decane, 3.4 ml (10 mmol) of tetrabutoxytitanium and 17.9 ml (115 mmol) of 2-Äthylhexylalkohol 2 hours at 130 ⁰ C in order to to build. 1.11 g (7.5 mmol) of phthalic anhydride was added to the solution, and the mixture was stirred at 130 ° C. for 1 hour to dissolve phthalic anhydride. The uniform solution was cooled to room temperature and entirely in the course of an hour added dropwise to 200 ml (1.8 moles) at -20 ⁰ C was added titanium tetrachloride kept. Thereafter, the same procedure as in Example 1 was used to obtain the solid titanium catalyst component (A).

polymerization:

Propylene was polymerized in the same manner as in Example 15 using the obtained solid titanium catalyst component (A). The results are given in Table VII.

Table VII

In game Activity. Cg-PPZmMoI Ti) II {%) of the entire polymer MI Bulk density (g / ml) 28 29 23. 200 24 .300 97.6 98.1 8,1 3,5 0.43 0.43

Example 30

Preparation of a Solid Titanium Catalyst Component (A)

A solid catalyst component (A) was prepared in the same manner as in Example 1, except using 1.43 ml. (10 mmol) of ethyl benzoate instead of 1.11 g (7.5 mmol) of phthalic anhydride. The catalyst component (A) corresponds

· _ 1_ J C '

47 3

polymerization:

Propylene was polymerized in the same manner as in Example 1 using the obtained solid catalyst component (A). The results are given in Table VIII.

Example 31

Preparation of a Solid Titanium Catalyst Component (A)

A solid catalyst component (A) was synthesized in the same manner as in Example 1 except that 1.80 ml (15.6 mmol) of benzoylchloride was used in place of 1.11 g (7.5 mmol) of phthalic anhydride, and 2-ethylhexyl benzoate was formed during the preparation of the catalyst. The obtained solid catalyst component (A) contained 3.1% by weight of titanium.

polymerization:

Propylene was polymerized in the same manner as in Example 1 using the obtained solid catalyst component (A). The results are given in Table VIII,

Example 32

Preparation of a Solid Titanium Catalyst Component (A)

A solid catalyst component (A) was prepared in the same manner as in Example 1 except using 1.47 ml (15 mmol) of methyl acetate instead of 1.11 g (7.5 mmol) of phthalic anhydride. The obtained solid catalyst component (A) contained 4.7% by weight of titanium.

polymerization:

Propylene was polymerized in the same manner as in Example 15 using the obtained solid titanium catalyst component (A). The results are shown in Table VII].

q,

Example 33

Preparation of a Solid Titanium Catalyst Component (A)

A solid catalyst component (A) was prepared in the same manner as in Example 1 except using 1.12 ml (15 mmol) of propionic acid instead of 1.11 g (7.5 mmol) of phthalic anhydride. The obtained solid catalyst component (A) contained 3.1% by weight of titanium.

polymerization:

Propylene was polymerized in the same manner as in Example 15; using the solid catalyst component (A). The results are given in Table VIII.

Example 34

Preparation of a Solid Titanium Catalyst Component (A)

A solid catalyst component (A) was prepared in the same manner as in Example 1 except that 1.46 ml (7.5 mmol) of diphenyl ketone was used instead of 1.11 g (7.5 mmol) of phthalic anhydride solid catalyst component (A) obtained contained 2.5% by weight of titanium.

polymerization:

Man.polymerized propylene in the same manner as in Example 15 using the obtained solid titanium catai satorator component. (A). The results are given in Table VIII.

Example 35

Preparation of a Solid Titanium Catalyst Component (A)

Mari synthesized a solid catalyst component (A) in the same manner as in Example 1 except using 1.82 ml (15 mmol) of diethyl carbonate instead of 1.11 g (7.5 mmol) of phthalic anhydride. The obtained solid catalyst component (A) contained 4.3% by weight of titanium.

24 4 7 4 7

polymerization:

Propylene was polymerized in the same manner as in Example 15 using the obtained solid catalyst component (A). The results are given in Table VIII.

Example 36

Preparation of a Solid Titanium Catalyst Component (A)

A solid catalyst component (A) was prepared in the same manner as in Example 1 except that 0.88 ml (7.5 mmol) of tetramethylsilicate was used instead of 1.11 g (7.5 mmol) of phthalic anhydride. The obtained solid catalyst component (A) contained 5.1% by weight of titanium.

polymerization:

Propylene was polymerized in the same manner as in Example 15 using the obtained solid titanium catalyst component (A), and the results are shown in Table VIII.

Example 37

Preparation of a Solid Titanium Catalyst Component (A)

A solid catalyst component (A) was prepared in the same manner as in Example 1 except that 0.99 ml (7.5 mmol) of n-butyl cellosolve was used instead of 1.11 g (7.5 mmol) of phthalic anhydride , The obtained solid catalyst component (A) contained 5.5% by weight of titanium.

polymerization:

Propylene was polymerized in the same manner as in Example 15 using the obtained solid catalyst component (A). The results are given in Table VIII.

-AS

Example 38

Preparation of a Solid Titanium Catalyst Component (A)

A solid catalyst component (A) was prepared in the same manner as in Example 1 except that 4.86 ml (20 mmol) of 2-ethylhexyl benzoate was used instead of 1.11 g (7.5 mmol) of phthalic anhydride. The resulting catalyst component (A) contained 3.1% by weight of titanium.

polymerization:

Propylene was polymerized in the same manner as in Example 15 using the obtained titanium catalyst component (A). The results are given in Table VIII-

Table VIII

at activity II MI bulk Particle size distribution (weight%) * > 1190 μ > 840 μ > 420 μ = ^ 250 μ > 177 μ > 105 μ > 44μ 44μ> game (βPP / mMdI Ti) 97.6 8.1 density (g / ml) 0 0 0 4.7 56.8 38.2 0.3 0 30 23,200 97.4 4.1 0.43 0 0 · 0 5.0 79.4 15.2 0.4 0 31 25,400 97.8 2.4 0.40 0 0 0.4 94.8 3.8 1.0 0 0 32 17,700 97.3 3.1 0.35, 0 0 0 0.3 4,4 ' 59.7 35.6 0 33 25 100  97.3 3.2 0.43 0 0 0 10.2 48.1 41.3 0.4 0 34 31 100 93.1 1.9 0.37 years 0  °; 2. 0.8 8.9 81.3 8.6 0.2 0 35 16,300 '97, 5 6.8 0.37 1 0 0 0 0.6 2.8 56.4 ^s 40.2 0 36 8,400 96.6 1.5 0.44 - 0 0 0.3 5.1 52.4 40.9 1 _; 3 0 37 17 100 97.7 5.5 0.36 -> 0 0.3 50.9 48.5 0.3 0 0 0 38 22,400 0.41.

24 47 47 3

Example 39

Charged to a 2 1 autoclave with 750 ml of purified hexane and under a propylene atmosphere at room temperature, 2.51 mmol of triethylaluminum, 0.15 mmol Phenyltriäthoxysilan and 0.015 mmol, calculated as the titanium atom, of the catalyst component described in Example 1 (A) the autoclave. After introducing 100 ml of hydrogen, the temperature was raised to 50 ⁰ C. When the temperature of the polymerization system reached 6Q ° C, the autoclave was charged with a gaseous mixture of propylene and ethylene containing 8.1 mol% of ethylene, and it was subjected to a polymerization.

5 ·· 2

pressure of 2 * 10 Pa overpressure (2 kg / cm G) kept for 2 hours. After the polymerization, the slurry containing the resulting polymer was filtered to separate into a white powdery polymer and a liquid layer. After drying, the amount of white powdery polymer obtained was 273.2 g. The polymer had an MI of 6.9 and an apparent density of 0.37 g / ml. By measuring its IR spectrum, it was found that the white powdery polymer contained 5.0 mole% of isolated ethylene. It was determined by DSC that the melting point (T) of this polymer was 135 ° C. Concentration of the liquid layer gave 14.8 g of a solvent-soluble polymer. The activity was therefore 19,200 g PP / mmol Ti and the yield of polymer was 94.9%.

Examples 40 to 47

Preparation of a catalyst component (A):

A catalyst component (A) was prepared in the same manner as in Example 1 except that 12.5 mmol of each of the compounds shown in Table IX were added instead of 2.68 ml of diisobutyl phthalate.

polymerization:

in

You pclytnerisierte propylene in the same way as

15, but using the catalyst catalyst prepared as described above (A). The results are in

244747 3

Table IX.

-AS

Table IX

In game Polycarbonsaueester Activity (g PP / mmol Ti) 900 II (% ) MI 1 Bulk density 40 Di-η-penty1 phthalate 25 600 96 4 3, ι 0 _; 43 41 Monoäthy1 phthalate 19 900 93 1 1O ₅ 9 0 _; 42 42 Dipheny1 phtha lat 23 200 95 ₃ 1 2, 5 0 _; 42 43 Di-2-ethylhexyl phthalate 24 700 96; 1 8'j 9 0 _; 42 44 Diäthy1-phenylmalonate 20 500 92 9  3, 8th 0.41 45 Di-2-ethylhexyl ethereal 19 400 ' 95; ¹ 1 0.41 46 ' Diethy1-T, 2-eyelo- hexanedicarboxylate 23 300 ¹ 12 _? ⁴ "Ό _; 4Ό. 47 1,2-diacetoxybenzene 21 92nd 8th 5, .... °, ^ -

Example 48

Preparation of a catalyst component (A):

50 mmol of a solid substance formed by reacting 3-methyl magnesium chloride with silicon tetrachloride, 25 ml of decane and 23.4 ml of 2-ethylhexyl alcohol were heated at 130 ° C. for 2 hours to form a uniform solution. Thereafter, 1.11 g of phthalic anhydride was added and reacted at the same temperature for one hour to form a uniform solution. The solution was worked up in the same manner as in Example 1 to give a catalyst component (A).

Polymerization: -

Propylene was polymerized in the same manner as in Example 15, except that those prepared as described above

24 47

5'Z.

Catalyst component (A) used. The results are given in • Table X.

Example 49

Preparation of a catalyst component (A):

5.73 g of diethoxymagnesium, 23.4 ml of 2-ethylhexyl alcohol and 50 ml of decane were reacted at 130 ° C. for 3 hours in the presence of hydrogen chloride. 1.11 g of phthalic anhydride was added to the resulting uniform solution and further reacted at the same temperature for one hour. The obtained uniform solution was worked up in the same manner as in Example 1 to give a catalyst component (A).

polymerization:

Propylene was polymerized in the same manner as in Example 15 except that the catalyst component (A) prepared as above was used. The results are given in Table X.

In game magnesium compound Activity (see PP / .m-Möl Ti) II (%) HI Bulk density 48 49 C ^ HgMgCl diethoxymagnesium 21 300 18 100 94.9 95.1   2.9 =. 8.3 0.41 0.42

Examples 50 and 51

Preparation of a catalyst component (A):

A catalyst component (A) was prepared. in the same

As in Example Ί ago, but one each of the.

used in Table XI compounds instead of 2-Atnylhexy! alcohol.

24 47 4 7 3

polymerization:

Propylene was polymerized in the same manner as in Example 15 except using the catalyst component (A) prepared as above. The results are given in Table XI.

Table XI

In game connection Activity (g PP / raMol Ti) II MI Bulk density 50 51 0Iey1 alcohol n-Buty1- Cellos ο Ive 19,300 24,100 96.1 5 _? 4 10.2 0j43 0 _; 42

Example 52

A 21-autoclave was charged with 1,000 ml of purified hexane, and then, 1.0 column of triisobutylaluminum, 0.05 mmol of phenyltriethoxysilane and 0.02 mmol, calculated as titanium atom, of the catalyst component (A) prepared in Example 1 were charged to the autoclave. The autoclave was kept continuously in a closed system and then the temperature was raised to 80 ° C. At 80 ⁰ C, the pressure was

 .- c ρ

brought to 2.95 * 10 Pa overpressure (3 kg / cm G) with hydrogen, and ethylene was further introduced to bring the total pressure to 7.85 * 10 Pa gauge (8 kg / cm G). The temperature was maintained at 90 ° C for 2 hours. 2 hours after introduction of the ethylene, the ethylene feed was stopped and the autoclave was rapidly cooled.

After the polymerization, the slurry containing the obtained polymer was filtered, and a white powdery polymer was collected. The amount of white powdery polymer obtained after drying was 316 g. It had an apparent density of 0.39 g / ml and a MI of 5.1. Its particle size distribution was very good, as shown in Table XII, "The molecular weight distribution of

244747 3

- 5-1 -

white powdered polymers were measured by gel permeation chromatography. and it was found that Kw / Mn was 3.9,

> 1190μ > 840μ. > 420y > 250μ > 177μ > 105μ > 4AY 44μ> O Oj 3 90.5 2.3 0.1 0 0

Example 53

A 2 liter autoclave purged with nitrogen was charged with 1,000 ml of 4-methylpentene-l, 1.0 mmol of triethylaluminum, 0.7 mmol of diphenyldimethoxysilane and 0.02 mmol, calculated as titanium atom, of the catalyst component (A) prepared as in Example 1, and then closed the catalyst feed port of the autoclave. 50 ml of hydrogen were introduced. The autoclave contents were heated to 60 ° C and then held at this temperature for 2 hours. After 2 hours, the autoclave was rapidly cooled.

After the polymerization, the slurry containing the resulting polymer was filtered and turned into a white one. powdered polymer and separated into a liquid phase. The amount of white powdery polymer obtained after drying was 213.2 g. This polymer had an apparent density of 0.31 g / ml and an intrinsic viscosity [τ] of 5.5. Concentration of the liquid phase gave 3.1 g of a solvent-soluble polymer. As a result, the activity was 10,800 g of polymer / ml of Ti and the yield of the polymer was 98.6% by weight.

Example 54

A 2 liter autoclave purged with nitrogen was charged with 11 (580 g) of purified butene-1, and at pH 1.0 mmol of triethylaluminum, 0.7 mmol of diphenyldimethoxysilane and 0.02 mmol, calculated as titanium atom, which was added in

2U747 3

- 52 -

game 1 prepared catalyst component (A) in the. Autoclave. The catalyst feed port of the autoclave was closed. 300 ml of hydrogen were introduced. The contents of the autoclave were heated to 35 C and held at this temperature for 2 hours. After 2 hours, 10 ml of methanol were added to stop the polymerization. The unreacted butene-1 'was purged from the autoclave. The resulting white powdery polymer was dried and its amount was determined. It was 26 3 g. The polymer had an extraction residue in boiling n-heptane of 96.5%. "

Claims (7)

61 615/11 claim for invention 1. A process for the preparation of Qlefinpolymeren or copolymers, characterized in that it is the polymerization of olefins or the copolymerization of olefins with each other or with dienes in the presence of a. Catalyst system comprising the following components (A), (3) and (G): (A) a solid titanium catalyst component containing magnesium, titanium, halogen and a sater selected from esters of polycarboxylic acids and esters of polyhydroxy compounds, the catalyst component being obtained by contacting a solution in liquid hydrocarbon of (1) a magnesium compound with (ii ) of a titanium compound in a liquid state to form a solid product, or first of all, a solution in liquid hydrocarbon of the magnesium compound (i) and the titanium compound (ii), followed by formation of the solid product thereof, the reaction of forming the solid solid product is carried out in the presence of (D) at least one S'lektronendonator selected from monocarboxylic esters, aliphatic carboxylic acids, carboxylic acid anhydrides, ketones, aliphatic ethers, aliphatic carbonates, an alkoxy group-containing alcohols, an aryloxy-containing alcohols, organosilicon compounds with an Si-Q-C-3 bond and organophosphorus compounds having a P-Q-C bond, and during or after formation of the solid product, contacting the solid product with (E) an ester selected from esters 24 4 7 kl 3 - ** AP C 08 F / 244 74 7/3 61 615/11 ' of polycarboxylic acids and esters of polyhydroxy compounds, (B) an organometallic compound of a metal selected from metals of Groups I to III of the Periodic Table, and (G) an organosilicon compound having a Si-Q-C bond or Si-H-C bond. 2 «Method according to item 1, characterized in that the magnesium compound (i) is a magnesium compound without reduction capability» 3. A process according to item 1, characterized in that the ileitane compound (ii) is a tetravalent I'itan compound of the formula wherein R is a hydrocarbon group, X is a halogen atom, and g is a number represented by 0 = g = 4. 4. Process according to item 1, characterized in that each of the esters of polycarboxylic acids (Jü) is a component chosen from C 1 -C 4 -aliphatic polyisocyanates. OjO· ^J carbonsäureester C ^ -CJ _{in n} alicyclic Polycarbönsäureestern, Cq-C ^ q-aromatic polycarboxylic acid and _a C -C-, _n -he.terocvclischen Polvcarbonsäureestern " ο ju "- .." .- 244747 3 23.6.1983 AP G 08 P / 244 747/3 61 615/11 A method according to item 1, characterized in that each of the esters of polyhydroxy compounds is a component selected from esters formed between Or-G ., Aromatic polyhydroxy compounds and Cj-Cp aliphatic carboxylic acids. Method according to item 1, characterized in that the electron donor (D) is chosen from C.-CpQ monocarboxylic esters, C.-CpQ-aliphatic carboxylic acids, G.-GpQ-garboxylic anhydrides, C ^ - ^ O "ketones, Cp -C ../-- aliphatic Ithern, G ^ -GP ^ aliphatic carbonates, C ^ -Cp ₀ -. a Aikoxygruppe containing alcohols, CSC ₂ Q- a Arylosygruppe alcohols containing, organosilicon compounds having an Si-OG-Blndung wherein the organic group has 1 to 10 carbon atoms, and organophosphorus compounds having a P-O-G bond wherein the organic group has 1 to 10 carbon atoms, Process according to item 1, characterized in that the organometallic compound (3) is an organoaluminium compound, 3 · Method according to item 1, characterized in that the organosilicon compound (G) is a compound of the formula is wherein R. is selected from G. _{Q-C -Aikyigruppen}} C ₅ -G ₁₂ -Cycloalkyigruppen, Cg-C ₂₀ -Aryigruppen, C ₁ -C alkenyl _{Q f} C ^ G ^ haloalkyl and G, 24 4 7 4 7 3 - ^ - 23.6.1983 . * .- »- * / - ,. .. AP G 08 P / 244 747/3 61 615/11 Amino groups, R is selected from G ^ -C ^ groups, C ^ -G p ^ -cycloalkyl groups, Gg-CgQ-Är G.-G. _n alkenyl groups and C ₀ -C r alkoxyalkyl groups ,. I 1U 4L JL η is a number represented by 0 = η = 3 »and nR groups or (4-n) -CR groups may be the same or different * 9. The method according to item 1, characterized in that the olefins are Cp-G.-.- olefins. 10, method according to item 1, characterized in that the polymerization at a temperature of about 20 to about 200 ⁰ G and at a pressure of atmospheric pressure to about 98 · 1Q- ³ Pa (1OÖ kg / cm) is performed. 11, Method according to item 1, characterized in that the polymerization under such quantitative. Conditions are carried out such that per liter of liquid reaction medium in the course of the liquid phase reaction or per liter of the volume of the reaction zone in the case of the gas phase reaction component (A) is calculated in an amount of 0.0001 to 1 mmol, calculated as "as" '^ itanatom, - .. is used; the component (B) in an amount of 1 to 2,000 mol as the metal atom herein per mole of the itanatom. used in component (A); and the component (G) is used in an amount of 0.001 to 10 moles as the silicon atom herein per mole of the metal atom in the component (B). 12, 'Sitan catalyst component for use in the polymerization of olefins or the copolymerization of olefins with each other or alt DieMhy'gekenxiaelch- 2ί Ll L 7 ^ -56a-. 23.6,1983 HH / H / ν AP ο 08 ΐ? / 244 747/3 61 615/11 in that it contains magnesium, titanium, halogen and an ester selected from among esters of polycarboxylic acids and esters of polyhydroxy compounds, the catalyst component being obtained by contacting a solution in liquid hydrocarbon of (i) a hagnesium compound (ii) a 'titanium compound in the liquid state, unter'Bildung a solid product or first preparing a solution in a liquid hydrocarbon of the magnesium compound (i) and ¹ ^ it he anv compound (ii) and then form a "solid product therefrom, said reaction of Formation of the solid product is carried out in the presence of (B) at least one electron donor selected from monocarboxylic acid esters, aliphatic carboxylic acids, carboxylic acid anhydrides, ketones, aliphatic ethers, aliphatic carbonates, alcohols containing alkoxy groups, aryloxy-containing alcohols, organosilicon compounds having a Si-O-C Bonds g and organic phosphorus compounds having a POG bond, and during or after formation of the solid product contacting the solid product ait (B) a bister selected from esters of polycarboxylic acids and esters of polyhydroxy compounds, 13. «Titanium catalyst component according to point. 12, characterized in that it is used in combination with (B) an organometallic compound of a metal selected from. Metals of Groups I to III of the Periodic Table, and- (C) an organosilicon compound having a. 3i-O-C bond or Si-C-C bond. L 4 7 4 7 3 - ⁵ ^ - ²³ · ⁶ · ¹⁹⁸³ _. -7 -τ w AP C 08 Ρ / 244 74 7/3 61 615/11 14. The titanium catalyst component according to item 12, characterized in that the magnesia / titanium atom ratio is from about 2 to about 100, the halogen / titanium atomic ratio is from about 4 to about 100, and the slektronendonator / titanium molar ratio is about 0.01 until about 100.