The solid titanium catalyst component, catalyst for polymerization of ethylene, containing it, and the method of polymerization of ethylene

 

(57) Abstract:

The invention relates to a solid catalyst component obtained by a process comprising a stage of bringing (a) a liquid magnesium compounds into contact with (b) a liquid compound of titanium in the presence of (C) organosilicon compounds having inactive hydrogen in an amount of from 0.25 to 0.35 mol per 1 mol of compound of magnesium (a) increasing the temperature of the obtained contact product (i) to a temperature of from 105 to 115oWith and holding the contact product at this temperature. Contact the product can then be brought into contact with not more than 0.5 moles of organosilicon compounds having inactive hydrogen (s). Also, a catalyst for polymerization of ethylene, obtained from solid titanium catalyst component and an ORGANOMETALLIC compound, and a method of polymerization using this catalyst. When using the solid titanium catalyst component for ethylene can be polymerized with high activity and can be obtained a polymer of ethylene having excellent particle properties. 4 S. p. f-crystals, 5 tab., 1 Il.

The invention relates to a solid titanium catalyst component, the particles, and also relates to a catalyst for polymerization of ethylene containing solid titanium catalyst component, and the method of polymerization of ethylene using the catalyst.

Ethylene polymers, such as homopolyamide and linear low density polyethylene (LLDPE) are widely used for films due to its excellent transparency and mechanical strength.

Various methods for producing polymers of ethylene are usually offered, and it is known that ethylene polymers can be obtained with high polymerization activity when a Ziegler catalyst comprising titanium, magnesium, halogen and optional electron-donating compound is used as catalyst in the polymerization. It is also known that high activity occur especially when the solid titanium catalyst component prepared from a halogen-containing compounds of magnesium in the liquid state, the liquid compound of titanium and electron-donating compound is used as the titanium catalytic component.

In these methods for producing polymers of ethylene, if the polymer is polymerized with higher activities, not only productivity increases, but also the residue was pushing RMI in the process of molding can be removed.

Therefore, it is desirable to create a solid titanium component capable of polimerizuet ethylene with higher activities.

Polymers of ethylene, obtained directly after polymerization, are mainly in the form of powder, even if the polymerization was carried out suspension polymerization method or a gas-phase polymerization method, and in this case, it is desirable that the resulting ethylene polymers had good fluidity, contains finely ground powder, had an excellent distribution of particle sizes. Polymers of ethylene, showing such excellent properties of the particles have various advantages, for example, they can be used as such, depending on the purpose, even if they are not grainy.

The purpose of the invention

The present invention was created under the circumstances described above, and the aim of the invention is to obtain a solid titanium catalyst component that ethylene can be polymerized with high activity and can be obtained a polymer of ethylene with excellent properties of the particles. Another objective of the invention to provide a catalyst for polymerization of ethylene containing solid Tetyana objective of the claimed invention achieved by that the solid titanium catalyst component for polymerization of ethylene get method, comprising: a stage of contacting (a) a liquid magnesium compounds with (b) a liquid compound of titanium in the presence of (c) organosilicon compounds having inactive hydrogen, and the stage of increasing the temperature of the obtained contact product (i) and keeping contact product (i) at this temperature, and mentioned solid titanium catalyst component comprises magnesium, titanium, halogen and an organosilicon compound having an inactive hydrogen (c), at this stage contacting is carried out at a molar ratio of organosilicon compound (C) the magnesium compound (a) equal to 0.25-0.35 mol per 1 mol of compound of magnesium (a) and curing the obtained contact product (i) is carried out at 105-115oC.

The technical effect is achieved also due to the fact that the solid titanium catalyst component for polymerization of ethylene get method, comprising: a stage of contacting (a) a liquid magnesium compounds with (b) a liquid compound of titanium in the presence of (c) organosilicon compounds having inactive hydrogen, and the stage temperature increase is perceived by the catalytic component includes magnesium, titanium, halogen and an organosilicon compound having an inactive hydrogen (C), at this stage contacting is carried out at a molar ratio of organosilicon compound (C) to the magnesium compound (a) equal to 0.25-0.35 mol per 1 mol of compound of magnesium (a) and curing the obtained contact product (i) is carried out at 105-115oC adding organosilicon compounds having inactive hydrogen (c) in an amount of not more than 0.5 mol per 1 mol of compound of magnesium (a), and the temperature of the contact product (i) rises from the temperature below 10oC, than the supported temperature, to a temperature at which the temperature rise is completed, or after the temperature rise is completed, bring into contact a compound (c) with the contact product (i), and also due to the fact that the catalytic polymerization of ethylene, containing (I) a solid titanium catalyst component and (II) alyuminiiorganicheskikh connection, contains as a solid titanium catalyst component of any of the above components, the method of polymerization of ethylene by polymerization of ethylene in the presence of a catalyst containing a solid titanium ka is olymerization ethylene, containing (I) a solid titanium catalyst component and (II) alyuminiiorganicheskikh connection.

The drawing shows a stage for preparing the solid titanium catalyst component according to the invention and shows the progress for the preparation of the catalyst for polymerization of ethylene according to the invention.

DETAILED DESCRIPTION OF THE INVENTION.

The solid titanium catalyst component, catalyst for polymerization of the polymer containing the catalytic component and method for the polymerization of ethylene according to the invention described in detail below.

The meaning of the term "polymerization" used here is not limited to "homopolymerization, but may include "copolymerization". Also, the term "polymer" used here is not limited to "homopolymer, but may include "copolymer".

The drawing shows the stage to obtain a solid titanium catalyst component in accordance with the invention and a stage for receiving the catalyst for polymerization of ethylene containing catalytic component.

[I] a Solid titanium catalyst component.

The solid titanium catalyst component according to izaberete the connection, having inactive hydrogen in a given volume per 1 mol of compound of magnesium (a) into contact with each other in the manner described below, and includes magnesium, titanium, halogen and an organosilicon compound having an inactive hydrogen (c).

First described each ingredient used to obtain a solid titanium catalyst component of the invention.

(a) a Liquid magnesium compound.

To obtain a solid titanium catalyst component of the invention, the magnesium compound used in the liquid state. When the magnesium compound is solid, it is made of liquid before use. As compounds of magnesium of any of (a-1) magnesium compounds having reducing ability, and (2) compounds of magnesium, not having resilience, can be used.

The magnesium compound having reducing ability (a-1) means, for example, magyarkanizsa the compound represented by the following formula:

XnMgR2-n,

where n represents the number 0 n 2; R is hydrogen, alkyl group of 1 to 20 carbon atoms, aryl group or cycloalkyl group; when n is 0, two of R may be the same the considerable ability, include:

dialkylamino compounds such as dimethylamine, diethylamine, dipropylamine, dibutylamine, diamylamine, directimage, dodecylamine, activprimary and ethylbutylamine;

alkalinity halide, such as etimani chloride, propylene chloride, butylamine chloride, hexylene chloride and nilmini chloride;

alkalinity alkoxides, such as butylacetamide, ethylbutane and ActiveDocument; and

other compounds, such as butylamine hydride.

Examples of magnesium compounds having no resilience (a-2) include:

halide magnesium, such as magnesium chloride, magnesium bromide, magnesium iodide and magnesium fluoride;

halide alkoxyamine, such as methoxamine chloride, ethoxyline chloride, isopropoxide chloride, butoxymethyl chloride and octocrylene chloride;

halide alloxane, such as enoximone chloride and methyleneimine chloride,

alkoxyimino, such as ethoxyline, isopropoxide, butoxymethyl, n-octoxide and 2 - ethylhexylamine;

aryloxyalkyl, such as enoximone and dimethyldioxirane;

the carboxylates of magnesium, such as laurate and stearate;

metallicity (a - 2), can be compounds, formed from the above-mentioned magnesium compounds having reducing ability (a-1), or compounds formed during the process of obtaining a catalytic component. To obtain compounds of magnesium, not having resilience (a-2), of the magnesium compounds having reducing ability (a-1), for example, magnesium compounds having reducing ability, (a-1) is brought into contact with alcohols, ketones, esters, ethers, siloxane compounds, halogenated compounds such as halogenated silane compounds, halogen-containing aluminum compounds and halide acids, or compounds having an Oh group or an active carbon-oxygen bond.

In the present invention compounds of magnesium, not having resilience (a-2) can be obtained from the magnesium compounds having reducing ability (a-1), using the following describes the organosilicon compound having an inactive hydrogen (c).

The magnesium compounds may be used in combination of two or more kinds.

Compounds of magnesium can form complex compounds or double the s, sodium and potassium (for example, the following described alyuminiiorganicheskikh connection), or can be mixed with these metal compounds.

To obtain a solid titanium catalyst component [I] other compounds of magnesium than described above may be used, but it is preferable that the magnesium compound is present in the form of a halogen-containing compounds of magnesium in the final solid catalyst component [I]. Therefore, if the magnesium compound not containing halogen, is used, the magnesium compound is preferably in contact with the halogen-containing compound during the process of obtaining a catalytic component.

Of the above compounds, preferred compounds of magnesium, not having resilience, particularly those containing halogen. Among them the most preferred magnesium chloride, chloride alkoxyamine and chloride arylacetamide.

When the magnesium compound is solid, the solid compound of magnesium, you can make liquid using electron-donating compound (d-1).

Electron-donating compound (d-1) include alcohols, carboxylic acids, aldehydes, amines and metallic acid esters.

Note tanol, pentanol, hexanol, 2-methylpentanol, 2-ethylbutanol, heptanol, 2-ethylhexanol, octanol, decanol, dodecanol, tetradecanoyl alcohol, octadecylamine alcohol, undecenol, alerby alcohol, stearyl alcohol and ethylene glycol;

alicyclic alcohols such as cyclohexanol and methylcyclohexanol;

aromatic alcohols such as benzyl alcohol, methylbenzylamine alcohol, isopropylbenzyl alcohol - methylbenzylamine alcohol , dimethylbenzylamine alcohol, phenethyl alcohol, tomilovy alcohol, phenol, cresol, Xylenol, ethylphenol, propylene, Nonylphenol and naphthol;

alcohols containing alkoxy group, such as n-butyl cellosolve, ethyl cellosolve, 1 butoxy-2-propanol and methylcarbamoyl; and

halogenated alcohols, such as trichloroethanol, trichloroethanol and trichloroethanol.

Carboxylic acids are preferred those that have 7 or more carbon atoms, such as Caprylic acid, atelophobia acid, pelargonia acid and undecylenoyl acid.

The preferred aldehydes are those who have 7 or more carbon atoms, such as caprellidae, 2-ethylhexaldehyde, undeclared, benzaldehyde, Truelove naphthoic aldehyde and aldehyde.

Amines of prepact the amine, the decylamine, undecillion and laurylamine.

Examples of metal acid esters include tetraethoxysilane, Tetra-n-propoxide, Tetra-isopropoxide, tetrabutoxide, tetrahexahedron, tetramethoxysilane and tetraethoxysilane. Metal acid esters do not include silicic acid esters, which are described as examples of the organosilicon compound having no active hydrogen (c).

Electron-donating compounds described above may be used in combination of two or more species, or they can be used in combination with these other electron-donor compounds (d) than the aforementioned electron-donating compound.

Which one is preferable alcohols and metallic acid esters, and particularly preferred alcohols with 6 or more carbon atoms.

If electron-donating compound having 6 or more carbon atoms, is used as an electron-donating compound (d-1) in order to make the connection of magnesium liquid, the amount of it is usually not less than 1 mol, preferably from 1 to 40 mol, more preferably from 1.5 to 12 mol, per 1 mol of compound of magnesium. If electron-donating compound, have nice, than 15 mol, per 1 mol of compound magnesium.

When the contact between the solid compound of magnesium and electron-donating compound (d-1) can be used a hydrocarbon solvent. Examples of hydrocarbon solvents 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 timol; and halogenated hydrocarbons such as carbon tetrachloride, dichloroethane, dichloropropane, trichloroethylene and chlorobenzene.

When aromatic hydrocarbons use of these solvents, alcohol as electron-donating compound (d-1) used in the same amount as described above in the case of electron-donating compounds of 6 or more carbon atoms, not paying attention to the type (the number of carbon atoms) used alcohol, whereby the magnesium compound may be dissolved. When using aliphatic hydrocarbon and/or alicyclic hydrocarbons, alcohols as electron-donating compound ispolnitel, solid magnesium compound is in contact with the electron-donating compound (d-1) in a hydrocarbon solvent.

In order to dissolve the solid magnesium compound in the electron-donating compound (d-1), usually choose the method of contacting the solid magnesium compounds with electron-donating compound (d-1), mainly in the presence of a hydrocarbon solvent and heating it if necessary. This contacting is carried out at a temperature of usually from 0 to 300oC, preferably from 20 to 180oC, more preferably from 50 to 150oC, for about from 15 minutes to 5 hours, preferably about from 30 minutes to 2 hours.

(b) Liquid connection titanium.

In the present invention is preferably used such tetravalent compound of titanium, as a liquid compound of titanium. Tetravalent compound of titanium, for example, is a compound represented by the following formula:

Ti(OR)gX4-g,

where R is a hydrocarbon group, X represents a halogen atom and 0 g 4.

Examples of such compounds include:

tetrahalide titanium, such as TiCl4, TiBr4and TiI4;

trihalide of alkoxysilane, such as Ti(OCH3)Cl3>)Br3;

dihalide of dialaction, such as Ti(OCH3)2Cl2, Ti(OC2H2)2Cl2, Ti(O-n-C4H9)2Cl2and Ti(OC2H2)2Br2;

monoglide of tralkoxydim, such as Ti(OCH3)3Cl, Ti(OC2H5)3Cl, Ti(O-n-C4H9)3Cl, Ti(OC2H5)3Br; and

tetraalkoxysilane, such as Ti(OCH3)4, Ti(OC2H5)4, Ti(O-n-C4H9)4, Ti(O-i-C4H9)4and Ti(O-2-ethylhexyl)4.

Of these the most preferred tetrahalide titanium and particularly preferred titanium tetrachloride. These titanium compounds may be used in combination of two or more species. Then these compounds can be diluted with the above-mentioned hydrocarbon solvents, which are used to create liquid compounds of magnesium (a).

(c) Organosilicon compounds having inactive hydrogen.

The organosilicon compound having an inactive hydrogen, which is used in the invention is represented, for example, by the formula, R1xR2ySi(OR3)z(R1and R2indicate each independently a carbohydrate organosilicon compounds, represented by the above formula include:

tetramethoxysilane, tetraethoxysilane, tetrapropoxide, tetramethoxysilane, tetrakis(2-ethylhexyloxy)silane, ethyltrimethoxysilane, ethyltriethoxysilane, VINYLTRIMETHOXYSILANE, methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, Cyclopentasiloxane, 2-methylcyclopentadienyl, 2,3-dimethylcyclopropanecarboxylate, cyclohexyltrichlorosilane, 2-norbornenedicarboxylic, 2-norbornenedicarboxylic, phenyltrimethoxysilane-chloropropionitrile, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, tributyltinoxide, n-butyltrichlorosilane, isobutyltrimethoxysilane, decyltrimethoxysilane, Cyclopentasiloxane, cyclohexyltrichlorosilane, 2-norbornenedicarboxylic, phenyltriethoxysilane-aminopropyltriethoxysilane, chlorotriethylsilane, ethyltriethoxysilane, VINYLTRIMETHOXYSILANE, tributyltinoxide, methylalumoxane, vinyltris (-methoxyethoxide), vinyltriethoxysilane, dimethyldiethoxysilane, diisobutyldimethoxysilane, tributyltinoxide, dicyclopentadienyliron, bis(2-methylcyclopentene)dimethoxysilane, bis(2,3-dimethylcyclobutyl metaldimension, bis-o-tridimensional, bis-m-tridimensional, bis-p-tridimensional, pisatelbnicaostaetsya, dimethyldiethoxysilane, tributyltinoxide, treatmentmedicationsother, dicyclopentadienyliron, diphenyldichlorosilane, bis-p-cardiotoxicity, cyclohexyltrichlorosilane, trimethyloxonium, trimethylaluminium, tricyclopentadiene, tricyclopentadiene, dicyclopentadienyltitanium, dicyclopentadienyliron, hexanitroethane, cyclopentadienylmagnesium, cyclopentadienylmagnesium, dicyclopentadienyltitanium, cyclopentadienylmagnesium and dimethylhydrogensiloxane.

One of them is preferably used tetramethoxysilane, tetraethoxysilane and cyclohexanedimethanol. From the viewpoint of catalytic activity of the tetraethoxysilane is particularly preferably used.

In the present invention it is sufficient that the organosilicon compound having no active hydrogen (c), is contained in the end-obtained solid titanium catalyst component. When receiving the solid titanium catalyst component, therefore, the organosilicon compound and the producing organosilicon compound, having inactive hydrogen during the process of obtaining the solid titanium catalyst component.

(d) Other electron-donating compound.

When receiving the solid titanium catalyst component of the invention of electron-donor compound with an inactive hydrogen (d) may be optionally used in addition to the organosilicon compound having an inactive hydrogen (s).

Examples of such electron-donating compound (d) include esters of organic acids, halide organic acids, anhydrides of organic acids, ethers, ketones, tertiary amines, esters of phosphorous acid, phosphoric esters, amides, carboxylic acids, NITRILES, aliphatic carbonates and pyridine.

More specifically there may be mentioned:

esters of organic acids having from 2 to 18 carbon atoms, such as methylformate, methyl acetate, ethyl acetate, vinyl acetate, propyl, isobutyl acetate, tributyltin, octylated, cyclohexylacetate, methylchloride, ethyldichlorosilane, ethylpropane, etherpiraat, ethyldimethylamine, methyl ester butyric acid, Etisalat, methyl methacrylate, etildronat, ethylcyclohexane, the benzyl benzoate, methyl ester Truelove acid, ethyl ester Truelove acid, amyl ester Truelove acid, ethyl ethylbenzoic, methyl ester anise acid, ethyl ester anise acid and utilitarians;

halide acids having from 2 to 15 carbon atoms, such as acetylchloride, benzoyl chloride and trouillard;

anhydrides of acids, such as acetic anhydride, phthalic anhydride, maleic anhydride, benzoic anhydride, trimellitic anhydride and tetrahydrophthalic anhydride;

ethers having from 2 to 20 carbon atoms, such as methyl ether, ethyl ether, isopropylene ether, butyl ether, amyl ether, tetrahydrofuran, ethylbenzylamine ether, ethylene glycol, disutility ether, anisole and diphenyl ether;

ketones having from 3 to 20 carbon atoms, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl n-butylketone, acetophenone, benzophenone, benzoquinone and cyclohexanone;

tertiary amines, such as trimethylamine, triethylamine, tributylamine, tribenzylamine, tetramethylethylenediamine;

esters of phosphorous acid, such as trimethylphosphite, triethylphosphite, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphate, triisobutylene, diethyl-n titleleft;

amides of acids, such as N,N-dimethylacetamide, N,N-diethylbenzamide and N,N-diethyltoluamide;

NITRILES, such as acetonitrile, benzonitrile tolunitrile;

aliphatic carbonates, such as dimethylcarbonate, diethylcarbamyl and ethylene carbonate resulting;

pyridine, such as pyridine, methylpyridine, ethylpyridine and dimethylpyridin.

These compounds can be used in combination of two or more kinds.

Preparation of solid titanium catalyst component.

In the present invention, the solid titanium catalyst component [I] can be obtained from the above ingredients in the following ways:

(1) a Liquid magnesium compound (a) and a liquid compound of titanium (b) contacting in the presence of an organosilicon compound having an inactive hydrogen (c) (referred to simply as "the organosilicon compound (c)" hereinafter), in the amount of from 0.25 to 0.35 mol per 1 mol of compound of magnesium (a). Then the temperature of the obtained contact product (i) is brought to a temperature of from 105 to 115oC and maintain at this temperature.

(2) the Temperature of the contact product (i) obtained above was adjusted to maintain the contact product (i) when the rate is than 0.5 mol per 1 mol of compound of magnesium (a), moreover, the temperature of the contact product (i) bring the temperature below 10oC, than the supported temperature, to a temperature at which the temperature rise is completed, or after the temperature rise is completed, resulting thus in contact with the organosilicon compound (C) with the contact product (i).

Of the above methods, the method (2) is preferred from the viewpoint of catalytic activity of the obtained solid titanium catalyst component.

According to the invention when the contact components of the organosilicon compound (C) used in a special number in the calculation of the magnesium compound (a).

Preferably, the compound of titanium (b) used in such a sufficient amount that the solid body could precipitate upon contact, even if a specific precipitating means not applicable. The number of used connections titanium (b) varies depending on its type, contact conditions, the amount of organosilicon compound (C), and so on, but it is usually not less than 1 mol, preferably about 5 to 200 moles, more preferably from about 10 to 100 moles, per 1 mol of compound magnesium (as). Next, the connection is based on 1 mol of organosilicon compounds (C).

The above methods are described below in more detail.

Liquid magnesium compound (a) and/or a compound of titanium (b) which are in contact with each other, can pre-contain organosilicon compound (c). In this case, the organosilicon compound (c) may optionally be added at the stage of contact connections of magnesium (a) and compounds of titanium (b). In any case, the total amount of organosilicon compound (c) in the calculation of the magnesium compound (c) is within the above limits.

In the present invention the contact liquid compounds of magnesium (a) and the liquid titanium compounds (b) is carried out at such a low temperature that the solid body is rapidly formed upon contact. Characteristically, the contact is preferably carried out at a temperature of from -70 to +50oC, preferably from -50 to +30oC, more preferably from -40 to +20oC. the Temperature of all solutions used for contact, can be different from each other. If the contact temperature is too low to precipitate solids in the contact product (i) at the beginning of the contact, the contact is at a low temperature may be held for a long period of time to precipitate a solid.

oC to precipitate the solid gradually, further supporting this temperature.

Time temperature is in the range usually from 0.5 to 6 hours, preferably from 1 to 4 hours.

The time required to achieve the temperature varies greatly depending on the size of the reactor, etc.

When the liquid magnesium compound (a) and a liquid compound of titanium (b) in contact with the above conditions in the presence of an organosilicon compound having an inactive hydrogen (c), can be obtained granular or spherical solid titanium catalyst component having a relatively large particle diameters and excellent distribution of particle sizes. When ethylene is subjected to suspension polymerization using the solid titanium catalyst component with such excellent properties of the particles can be obtained granular or spherical ethylene polymer having excellent distribution of particle sizes, high volume weight and good fluidity.

According to the method (2) under method (1), where the temperature of the contact product (i) reaches a temperature of 105 to 115oC and maintained at this pace the of (c) in an amount of not more than 0.5 mol per 1 mol of compound of magnesium (a), moreover, the temperature of the contact product (i) is increased from a temperature below 10oC, than the supported temperature, to a temperature at which the temperature rise is finished, or after, preferably immediately after the temperature rise is completed, thus enabling the contact organosilicon compounds (c) the contact product (i).

The solid titanium catalyst component of the invention obtained by the above methods includes magnesium, titanium, halogen and an organosilicon compound having an inactive hydrogen (c).

In the solid titanium catalyst component, it is desirable that:

the magnesium/titanium ratio (by atoms) were in the range of about 2 to 100, preferably from about 4 to 50, more preferably from 5 to 30;

the halogen/titanium ratio (by atoms) were in the range from 4 to 100, preferably from about 5 to 90, more preferably from about 8 to 50;

the organosilicon compound/titanium ratio (in moles) were in the range of about from 0.01 to 100, preferably from about 0.2 to 10, more preferably from about 0.4 to 6;

and the organosilicon compound (C)/magnesium ratio (moles) was 2">

The solid titanium catalyst component may also contain other ingredients than the above, such as the media, and especially other ingredients may be contained in amounts of not more than 50% by weight, preferably not more than 40% by weight, more preferably not more than 30% by weight, particularly preferably not more than 20% by weight.

The composition of the solid titanium catalyst component can be determined, for example, ICP (atomic absorption spectrometry) or gas chromatography, after which the catalytic component is enough to wash a large amount of hexane and dried at room temperature and 0.1 to 1 Torr, of not less than 2 hours.

The solid titanium catalyst component of the invention is preferably in granular or spherical form, and its specific surface area is preferably not less than 10 m2/g, preferably about from 100 to 1,000 m2/,

In the present invention, the solid titanium catalyst component is usually washed with a hydrocarbon solvent prior to use.

The catalyst for polymerization of ethylene.

The catalyst for polymerization of ethylene according to izopet the component.

ORGANOMETALLIC compound used in the invention, means are preferably ORGANOMETALLIC compound containing a metal selected from Group I or Group II of the Periodic table.

Examples of such compounds include alyuminiiorganicheskikh connection, alkyl compound of a metal of Group I and aluminum, and an ORGANOMETALLIC compound of a metal from Group II.

Alyuminiiorganicheskikh connection means, for example, a compound represented by the following formula:

RanAlX3-n,

where Rameans hydrocarbon group of 1 to 12 carbon atoms, X is halogen or hydrogen, and n means 1 to 3.

Rameans hydrocarbon group of 1 to 12 carbon atoms, i.e., alkyl group, cycloalkyl group or aryl group. Some examples of this include methyl, ethyl, n-propyl, isopropyl, isobutyl, pentyl, hexyl, octyl, cyclopentyl, cyclohexyl, phenyl and tolyl. Examples of such alyuminiiorganicheskikh compounds include:

trialkylaluminium, such as trimethylaluminum, triethylaluminum, triisopropanolamine, triisobutylaluminum, trioctylamine and three 2-ethylhexylamine;

alkenylacyl mini chloride, Diisopropylamine chloride, diisobutylaluminum chloride and dimethylaluminum bromide;

alkylamines polytonality, such as methylamine polutoraglazy, ethylaluminum polutoraglazy, Isopropylamine polutoraglazy, bucillamine polutoraglazy and ethylaluminum polycarbonic;

alkylamines dihalide, such as dichloride methylalanine, dichloride ethylamine, dichloride Isopropylamine and dibromide ethylaluminum; and

alkylamines hydrides, such as diethylaluminum hydride and diisobutylaluminum hydride.

You can also use as alyuminiiorganicheskikh connection, the connection represented by the formula:

RanAlY3-n,

where Rameans the same as above; Y represents-ORbgroup, - OSiRc3group-OAlRd2group, - NRe2group-SiRf3group or - N(Rg)AlRh2group; n indicates 1 or 2; Rb, Rc, Rdand Rhmean each methyl, ethyl, isopropyl, isobutyl, cyclohexyl, phenyl or the like; Remeans hydrogen, methyl, ethyl, isopropyl, phenyl, trimethylsilyl or the like; and Rfand Rgmean each methyl, ethyl or the like.

An example is-n for example dimethylaluminum methoxide, diethylaluminum ethoxide and diisobutylaluminum methoxide;

(ii) the compounds of formula RanAl(OSiRc)3-nsuch as Et2Al(OSiMe3), (iso-Bu)2Al(OSiMe3and (iso-Bu)2Al(OSiEt3);

(iii) the compounds of formula RanAl(OAlRd2)3-nsuch as Et2AlOAlEt2and (iso-Bu)2AlOAl(iso-Bu)2;

(iv) compounds of the formula RanAl(NRe2)3-nsuch as Me2AlNEt2Et2AlNHMe, Me2AlNHEt, Et2AlN(Me3Si)2and (iso-Bu)2AlN(Me3Si)2;

(v) the compounds of formula RanAl(SiRf2)3-nfor example, (iso-Bu)2AlSiMe3;

(vi) the compounds of formula RanAl[N(Rg)-AlRh2]3-nsuch as Et2AlN(Me)-AlEt2and (iso-Bu)2AlN(Et)Al(iso-Bu)2.

In addition, compounds similar to the above compounds, for example alyuminiiorganicheskikh connection, where two or more atoms of aluminum are linked via an oxygen atom or a nitrogen atom, can also be used. Examples of such compounds include (C2H5)2AlOAl(C2H5)2, (C4H9)2AlOAl(C4H9)2and (Cs as methylaluminoxane, can also be used.

Alkyl complex compound of a metal of Group I and aluminum, for example, means a compound represented by the following formula:

M1AlRj4,

where M1means Li, Na or K, and Rjmeans hydrocarbon group of 1 to 15 carbon atoms.

Examples of such compounds include LiAl(C2H5)4and LiAl(C7H15)4.

ORGANOMETALLIC compound of a metal of Group II represented by the following formula:

RkR1M2,

where Rkand R1indicate each a hydrocarbon group of 1 to 15 carbon atoms or halogen, Rkand R1may be the same or different except that both of them are halogen, and M2means Mg, Zn or Cd.

Examples of such compounds include diethylzinc, determine, butylamine, etimani chloride and butylamine chloride.

From alyuminiiorganicheskikh compounds described above are preferably used compounds of the formula Ra3AlX3-n, RanAl(ORb)3-nand RanAl(OAlRd2)3-nespecially trialkylaluminium.

The above compound could is talesfore polymerization of ethylene invention.

The catalyst for polymerization of ethylene invention may in addition contain other components for the polymerization of ethylene in addition to the above components.

The method of polymerization of ethylene.

In the method of polymerization of ethylene according to the invention, the ethylene will polimerizuet in the presence of a catalyst for polymerization of ethylene, comprising a solid titanium catalyst component [I] and the ORGANOMETALLIC compound [II], but the ethylene can be copolymerization with a small number of other olefins.

Examples of olefins include-olefins of 3 to 20 carbon atoms, such as propylene, 1-butene, 1-penten, 1-hexene, 3-methyl-1-butene, 3-methyl-1-penten, 3-ethyl-1-penten, 4-methyl-1-penten, 4,4-dimethyl-1-penten, 4-methyl-1-hexene, 1-octene, 1-mission 1-dodecene, 1-tetradecene, 1-hexadecene, 1 octadecene and 1 achozen. In addition, vinyl compounds, other unsaturated compounds and unsaturated compounds can also copolymerizate. For example, there may be mentioned:

aromatic vinyl compounds such as styrene, substituted styrene, Olivenza, substituted allylbenzene, vinylnaphthalene, substituted vinylnaphthalene, alienation and substituted Allington;

Alice is, substituted vinylcyclohexane, vinylcyclopentane, substituted vinylcyclohexane and allylnormorphine;

cycloolefin, such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclinea and 2-methyl-1,4,5,8-dimethano-1,2,3,4,4 a, 5,8,8-octahydronaphthalene; and

unsaturated silane compounds such as allyltrimethylsilane, allyltrimethylsilane, 4-trimethylsilyl-1-butene, 6-trimethylsilyl-1-hexene, 8-trimethylsilyl-1-octene and 10-trimethylsilyl-1-the mission.

Two or more kinds of the above can copolymerizate monomers can be copolymerizable with ethylene.

In the method of polymerization of ethylene invention, it is desirable that the solid titanium catalyst component [I] was used in the amount of usually about 0.0001 to 1.0 mmol with respect to the titanium atom, based on 1 liter of the polymerization volume, and ORGANOMETALLIC compound [II] is used in such amount that the number of the metal atom in the compound [II] becomes usually about 1 to 2,000 mol, preferably about 5 to 500 mol per 1 mol of titanium atom in the polymerization system.

The polymerization can be carried out as a liquid-phase polymerization, such as polymerization in solution or arizala, polymerization-inactive organic solvent is generally used as a polymerization solvent. Examples of organic solvents include aliphatic hydrocarbons, such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane and Methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; and halogenated hydrocarbons such as ethylene chloride and chlorobenzene. These solvents may be used in combination. Together with an organic solvent capable of copolymerizate monomer, which is also used as a liquid at the reaction temperature.

The conditions of polymerization varies depending on the type of polymerization, the final ethylene polymer and so on, but the polymerization is carried out usually at a temperature of about from 20 to 300oC, preferably from 50 to 150oC, under pressure from atmospheric to 100 kg/cm2preferably from about 2 to 50 kg/cm2.

If hydrogen is used in the method of polymerization, the molecular weight of the final polymer can be modified.

The polymerization can be carried out periodically reaction conditions.

According to the invention in the polymerization of ethylene, the catalyst is formed by using the above-described specific solid titanium catalyst component, and therefore, the polymer of ethylene having excellent particle properties can be obtained with a remarkably high polymerization activities. In the final polymer of ethylene, respectively, the amount of catalyst residue in the polymer link, especially halogen, low, and, therefore, corrosion of the form hardly takes place in the molding process. Thus, the polymer of ethylene has a low content of finely ground powder and shows excellent properties of the particles, whereby the polymer can be used without granulation.

The polymer of ethylene, obtained in the present invention preferably has a specific gravity of from 0.20 to 0.60 g/cm3preferably from 0.25 to 0.60 g/cm3.

The polymer of ethylene preferably has a flow rate of melting (MFR, measured according to ASTM D E, 190oC) from 0.01 to 5,000 g/10 min.

The polymer of ethylene is obtained in the invention can optionally be added additives such as heat stabilizer, a stabilizer against the destruction of podsokratili, pigment, dye, and inorganic or organic filler.

THE EFFECT OF THE INVENTION.

According to the present invention, the solid titanium catalyst component which is a polymer of ethylene having a low content of finely ground powder and showing excellent particle properties can be obtained with a very high yield per unit of catalyst, the catalyst for polymerization of ethylene containing solid titanium catalyst component, and the method of polymerization of ethylene using the catalyst are provided.

EXAMPLES.

The present invention will be described hereinafter in accordance with the following examples, but it should be construed that the invention is not limited to these examples.

In the following examples, the composition, the particle size and the volume weight of the solid titanium catalyst component were determined by methods described below.

(1) the magnesium Content, the content of titanium

ICP analysis (ICPF 1000TR, produced by Shimazu Seisakusho K. K.)

(2) chlorine Content

The chlorine content was determined by the method of titration with silver nitrate.

(3) the Content OR group

Carefully dried catalizer gas chromatography.

(4) the Distribution of particles sizes

The distribution of particles sizes were determined by vibrating apparatus (low-tap type, produced by Iida Seisakusho K. K. ) and SITA (inner diameter 200 mm, available from Bunsei Furui, K. K.).

(5) Unit weight

Specific gravity was determined in accordance with JIS K 6721.

Example 1.

Preparation of solid titanium catalyst component.

value of 4.76 g (50 mmol) of anhydrous magnesium chloride, 28,1 ml of decane and 16.3 g (125 mmol) of 2-ethylhexanol alcohol reacted with each other under heating at 130oC for 3 hours, giving a homogeneous solution. To the solution was added 3.1 g (15 mmol) of tetraethoxysilane and stirred at 50oC for 2 hours for dissolution of tetraethoxysilane.

The entire quantity of the homogeneous solution obtained above was cooled at room temperature and then dropwise added to 200 ml (1.8 mol) of titanium tetrachloride, maintaining the temperature at 0oC for 1 hour under stirring. After the addition was completed, the temperature of the mixture maintained at 0oC for 1 hour, then brought to 110oC for one hour and 45 minutes and maintained at this temperature in techenie separated by hot filtration. The solid was thoroughly washed with hexane and decane at 110oC up until any connection of titanium in the wash liquid has ceased to be detected, to obtain a hexane slurry of the solid titanium catalyst component.

The composition of the solid titanium catalyst component described further in Table 2.

The polymerization.

In a 1 liter autoclave were placed 500 ml of purified n-heptane in nitrogen atmosphere. Then 0.5 mmol of triethylaluminum and 0.005 mmol (in relation to the titanium atom) of the hexane slurry of the solid titanium catalyst component were added and the temperature brought to 80oC. the system was applied to hydrogen so that the pressure was 4.0 kg/cm2-G, and then ethylene was continuously applied for 2 hours so that the total pressure became 8.0 kg/cm-1-G. the polymerization Temperature was maintained at 80oC.

After the polymerization was completed, the polymer of ethylene is separated from the n-heptane solvent and dried.

After drying the powdery polymer obtained in the amount of 184,9, This powdery polymer had MFR of 2.8 g/10 min and estimated the weight of 0.33 g/cm3. The results below e 1.

Example 2. A catalytic component was obtained in the same manner as in Example 1, except that upon receipt of the catalytic component of reaction time at 110oC was changed to 1.5 hours-2 hours. Using catalyst component, polymerization was conducted in the same manner as in Example 1. The results are shown in the following Table 2 and Table 3.

Example 3. A catalytic component was obtained in the same manner as in Example 1, except that upon receipt of the catalytic component, the reaction temperature was changed to 105oC 110oC. Using the catalyst component, polymerization was performed in the same way as in Example 1. The results are shown in the following Table 2 and Table 3.

Example 4. A catalytic component was obtained in the same manner as in Example 1, except that upon receipt of the catalytic component, the number of Dean changed 29.3 ml from 28.1 ml and the number of 2-ethylhexanol alcohol changed 15.3 g (117,5 mmol) with 16.3 g (125 mol). Using catalyst component, polymerization was conducted in the same manner as in Example 1. The results are shown in the following Table 2 and Table 3.

Example 5. The catalytic component is the number of Dean changed by 37.3 ml from 28.1 ml Using catalyst component, polymerization was conducted in the same manner as in Example 1. The results are shown in the following Table 2 and Table 3.

Comparative example 1.

Preparation of solid titanium catalyst component.

value of 4.76 g (50 mmole) of anhydrous magnesium chloride, 29.3 ml of decane and 15.3 g (117,5 mmole) 2-ethylhexanol alcohol reacted with each other under heating at 130oC for 3 hours to obtain a homogeneous solution. To the solution was added 0.88 g (5,85 mmole) of ethylbenzoic and stirred at 130oC for 1 hour to dissolve ethylbenzoic in solution.

The entire quantity of the homogeneous solution obtained above was cooled to room temperature and then was added dropwise to 200 ml (1.8 mol) of titanium tetrachloride supported at 0oC for one hour under stirring. After the addition was completed, the temperature of the mixture was brought to 80oC for 1.5 hours. When the temperature of the mixture reached 80oWith, of 2.34 g (15.6 mmole) of ethylbenzoic added, and the resulting mixture was maintained at the same temperature for 2 hours under stirring.

After a two-hour reaction, the solid was separated hot Phil is at the 90oC for 2 hours. After the reaction was completed, the solid was separated again by hot filtration. The solid was thoroughly washed with decane at 110oC and hexane until such time as any compound of titanium in the wash liquid has ceased to be detected, to obtain a hexane slurry of the solid titanium catalyst component. The composition of the solid titanium catalyst component are listed in the following Table 2.

Then the polymerization was conducted in the same manner as in Example 1, except that there was used the result of the above solid titanium catalyst component. The results are shown below in Table 3.

Comparative example 2.

Preparation of solid titanium catalyst component.

7,14 g (75 mmole) of anhydrous magnesium chloride, 37.5 ml of decane and of 29.3 g (225 mmole) 2-ethylhexanol alcohol reacted with each other under heating at 130oC for 2 hours, giving a homogeneous solution. To the solution was added to 1.67 g (11.3 mmole) of phthalic anhydride and stirred at 130oC for 1 hour to dissolve the phthalic anhydride in the solution.

The whole amount of the obtained homogeneous solution was cooled to room temperature and the after completed the addition, the temperature of the mixture was raised to 110oC for 4 hours and maintained at the same temperature for 2 hours under stirring.

After a two-hour reaction, the solid was separated by hot filtration. Solid resuspendable in 200 ml of titanium tetrachloride and then reaction was performed again when heated at 110oC for 2 hours. After completion of the reaction, the solid was separated again by hot filtration. The solid was thoroughly washed with hexane and decane at 110oC up until any titanium compound in the wash liquid has ceased to be detected, to obtain a hexane slurry of the solid titanium catalyst component. The composition of the solid titanium catalyst component are listed in the following Table 2.

Then polymerization was performed in the same manner as in Example 1, except that used was obtained above solid titanium catalyst component. The results are shown in Table 3.

Comparative example 3.

Preparation of solid titanium catalyst component.

400 ml chetyrehkolkoy flask suspended 2.86 g (30 mmole) of anhydrous magnesium chloride in 150 ml of decane. In the suspension deagle at room temperature for 1 hour. Then 10.1 g (84 mmole) of monochloride diethylaluminum dropwise added to the ongoing reaction at 30oC for 1 hour.

Then added 56,9 g (300 mmol) of titanium tetrachloride. The resulting mixture was heated and stirred at 80oC for 3 hours.

After completion of the reaction the obtained solid was separated from the liquid phase. The solid was thoroughly washed with hexane until such time as any compound of titanium in the wash liquid has ceased to be detected, to obtain a hexane slurry of the solid titanium catalyst component thus. The composition of the solid titanium catalyst component are listed in the following Table 2.

Then polymerization was performed in the same manner as in Example 1, except that used the above solid titanium catalyst component. The results are shown below in Table 3.

Comparative example 4.

The solid titanium catalyst component was obtained in the same manner as in Example 1, except that in the preparation of solid titanium catalyst component temperature after exposure of a solution of magnesium and titanium tetrachloride (high temperature) was changed to 90

The result was obtained powdery polymer of ethylene with access 76,1, This powdered ethylene polymer had MFR of 2.4 g/10 min and a specific weight of 0.31 g/cm3. The results are presented in Table 3.

Comparative example 5.

The solid titanium catalyst component was obtained in the same manner as in Example 1, except that the temperature after exposure of a solution of magnesium and titanium tetrachloride (high temperature) is changed to 120oC 110oC. Using a solid titanium catalyst component, polymerization was conducted in the same manner as in Example 1.

The results are presented in the following Table 2 and Table 3.

Comparative example 6.

The solid titanium catalyst component was obtained in the same manner as in Example 1, except that upon receipt of the catalytic component, the amount of tetraethoxysilane was changed to 2.1 g (10 mmol) with 3.1 g (15 mmol). Using the solid titanium catalyst component, polymerization was performed tyrannically example 7.

The solid titanium catalyst component was obtained in the same manner as in Example 1, except that upon receipt of the catalytic component, the amount of tetraethoxysilane was changed to 4.2 g (20 mmol) with 3.1 g (15 mmol). Using the solid titanium catalyst component, polymerization was conducted in the same manner as in Example 1.

The results are presented in the following Table 2 and Table 3.

Comparative example 8.

The solid titanium catalyst component was obtained in the same manner as in Example 1, except that upon receipt of the catalytic component, the amount of tetraethoxysilane was changed to 2.1 g (10 mmol) with 3.1 g (15 mmol) and temperature after exposure of a solution of magnesium and titanium tetrachloride (fever) changed to 90oC 110oC. Using a solid titanium catalyst component, polymerization was conducted in the same manner as in Example 1.

The results are presented in the following Table 2 and Table 3.

Example 6.

Preparation of solid titanium catalyst component

value of 4.76 g (50 mmol) of anhydrous magnesium chloride, 28,1 ml of decane and 16.3 g (125 mmol) of 2-ethylhexanol alcohol responded one ( 3.1 g (15 mmol) of tetraethoxysilane and stirred at 50oC for 2 hours to dissolve the tetraethoxysilane solution.

The entire quantity of the homogeneous solution obtained above was cooled to room temperature and then dropwise added to 200 ml (1.8 mol) of titanium tetrachloride supported at 0oC for 1 hour under stirring. After completion of the addition the temperature of the mixture was maintained at 0oC for 1 hour and 45 minutes. When the temperature of the mixture reached 110oC, was added 1.0 g (5 mmol) of tetraethoxysilane.

Next, the mixture was stirred at 110oC for 2 hours. After 2 hours reaction, the obtained solid was separated by hot filtration. The solid was thoroughly washed with hexane and decane at 110oC up until any connection of titanium in the wash liquid has ceased to be detected, to obtain a hexane slurry of the solid titanium catalyst component. The composition of the solid titanium catalyst component below in Table 4.

The polymerization.

In a 1-liter autoclave were placed 500 ml of purified n-heptane in nitrogen atmosphere. Then 0.5 mmole of triethylaluminum and 0.005 mmole (with respect to the titanium atom) of the hexane slurry of the solid titanoboa, so the pressure was 4.0 kg/cm2-G and then ethylene was continuously applied for 2 hours so that the total pressure became 8.0 kg/cm2-G. the polymerization Temperature was maintained at 80oC.

After the polymerization was completed, the polymer of ethylene is separated from the n-heptane solvent and dried.

Example 7.

A catalytic component was obtained in the same manner as in Example 6, except that the amount of tetraethoxysilane (second Addendum) added when the temperature reached 110oC changed to 2.1 g (10 mmol) with 1.0 g (5 mmol). Using the catalytic component, polymerization was conducted in the same manner as in Example 6. The results are shown in Table 4 and Table 5.

Comparative example 9.

A catalytic component was obtained in the same manner as in Example 6, except that the temperature achieved in obtaining a catalytic component was changed to 120oC 110oC and the second adding tetraethoxysilane carried out when the temperature reached 120oC. Using the catalyst component, polymerization was conducted in the same manner as in Example 6. The results are shown in Table 4 and the m as in Example 6, except that the temperature achieved in obtaining a catalytic component was changed to 90oC 110oC and the second adding tetraethoxysilane carried out when the temperature reached 90oC. Using the catalyst component, polymerization was conducted in the same manner as in Example 6. The results are shown in Table 4 and Table 5.

1. The solid titanium catalyst component for polymerization of ethylene, obtained by a process comprising a stage of contacting (a) a liquid magnesium compounds with (b) a liquid compound of titanium in the presence of (c) organosilicon compounds having inactive hydrogen, and the stage of increasing the temperature of the obtained contact product (i) and keeping contact product (i) at this temperature, and mentioned solid titanium catalyst component comprises magnesium, titanium, halogen and an organosilicon compound having an inactive hydrogen (c), characterized in that stage contacting is carried out at a molar ratio of organosilicon compound (c) the magnesium compound (a) equal to 0.25 - 0.35 mol per 1 mol of compound of magnesium (a) and the curing of the obtained contact product (i) is on, received by a process comprising a stage of contacting (a) a liquid magnesium compounds with (b) a liquid compound of titanium in the presence of (c) organosilicon compounds having inactive hydrogen, and the stage of increasing the temperature of the obtained contact product (i) and keeping it at this temperature, and mentioned solid titanium catalyst component comprises magnesium, titanium, halogen and an organosilicon compound having an inactive hydrogen (c), characterized in that stage contacting is carried out at a molar ratio of organosilicon compound (c) to the magnesium compound (a), equal to 0.25 - 0.35 mol per 1 mol of compound of magnesium (a) and the curing of the obtained contact product (i) is carried out at 105 - 115oC adding organosilicon compounds having inactive hydrogen (c) in an amount of not more than 0.5 mol per 1 mol of compound of magnesium (a), and the temperature of the contact product (i) rises from the temperature below 10oC, than the supported temperature, to a temperature at which the temperature rise is completed, or after the temperature rise is completed, resulting in a contact connection (c) the contact product (i)and (II) alyuminiiorganicheskikh connection, characterized in that the solid titanium catalyst component, the catalyst contains a component under item 1 or 2.

4. The method of polymerization of ethylene by polymerization of ethylene in the presence of a catalyst containing a solid titanium catalyst component and alyuminiiorganicheskikh connection, characterized in that the catalyst used catalyst under item 3.

 

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