The solid titanium catalyst component for polymerization of olefins, process for its production, the catalyst for polymerization of olefins and polymerization of olefins

 

(57) Abstract:

The solid titanium catalyst component for polymerization of olefins comprises, by weight. %: magnesium 5-35; titanium 0.3 to 10; halogen 30-75 100 wt.% of the total product; a compound having at least two ether ties, 0.5 to 30; the carbon of 0.5 to 20 and the electron donor of 0.05-7. When using titanium component of the specified personnel get olefins having a uniform particle size, high bulk density and high stereoregularity. 6 C. and 5 C.p. f-crystals, 4 tab., 2 Il.

The invention relates to a solid titanium catalyst component for use as a catalyst in the production of homopolymers or copolymers of olefins and to a method for producing a solid titanium catalyst component. The present invention also relates to a catalyst for polymerization of olefins containing solid titanium catalyst component and to a method of polymerization of olefin using the catalyst for polymerization of olefins.

Background of the invention

In the technique known catalyst containing magnesium halide and the applied compound of titanium, for use in the production of polymers of olefins, including nd the liberizatsii olefins contains, for example, the solid titanium catalyst component, which includes magnesium, titanium, halogen and an electron donor, and a component of a catalyst comprising an ORGANOMETALLIC compound.

Proposed different ways of obtaining the above-mentioned solid titanium catalyst component containing magnesium, titanium, halogen and an electron donor as essential components. In the technique is also known that a polymer having a high stereoregularity can be obtained with high yield in the polymerization of olefin containing at least three carbon atoms, in the presence of the solid titanium catalyst component.

The usual way to obtain a solid titanium catalyst component contains stage, which consists in bringing into contact of the hydrocarbon solution galogensoderjasimi connection with liquid magnesium compound of titanium with the formation of a solid product. It also contains stage, which consists in obtaining a hydrocarbon solution of a halogen-containing compounds of magnesium and titanium, followed by the formation of a solid product in the presence of at least one electron donor selected from the group compiled the esters of polybasic compounds, anhydrides of acids, ketones, simple aliphatic esters, aliphatic carbonates, alkoxycarbonyl alcohols, alcohols having alloctype, organosilicon compounds containing a bond of Si-O-C, and organophosphorus compounds containing a bond P-O-C

In this regard, it is known that the choice of electron donor polycarboxylic acid (for example, phthalic anhydride/ leads to the production of solid titanium catalyst component, which can be obtained /co/olefin polymer having particles, uniform in size, and value less dust /less dust quanlity/.

The authors of the present invention conducted a study for the development of Ti-catalyst for polymerization of olefins, which can be obtained from /from/polymers of olefins with homogeneous particle size value less dust and high volume weight /bulk density/. In the result, it was found that /co/polymers having uniform particle size value less dust and high bulk density can be obtained when using catalyst for polymerization of olefins containing solid titanium component as an essential component includes (a) magnesium, (b) titanium, (c) gegliedert and (f) an electron donor, other than the compound (d). Based on the results of searches completed the present invention.

The purpose of the invention

The aim of the present invention is a solid titanium catalyst component as a component of the catalyst with a high polymerization activity, which can be obtained from /from/polymers of olefins with homogeneous particle size value less dust, high bulk density and high stereoregularity.

Another objective of the present invention is a method of obtaining a solid titanium catalyst component.

The next objective of the present invention is a catalyst for polymerization of olefins containing solid titanium catalyst component.

Another objective of the present invention is to provide a method for the polymerization of olefins using the catalyst for polymerization of olefins.

Summary of the invention

The solid titanium catalyst component for the polymerization of olefins corresponding to the present invention, containing:

(a) magnesium - 5 ~35 wt.%,

(b) titanium - 0.3 to ~10 wt.%,

(c) halogen - 30 ~75 wt.%,

(d) connecting the hydrocarbon - 0,05 ~20 wt.%, and

(f) an electron donor, other than the compound (d) is 0.05 ~7 wt.%.

The first way to obtain a solid titanium catalyst component for the polymerization of olefins corresponding to the present invention contains stage:

- bringing into contact halogenated compounds of magnesium with a compound selected from the group consisting of alcohol, simple ester, complex ester, a hydrocarbon solvent to obtain a solution of compounds of magnesium;

- bringing into contact of a solution of the compound of magnesium with a compound having at least two ether linkages provided by a particular set of atoms;

- bringing into contact of the resulting solution with a liquid compound of titanium.

The second way to obtain a solid titanium catalyst component for the polymerization of olefins corresponding to the present invention contains stage:

- bringing into contact halogenated compounds of magnesium with a compound selected from the group consisting of alcohol, simple ester, complex ester, a hydrocarbon solvent to obtain a solution of compounds of magnesium;

- bringing into contact of a solution of the compound of magnesium with a compound having, is received in the solution with a liquid compound of titanium, and, further, the bringing into contact with the electron donor.

The first catalyst for polymerization of olefins corresponding to the present invention contains:

(I) a solid titanium catalyst component (A) containing:

(a) magnesium - 5 ~35 wt.%,

(b) titanium - 0.3 to ~10 wt.%,

(c) halogen - 30 ~75 wt.%,

(d) a compound having at least two ether linkages provided by a particular set of atoms is 0.5 ~30 wt.%,

(e) the hydrocarbon - 0,05 ~20 wt.%, and

(f) an electron donor, other than the compound (d) is 0.5 ~7 wt.%;

(II) component of the catalyst (B), representing alyuminiiorganicheskikh connection, and, if necessary,

(III) an electron donor (C).

The second catalyst for polymerization of olefins corresponding to the present invention contains:

(I) prepolymerisation component of catalyst obtained by prepolymerisation of olefin in the presence of the solid titanium catalyst component (A) and catalyst component (B), representing alyuminiiorganicheskikh connection, and mentioned solid titanium catalyst component (A) contains:

(a) magnesium - 5 ~35 wt.%,

(b) titanium - 0.3 to ~10 wt.%,

(c) halogen - 30 ~75 wt.%,

(d) a compound having at Mr>
(f) an electron donor, other than the compound (d) is 0.05 ~7 wt.%;

(II) component of the catalyst (B), representing alyuminiiorganicheskikh connection, and if necessary,

(III) an electron donor C.

The method of polymerization of olefin corresponding to the present invention is the polymerization of olefins in the presence of the above-mentioned first or second catalyst for polymerization of olefins.

The catalyst for polymerization of olefins corresponding to the present invention has high polymerization activity.

When using the catalyst for polymerization of olefins corresponding to the present invention can be homopolymers or copolymers of olefins having particles of uniform size by value less dust, high bulk density and high stereoregularity.

Brief description of figures

Fig. 1 illustrates the method of producing catalyst for polymerization of olefins corresponding to the present invention.

Fig. 2 explains another method of producing catalyst for polymerization of olefins corresponding to the present invention.

Detailed description of the invention

Below will be p the CSO component of the catalyst, the catalyst for polymerization of olefins and polymerization of olefins corresponding to the present invention.

The value used here, the term "polymerization" is not limited to "homopolymerization", but may involve and "copolymerization". The value used here, the term "polymer" is not limited to "homopolymers", but can mean "copolymer".

Now, description will be given of compounds used in a method of producing a solid titanium catalyst component corresponding to the present invention, i.e., halogenated compounds magnesium compounds selected from the group consisting of alcohol, simple ester and ether complex, especially alcohol; hydrocarbon solvents; compounds having at least two ether linkages separated by many atoms; liquid compounds of titanium and an electron donor (f), other than the compound having at least two ether linkages existing among many atoms.

Specific examples of halogenated magnesium compounds for use in the present invention include:

- dihalogenide magnesium, such as magnesium dichloride, magnesium dibromide, diiodide m is, anisotropically, minibufexplorer and maniacmarshall; and

- aryloxyalkanoic magnesium, such as minifootball and manometerventile.

These magnesium compounds may be used in the form of a complex or double compounds with other metal, or in the form of a mixture with the compound of another metal. In addition, a mixture of at least two compounds of the aforementioned magnesium compounds can be used in the present invention. Of these preferred compounds are magnesium halides, and the most preferred magnesium chloride.

Alcohol for use in the present invention has no particular restrictions as he dissolves the above-mentioned halogen-containing compounds of magnesium. Specific examples of such alcohols include:

- aliphatic alcohols, such as ethylene glycol, methylcarbamoyl, 2-methylpentanol, 2-ethylbutanol, n-heptanol, n-octanol, 2-ethylhexanol, decanol, dodecanol, tetradecanoyl alcohol, undecenol, alerby alcohol and stearyl alcohol;

- alicyclic alcohols such as cyclohexanol and methylcyclohexanol;

aromatic alcohols such as benzyl alcohol, methylbenzylamine alcohol, isopropylbenzyl alcohol-medicalrelated and 1 butoxy-2-propanol.

among them, preferred is an aliphatic alcohol, the most preferred is 2-ethylhexanol.

Ethers and esters for use in the present invention, other than the compound (d) will be described later.

Specific examples of the hydrocarbon solvents used in the present invention 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;

- halogenated hydrocarbons, such as telengard and chlorobenzene; and

mixtures thereof.

Among these compounds, preferred are aliphatic hydrocarbons, the most preferred is the Dean.

In the compound having at least two ether linkages provided by a particular set of atoms (hereinafter sometimes referred to as "simple polyester"/ used in the present invention, the set of atoms can represent at least one selected from the group consisting of atoms of carbon, silicon, oxygen, nitrogen, phosphorus, boron is n relative volumetric Deputy, moreover, the mentioned atoms include a variety of carbon atoms.

Relatively bulky substituents contain more than 2 carbon atoms, preferably 3 carbon atoms, and have promoteyou, branched or cyclic structure. Preferably, when the volume substituents are branched or cyclic structure.

Bulky substituents contain ~3 to 20 carbon atoms, preferably about 3 to 10 carbon atoms, preferably about 3 to 7 carbon atoms.

Such compounds containing at least two ether linkages, provide many atoms include ethers are represented by the following formula

< / BR>
where n is an integer that satisfies the relation 2n10; R1for R26represent substituents, each of which contains at least one element selected from among carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron and silicon; any arbitrary combination of the groups R1for R26preferably R1for R20may form together a ring other than benzene; and the main chain may contain an atom other than carbon atom.

A specific example is in, include:

2-(2-ethylhexyl)-1,3-dimethoxypropane;

2-isopropyl-1,3-dimethoxypropane;

2-butyl-1,3-dimethoxypropane;

2-sec-butyl-1,3-dimethoxypropane;

2-cyclohexyl-1,3-dimethoxypropane;

2-phenyl-1,3-dimethoxypropane;

2-Cumyl-1,3-dimethoxypropane;

2-(2-phenylethyl)-1,3-dimethoxypropane;

2-(2-cyclohexylethyl)-1,3-dimethoxypropane;

2-(n-chlorophenyl)-1,3-dimethoxypropane;

2-(diphenylmethyl)-1,3-dimethoxypropane;

2-(1-naphthyl)-1,3-dimethoxypropane;

2-(2-forfinal)-1,3-dimethoxypropane;

2-(1-decahydronaphthalene)-1,3-dimethoxypropane;

2-(p-tert-butylphenyl)-1,3-dimethoxypropane;

2,2-DICYCLOHEXYL-1,3-dimethoxypropane;

2,2-dicyclopentyl-1,3-dimethoxypropane;

2,2-diethyl-1,3-dimethoxypropane;

2.2-dipropyl-1,3-dimethoxypropane;

2,2-aminobutiramida 1,3-dimethoxypropane;

2,2-dibutil-1,3-dimethoxypropane;

2-methyl-2-propyl-1,3-dimethoxypropane;

2-methyl-2-benzyl-1,3-dimethoxypropane;

2-methyl-2-ethyl-1,3-dimethoxypropane;

2-methyl-2-isopropyl-1,3-dimethoxypropane;

2-methyl-2-phenyl-1,3-dimethoxypropane;

2-methyl-2-cyclohexyl-1,3-dimethoxypropane;

2,2-bis-(p-chlorophenyl)-1,3-dimethoxypropane;

2,2-bis-(2-cyclohexylethyl)-1,3-dimethoxypropane;

2-methyl-2-isopropyl-1BR>2,2-diphenyl-1,3-dimethoxypropane;

2.2-dibenzyl-1,3-dimethoxypropane;

2,2-bis-(cyclohexylmethyl)-1,3-dimethoxypropane;

2.2-Diisobutyl-1,3-diethoxypropane;

2.2-Diisobutyl-1,3-dibutoxy;

2-isobutyl-2-isopropyl-1,3-dimethoxypropane;

2-(1-methylbutyl)-2-isopropyl-1,3-dimethoxypropane;

2-(1-methylbutyl)-2-sec-butyl-1,3-dimethoxypropane;

2,2-di-sec-butyl-1,3-dimethoxypropane;

2,2-di-tert-butyl-1,3-dimethoxypropane;

2,2-dineopentyl-1,3-dimethoxypropane;

2-isopropyl-2-isopentyl-1,3-dimethoxypropane;

2-phenyl-2-isopropyl-1,3-dimethoxypropane;

2-phenyl-2-sec-butyl-1,3-dimethoxypropane;

2-benzyl-2-isopropyl-1,3-dimethoxypropane;

2-benzyl-2-sec-butyl-1,3-dimethoxypropane;

2-phenyl-2-benzyl-1,3-dimethoxypropane;

2-cyclopentyl-2-isopropyl-1,3-dimethoxypropane;

2-cyclopentyl-2-sec-butyl-1,3-dimethoxypropane;

2-cyclohexyl-2-isopropyl-1,3-dimethoxypropane;

2-cyclohexyl-2-sec-butyl-1,3-dimethoxypropane;

2-isopropyl-2-sec-butyl-1,3-dimethoxypropane;

2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane;

2,3-diphenyl-1,4-diethoxybutane;

2,3-DICYCLOHEXYL-1,4-diethoxybutane;

2.2-dibenzyl-1,4-diethoxybutane;

2,3-DICYCLOHEXYL-1,4-diethoxybutane,4-diethoxybutane;

2,3-bis-(p-forfinal)-1,4-diethoxybutane;

2,4-diphenyl-1,5-dimethoxyethane;

2,5-diphenyl-1,5-digitoxigenin;

2,4-aminobutiramida 1,5-dimethoxyethane;

2,4-Diisobutyl-1,5-dimethoxyethane;

2,4-vitamin-1,5-dimethoxyethane;

3-methoxyethylmercury;

3-methoxymethylethoxy;

1,3-dibutoxy;

1,2-diisobutyrate;

1,2-diisobutyrate;

1,3-diatomologica;

1,3-diamination;

1,3-disapointingvery;

1,3-disapointingvery;

2,2-tetramethylene 1,3-dimethoxypropane;

2.2-pentamethylene-1,3-dimethoxypropane;

2.2-hexamethylen-1,3-dimethoxypropane;

1,2-bis-(methoxymethyl)cyclohexane;

2,8-dioxaspiro-5,5-undecane;

3,7-dioxabicyclo-3,3,1-nonan;

3,7-dioxabicyclo-3,3,0-octane;

3,3-Diisobutyl-1,5-Oksanen;

6,6-diisobutyldimethoxysilane;

1,1-dimethoxymethylsilane;

1,1-bis-(dimethoxymethyl)cyclohexane;

1,1-bis-(methoxymethyl)bicyclo-2,2,1-heptane;

1,1-dimethoxymethylsilane;

2-methyl-2-methoxymethyl-1,3-dimethoxypropane;

2-cyclohexyl-2-ethoxymethyl-1,3-diethoxypropane;

2-cyclohexyl-2-methoxymethyl-1,3-dimethoxypropane;

2.2-Diisobutyl-1,3-dimethoxysilane;

2-isopropyl-2-methoxymethyl-1,3-dimethoxysilane;

2-isobutyl-2-methoxymethyl-1,3-dimethoxysilane;

2-cyclohexyl-2-ethoxymethyl-1,3-dimoxystrobin;

2-cyclohexyl-2-ethoxymethyl-1,3-dimethoxycoumarin;

2-isopropyl-2-ethoxymethyl-1,3-dimoxystrobin;

2-isopropyl-2-ethoxymethyl-1,3-dimethoxysilane;

2-isobutyl-2-ethoxymethyl-1,3-dimoxystrobin;

2-isobutyl-2-ethoxymethyl-1,3-dimethoxysilane;

Tris-(p-methoxyphenyl)phosphine;

were-bis-(methoxymethyl)silane;

diphenyl-bis-(methoxymethyl)silane;

methylcyclohexyl-bis-(methoxymethyl)silane;

di-tert-butyl-bis-(methoxymethyl)silane;

cyclohexyl-tert-butyl-bis-(methoxymethyl)silane;

isopropyl-tert-butyl-bis-(methoxymethyl)silane.

Of these preferred compounds are simple 1,3-diesters. Especially preferred is 2,2-Diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-DICYCLOHEXYL-1,3-dimethoxypropane, 2,2-bis-(cyclohexylmethyl)-1,3-dimethoxypropane, 2-isopropyl-2-cyclohexyl-1,3-dimethoxypropane, 2-isopropyl-2-sec-butyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane and 2-isopropyl-2-cyclopentyl-1,3-dimethoxypropane.

Liquid titanium compounds used in the present izopet the , where R represents a hydrocarbon group, X is a halogen atom, and m satisfies the relation 0 m < 4.

Specific examples of such titanium compounds include:

- tetrachloride titanium, such as TiCl4, TiBr4and TiI4;

- alkoxysilylated titanium such as Ti (OCH3)Cl3, Ti(OC2H5)Cl3, Ti(OH-C4H9)Cl3, Ti(OC2H5)Br3and Ti(O-ISO-C4H9) Br3;

- dialkoxybenzene titanium such as Ti(OCH3)2Cl2, Ti(OC2H5)2Cl2, Ti(O-n-s4H9)2Cl2and Ti(OC2H5)2Br2;

dialkoxybenzene titanium such as Ti(OCH3)3Cl, Ti(OC2H5)3Cl, Ti(O-n-C4H9)3Cl and Ti(OC2H5)3Br;

tetraethoxide titanium such as Ti(OCH3)4, Ti(OC2H5)4, Ti(O-n-C4H9)4, Ti(O-ISO-C4H9)4and Ti(O-2-ethylhexyl)4.

Of these preferred compounds are tetrachloride titanium, and particularly preferred is titanium tetrachloride.

These titanium compounds may be used one by one or in combination. Before pryeonov (f), other than the compound (d), including alcohols, esters, including esters of acids containing a metal, and ethers. These electron donors (f) can cause the dissolution of the above-mentioned halogen-containing compounds of magnesium.

Examples of alcohols that can cause the dissolution of halogen-containing compounds of magnesium, above.

Examples of esters that can cause the dissolution of halogenated magnesium compounds include esters of organic acids containing from 2 to 18 carbon atoms, such as methylformate, methyl acetate, ethyl acetate, vinyl acetate, propyl, octylated, cyclohexylacetate, ethylpropane, methylbutyrate, Etisalat, methylchloride, ethyldichlorosilane, methyl methacrylate, etildronat, ethylcyclohexylamine, methylbenzoate, ethylbenzoic, propylbenzoate, butylbenzoate, octylbenzoic, cyclohexylbenzene, phenylbenzoate, benzyl benzoate, methylfolate, atilola, amitola, utilitybased, methyl ester anise acid, ethyl ester anise acid, utilitariansim, -butyrolactone, -valerolactone, coumarin, phtalic and ethylcarbonate.

Examples of esters of acids containing a metal that can cause dissolution galleymore of titanates include:

- orthotitanate, such as methylacetylene, utilitarian, n-proportation, isopropylacetate, n-utilitarianist, isobutylacetate, n-abilitation, 2-ethylhexylamine, n-accelertation, phenylacetylene and cyclohexylacetate;

- polytitanate, such as polymethylsilane polititians, poly-n-propertythat, poly-isopropylidene, poly-n-butylsilane, polyisobutylene, poly-n-millitant, poly-2-ethylhexylamine, poly-n-octylsilane, polyvinylidene and polycyclohexylene.

Like the above as examples of the titanate, as examples of vanadates, niobates and zirconates can be mentioned, for example, orthovanadate, polyvanadate, antoniobuy, polymyopathy, orthocarbonate and polycarbonate.

Examples of ethers that may cause the dissolution of halogenated magnesium compounds are ethers containing from 2 to 20 carbon atoms, such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole and diphenyl ether.

The solid titanium catalyst component for the polymerization of olefins corresponding to the present invention may moans (g) includes alcohols, other than those described above, phenols, ketones, aldehydes, carboxylic acids, galodamadruga organic acids, acid amides, acid anhydrides, alkoxysilane, Amici, amines, NITRILES, pyridine and isocyanates.

Specific examples of such electron donor (g) include:

alcohols, such as methanol, ethanol, propanol, butanol, trichloroethanol, trichloroethanol and trichloroethanol;

phenols containing from 6 to 20 carbon atoms, which may contain a lower alkyl group, such as phenol, cresol, Xylenol, ethylphenol, propylene, Nonylphenol, cumylphenol and naphthol;

ketones containing from 3 to 15 carbon atoms, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone and benzoquinone;

aldehydes containing from 2 to 15 carbon atoms, such or acetaldehyde, Propionaldehyde, octillery, benzaldehyde, tolualdehyde and naphthaldehyde;

halides containing from 2 to 15 carbon atoms, such as acetylchloride, benzoyl chloride, talwalkar and antillarum;

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

amines, such as trimethylamine, triethylamine, tributylamine, tribenzylamine and tetramethylethylenediamine, ethylpyridine and dimethylpyridin; and

anhydrides of acids, such as acetanhydride, phthalic anhydride and benzoic anhydride.

Examples of preferred esters of organic acids are polycarboxylate having the skeleton represented by formula

< / BR>
In the above formulas, R1represents an unsubstituted or substituted hydrocarbon group; each of R2, R5and R6independently represents hydrogen or unsubstituted or substituted hydrocarbon group; and each of R3and R4independently represents hydrogen or unsubstituted or substituted hydrocarbon group, and preferably, at least one of them was an unsubstituted or substituted hydrocarbon group. R3and R4can be connected to each other to form a cyclic structure. When the hydrocarbon group R1for R6are substituted, Deputy contains a heteroatom, such as N, O and S, and includes groups C-O-C, COOR, COOH, OH, SO3H-C-N-C - NH2.

Specific examples of the carboxylates include aliphatic polycarboxylate; alicyclic polycarboxylate; aromatic polycarboxylate and Guatemala, diisobutylamine, di-n-exercisesexercises, diethylmaleate, diisopropylethylamine, diethylphthalate, diisobutylphthalate, di-n-butylphthalate, di-2-ethylhexylphthalate and dibutil-3,4-furandicarboxylic.

Especially preferred polycarboxylate are phthalates.

From the above-mentioned electron donor especially preferred are compounds having at least two ether linkages provided by a particular set of atoms.

The solid titanium catalyst component for the polymerization of olefins corresponding to the invention, receive the following way.

When receiving the solid titanium component of the catalyst is first introduced into the contact of the above-mentioned halogen-containing magnesium compound with the above alcohol in the above-mentioned hydrocarbon solvent to obtain a homogeneous solution (a solution of compounds of magnesium), in which the halogen-containing magnesium compound dissolved in a solvent which is a mixture of alcohol and hydrocarbon.

Alcohol is used in an amount of from 1 to 40 moles, preferably from 1.5 to 20 moles, per mole haloesters compounds of magnesium. The hydrocarbon solvent and the magnesium. It is preferable to make the contact at a temperature of from 65 to 300oC, especially in the range from 100 to 200oC, for 15 to 300 minutes, especially within 30 - 120 minutes.

Then a solution of the compound of magnesium is introduced into contact with the compound having at least two ether linkages provided by a particular set of atoms, to obtain a homogeneous solution (polyester solution compounds of magnesium).

The compound having at least two ether linkages provided by a particular set of atoms, is used in an amount of from 0.01 to 1.0 mole, preferably from 0.1 to 0.5 mole, per mole of the halogenated compounds of magnesium in solution compounds of magnesium. It is preferable to make the contact at a temperature of from -20 to 300oC, especially in the range from 20 to 200oC, for 5 to 240 minutes, especially for 10 to 120 minutes.

Further, the polyester solution of magnesium compounds is introduced into contact with the liquid compound of titanium to obtain a liquid mixture containing a halogen-containing magnesium compound and a liquid compound of titanium (magnesium-titanium solution).

Liquid compound of titanium is used in an amount of from 2 to 100 grams-atoms, preferably from 4 to 50 gram atoms per gram - from -70 to 200oC, especially in the range from -70 to 50oC, for 5 to 300 minutes, especially during the 30 - 180 minutes.

Heating the thus obtained magnesium-titanium solution at 20 - 300oC, preferably at 50 to 150oC, causes the precipitation of the solid titanium catalyst component and the formation of a suspension in a hydrocarbon solvent. It is proposed to heat for 10 to 360 minutes, preferably for 30 to 300 minutes.

In the present invention, after bringing into contact of the polyester solution of compounds with liquid magnesium compound with titanium magnesium-titanium solution can then be put in contact with the electron donor. When making contact with the electron donor preferably, the magnesium-titanium solution was heated before contact. The compound having at least two ether linkages provided by a particular set of atoms, when used as an electron donor may be identical or may differ from the compounds used to prepare the polyester solution of magnesium compounds.

The electron donor is used in an amount of from 0.01 to 5 moles, preferably from 0.1 to 1 mole, per mole of the compounds of magnesium.

Filtratio or similar, to get the hard part (the solid titanium catalyst component), and, if necessary, to bring the solid is in contact with the liquid compound of titanium.

The thus obtained solid titanium catalyst component is washed preferably hydrocarbon solvent mentioned above.

The obtained solid titanium component of the catalyst may be suspended in a hydrocarbon solvent and used as catalyst for the polymerization of olefins. However, it can be separated from the liquid by filtration or similar, and the solid may be dried before use in the polymerization of olefins.

The solid titanium catalyst component corresponding to the present invention contains:

(a) magnesium - 5 ~35 wt.%,

(b) titanium - 0.3 to ~10 wt.%,

(c) halogen - 30 ~75 wt.%,

(d) a compound having at least two ether linkages separated by many atoms of 0.5-30 wt.%,

(e) a hydrocarbon of 0.5-20 wt.%,

(f) an electron donor, other than the compound (d) is 0.05 to 7 wt.%.

The electron donor (f) represents such a connection, which is described above, and as an electron donor (f) can you encodergasm compounds of magnesium.

Preferably, in the solid titanium catalyst component for the polymerization of olefins magnesium (a) is contained in an amount of 5 to 35 wt.%, preferably from 8 to 30 wt.%, more preferably in the range from 10 to 28 wt.%, particularly preferably 12 to 25 wt.%; titanium (b) is contained in an amount of from 0.3 to 10 wt.%, preferably from 0.5 to 8 wt.%, more preferably from 0.8 to 6 wt.%, particularly preferably in amounts of from 1 to 5 wt.%; and halogen (c) is contained in an amount of from 30 to 75 wt.%, preferably from 35 to 75 wt.%, more preferably from 38 to 72 weight. %, and particularly preferably from 40 to 70 wt.%. In addition, it is desirable that the compound (d) having at least two simple polyester ties divided by the mass of atoms contained in an amount of from 0.5 to 30 wt.%, preferably from 1 to 27 wt.%, more preferably from 3 to 25 wt.%, particularly preferably from 5 to 23 wt.%; hydrocarbon (e) is contained in an amount of from 0.05 to 20 wt.%, preferably from 0.1 to 15 wt.%, more preferably from 1 to 12 wt.%, particularly preferably from 2 to 10 wt.%; and the electron donor (f) other than the compound (d) contained in an amount of from 0.05 to 7 wt.%, preferably from 0.1 to 5 weight. %, more preferably from 0.15 to 4 esponente catalyst for polymerization of olefins the corresponding present invention, exceeds 20%, the adhesion of the catalyst particles, which causes deterioration of the catalyst particles and, accordingly, the polymer particles obtained by using particles of the catalyst degraded properties. On the other hand, if the amount of hydrocarbon is less than 0.05 wt.%, worse, not only the properties of the catalyst particles, the catalytic activity decreases, but also reduces stereoregularity of the obtained polymer and, accordingly, the polymer particles obtained by using particles of the catalyst degraded properties.

The way to determine the above-mentioned composition, comprises washing the obtained solid titanium catalyst component a sufficiently large quantity of hexane, followed by drying at room temperature and a pressure of 0.1 - 1 Torr for 2 hours and measured the contents by AAS (atomic absorption spectroscopy), GC or similar.

The solid titanium catalyst component of the present invention may contain other components in addition to the aforementioned components (a) to (f), such as the media, and it is desirable that these other components Materialien preferably not more than 20 wt.%.

The solid titanium catalyst component for the polymerization of olefins, obtained as described above is used together with the component catalyst consisting of ORGANOMETALLIC compounds containing a metal of groups I - III of the periodic table, such as ORGANOMETALLIC compound, described later, to obtain a catalyst for polymerization of olefins.

Further, the catalyst for polymerization of olefins corresponding to the present invention will be described similarly.

The first catalyst for polymerization of olefins corresponding to the present invention comprises a solid titanium catalyst component (A), the catalyst (B), representing alyuminiiorganicheskikh connection, and, if necessary, an electron donor (C).

In Fig. 1 and 2 explains the method for producing a catalyst for polymerization of olefins corresponding to the present invention.

Component of the catalyst (B) used for the formation of a catalyst for polymerization of olefins corresponding to the present invention, which alyuminiiorganicheskikh compound includes, for example, alyuminiiorganicheskikh compound represented HUF the volume of carbon X represents a halogen or hydrogen, and n is from 1 to 3.

In the above formula, Rarepresents a hydrocarbon group such as alkyl, cycloalkyl or aryl, having from 1 to 12 carbon atoms. Typical examples of such groups are methyl, ethyl, n-propyl, isopropyl, isobutyl, pentyl, hexyl, octyl, cyclopentyl, cyclohexyl, phenyl and tolyl.

Specific examples alyuminiiorganicheskikh compounds include such compounds as

connection trialkylamine, such as trimethylaluminum, triethylaluminum, triisopropanolamine, triisobutylaluminum, trioctylamine, three 2-ethylhexylamine and so on:

connection alkenylamine, such as isoprenaline etc.;

halides dialkylamide, such as dimethylammoniumchloride, diethylaluminium, diisopropylaminoethanol, diisobutylaluminium, dimethylaminopropyl etc.;

sesquichloride alkylamine, such as methylaluminoxane, ethylaminoethanol, isopropylaminocarbonyl, butylaminoethyl, ethylaluminum etc.;

dihalogenide alkylamine, such as methylaluminoxane, ethylaminoethanol, Isopropylamine outlineitem, and so on

As alyuminiiorganicheskikh connections are also able to work the compound represented by the formula, RnaAlY3-nin which Randis such as described above, Y represents-ORb, -OSiR3, -OAlR2d, -NR2e, -SiR3for-N(Rg)AlR2hand n is 1 or 2. Rb, Rc, Rdand Rheach represents methyl, ethyl, isopropyl, isobutyl, cyclohexyl, phenyl, etc.; Rerepresents hydrogen, methyl, ethyl, isopropyl and phenyl, trimethylsilyl, and so on; and Rfand Rgeach represents methyl, ethyl, etc.

Specific examples of such alyuminiiorganicheskikh compounds include:

(i) compounds of the formula RnaAl(ORb)3-nsuch as dimethylaminoethoxy, diethylaminoethoxy, diisobutylaluminium etc.;

(ii) the compounds of formula RnaAl(OSiR3c)3-nsuch as Et2Al(OSiMe3), (ISO-Bu)2Al (OSiMe3), (ISO-Bu)2Al(OSiEt3and so on;

(iii) the compounds of formula RnaAl(OAlR2o)3-nsuch as Et2AlOAlEt2, (ISO-Bu)2AlOAl (ISO-Bu)2and so on;

(IV) compounds forms the/SUB>AlN(Me3Si)2and (ISO-Bu)2AlN(Me3Si)2and so on;

(V) the compounds of formula RnaAl(SiR3f)3-nsuch as (ISO-Bu)2AlSiMe3and so on; and

(vi) the compounds of formula RnaAl[N(Rg)AlR2n]3-nsuch as Et2AlN(Me)AlEt2and (ISO-Bu)2AlN(Et)Al(ISO-Bu)2and so on

From the above alyuminiiorganicheskikh compounds, preferred compounds are compounds of formula R3aAl, RnaAl(ORb)3-nand RnaAl(OAlR2b)3-n.

The electron donor (C) used for the formation of a catalyst for polymerization of olefins corresponding to the present invention, includes, for example, an electron donor, preferably used for preparing the above-mentioned solid titanium catalyst component (A) and the silicon compound represented by the formula (i)

Rna- Si - (ORb)4-n(i)

in which n is 1, 2 or 3: when n is 1, Randrepresents a secondary or tertiary hydrocarbon group; when n is 2 or 3, at least one Rarepresents a secondary or tertiary hydrocarbon group, and many of the th group, containing from 1 to 4 carbon atoms; and when 4-n is 2 or 3, all Rbcan be the same or different from each other.

In the silicon compound represented by the abovementioned formula (i), secondary, or tertiary hydrocarbon group is cyclopentyloxy group, substituted cyclopentyl group, cyclopentyloxy group, substituted cyclopentadienyl group, cyclopentadienyls group, substituted cyclopentadienyls group and a hydrocarbon group in which the carbon adjacent to Si is secondary or tertiary carbon.

Examples of substituted cyclopentyl groups are cyclopentyl groups containing alkyl group, such as 2-methylcyclopentadienyl group, 3-methylcyclopentadienyl group, 2-ethylcyclopentadienyl group, 2-n-butylcyclopentadienyl group, 2,3-dimethylcyclopentene group, 2,4-dimethylcyclopentene group, 2,5-dimethylcyclopentene group, 2,3-diethylcathinone group, 2,3,4-trimethylcyclopentanone group, 2,3,5-trimethylcyclopentanone group, 2,3,4-triethylchlorosilane group, tetramethylcyclopentadienyl group and tetramethylcyclopentadienyl group.

Examples of substituted cyclopentyl groups included pencilina group, 2-ethylcyclopentadienyl group, 2-n-butylcyclopentadienyl group, 2,3-dimethylcyclopentene group, 2,4-dimethylcyclopentene group, 2,5-dimethylcyclopentene group, 2,3,4-trimethylcyclopentanone group, 2,3,5-trimethylcyclopentanone group, 2,3,4-triethylchlorosilane group, tetramethylcyclopentadienyl group and tetramethylcyclopentadienyl group.

Examples of the substituted cyclopentadienyls groups include cyclopentadienyls groups containing alkyl group, such as 2-methylcyclopentadienyl group, 3-methylcyclopentadienyl group, 2-ethylcyclopentadienyl group, 2-n-butylcyclopentadienyl group, 2,3-dimethylcyclopentane group, 2,4-dimethylcyclopentane group, 2,5-dimethylcyclopentane group, 2,3-diethyltoluenediamine group, 2,3,4-trimethylcyclopentanone group, 2,3,5-trimethylcyclopentanone group, 2,3,4-Triethylenetetramine group, 2,3,4,5-tetramethylcyclopentadienyl group, 2,3,4,5-tetramethylcyclopentadienyl group, 1,2,3,4,5-pentamethylcyclopentadienyl group and 1,2,3,4,5-pentamethylcyclopentadienyl group.

Examples of the hydrocarbon groups in which the carbon adjacent to Si, predstavleniya group; and examples of the hydrocarbon groups in which the carbon adjacent to Si is a tertiary carbon, are tert-bucilina group, tert-Amelina group ,-dimethylbenzidine group and adamantly group.

Examples of silicon compounds represented by formula (i) in which n is 1, includes tralkoxydim, such as Cyclopentasiloxane, 2-methylcyclopentadienyl, 2,3-dimethylcyclopropanecarboxylate, Cyclopentasiloxane, isobutyltrimethoxysilane, tert-butyltrichlorosilane, cyclohexyltrichlorosilane, cyclohexyltrichlorosilane, 2-nonmarketability and 2-norbornadienes.

Examples of silicon compounds represented by formula (i) in which n is equal to 2, include dialkoxybenzene, such as dicyclopentadienyliron, tert-butylmethylether, tert-butylmethylether, tert-amiloridesensitive, dicyclohexylammonium, cyclohexanedimethanol, cyclohexyltrichlorosilane and 2-norbornenedicarboxylic.

The silicon compound represented by formula (i) in which n is equal to 2, preferably is dimethoxysilane represented by formula (ii)

< / BR>
in which Raand Rwho pantanillo group, substituted cyclopentadienyl group, cyclopentadienyls group, substituted cyclopentadienyls group, or a hydrocarbon group in which the carbon adjacent to Si is a secondary or tertiary carbon.

Examples of silicon compounds represented by formula (ii) include the following compounds:

dicyclopentadienyliron,

dicyclopentadienyliron,

dicyclopentadienyltitanium,

di-tert-butyldimethylsilyl,

di(2-methylcyclopentene)dimethoxysilane,

di(3-methylcyclopentene)dimethoxysilane,

di(2-ethylcyclopentane)dimethoxysilane,

di(2,3-dimethylcyclobutyl)dimethoxysilane,

di(2,4-dimethylcyclobutyl)dimethoxysilane,

di(2,5-dimethylcyclobutyl)dimethoxysilane,

di(2,3-diethylcarbamyl)dimethoxysilane,

di(2,3,4-trimethylcyclohexyl)dimethoxysilane),

di(2,3,5-trimethylcyclohexyl)dimethoxysilane,

di(2,3,4-triethylsilanol)dimethoxysilane,

di(tetramethylcyclopentadienyl)dimethoxysilane,

di(tetramethylcyclopentadienyl)dimethoxysilane,

di(2-methylcyclopentanol)dimethoxysilane,

di(3-methylcyclopentanol)dimethoxysilane,

di(2-ethylcyclopentane)dimethoxysilane,

di(2-n-butilka ethoxysilane,

di(2,5-dimethylcyclopentene)dimethoxysilane,

di(2,3,4-trimethylcyclopentanone)dimethoxysilane,

di(2,3,5-trimethylcyclopentanone)dimethoxysilane,

di(2,3,4-triethylsilanol)dimethoxysilane,

di(tetramethylcyclopentadienyl)dimethoxysilane,

di(tetramethylcyclopentadienyl)dimethoxysilane,

di(2-methylcyclopentadienyl)dimethoxysilane,

di(3-methylcyclopentadienyl)dimethoxysilane,

di(2-ethylcyclopentadienyl)dimethoxysilane,

di(2-n-butylcyclopentadienyl)dimethoxysilane,

di(2,3-dimethylcyclopentane)dimethoxysilane,

di(2,4-dimethylcyclopentane)dimethoxysilane,

di(2,5-dimethylcyclopentane)dimethoxysilane,

di(2,3-diethyltoluenediamine)dimethoxysilane,

di(2,3,4-trimethylcyclopentanone)dimethoxysilane,

di(2,3,5-trimethylcyclopentanone)dimethoxysilane,

di(2,3,4-triethylchlorosilane)dimethoxysilane,

di(2,3,4,5-tetramethylcyclopentadienyl)dimethoxysilane,

di(2.3,4,5-tetramethylcyclopentadienyl)dimethoxysilane,

di(1,2,3,4,5-pentamethylcyclopentadienyl)dimethoxysilane,

di(1,2,3,4,5-pentamethylcyclopentadienyl)dimethoxysilane,

di-tert-millimeterscale,

di (- dimethylbenzyl)dimethoxysilane,

di(adamant the
diisobutyldimethoxysilane,

di-sec-butyldimethylsilyl,

di-sec-millimeterscale and

isopropyl-second-butyldimethylsilyl.

Examples of silicon compounds represented by formula (i) in which n is equal to 3, include monoatomically, such as tricyclopentadiene, tricyclopentadiene, dicyclopentadienyltitanium, dicyclopentadienyliron, dicyclopentadienyltitanium, Cyclopentasiloxane, cyclopentadienylmagnesium and cyclopentadienylmagnesium.

The second catalyst for polymerization of olefins corresponding to the present invention contains:

(I) prepolymerisation component of catalyst obtained by prepolymerisation of olefin in the presence of the above-mentioned solid titanium catalyst (A) and the above catalyst component (B), representing alyuminiiorganicheskikh connection,

and, if necessary,

(II) component of the catalyst (B), representing alyuminiiorganicheskikh connection, and/or

(III) an electron donor (C).

Prepolymerisation component of the catalyst can be obtained by prepolymerisation of olefin in an amount of from 0.1 to 1000 g, preferably from 0.3 catstye solid titanium catalyst component (A) and catalyst component (B), which alyuminiiorganicheskikh connection.

If prepolymerisation concentration of the catalyst may be higher than during the polymerization, which is described later. If prepolymerisation the concentration of the solid titanium catalyst component is in the range from 0.001 to 200 mmol, preferably from 0.01 to 50 mmol, more preferably from 0.1 to 20 mmol, per the titanium atoms in 1 liter of an inert hydrocarbon solvent, as will be described later.

Component of the catalyst, which alyuminiiorganicheskikh connection is used in such quantity that prepolymer was obtained in an amount of from 0.1 to 1000 g, preferably 0.3 to 500 g, per 1 g of the solid titanium catalyst component. That is component of the catalyst, which alyuminiiorganicheskikh connection, use the number of, usually, from 0.1 to 300 moles, preferably from 0.5 to 100 moles, more preferably from 1 to 50 moles, per 1 mol of titanium atoms contained in the solid titanium catalyst component.

The compound having at least two ether linkages separated by many atoms and an electron donor (h), which will be described in p is their invention. Each of these agents are used in quantities of from 0.1 to 50 moles, preferably from 0.5 to 30 moles, more preferably from 1 to 10 moles, per 1 mol of titanium atoms contained in the solid titanium catalyst component.

Prepolymerisation can be carried out under mild conditions by introducing the olefin and the above-mentioned catalyst components in an inert hydrocarbon solvent.

Specific examples of such inert hydrocarbon solvents are:

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;

halogenated hydrocarbons, such as telengard and chlorobenzene; and

mixtures of these hydrocarbons.

Of these compounds, preferred are aliphatic hydrocarbons.

When an inert hydrocarbon solvent, it is preferable to carry out prepolymerisation in a periodic process. Prepolymerisation can be carried out in a solvent for the olefin or in the system, the et to be the same as or different from the olefin, which is used in the polymerization process, as described later. In particular, it is preferable that the olefin was propylene.

The reaction temperature when prepolymerisation is usually in the range of from -20 to 100oC, preferably from -20 to 80oC, and more preferably in the range from 0 to 40oC.

During prepolymerisation can be used as a molecular weight regulator such as hydrogen. The regulator of the molecular weight are preferably used in an amount such that the characteristic viscosity () of a polymer obtained by prepolymerisation was, at least, of 0.2 DL/g, preferably, would be in the range from 0.5 to 10 DL/g when measured in decaline at 135oC.

As mentioned above, prepolymerisation carry out up until not formed 0.1 to 1000 g, preferably 0.3 to 500 g, more preferably 1-200 g, prepolymer on 1 g of the solid titanium catalyst component (A).

Compounds that can act as electron donor (h) in the process of prepolymerisation are, for example, nitrogen-containing compounds, oxygen-containing compounds and phosphorus-containing compounds.

The Con Is R>
< / BR>
< / BR>
< / BR>
< / BR>
< / BR>
2,5-substituted piperidine represented by the formula:

< / BR>
substituted methylenediamine, such as N,N,N',N'-tetramethylmethylenediamine and N,N,N',N'-tetraethylethylenediamine; and

substituted imidazolidine, such as 1,3-bibenzimidazole and 1,3-dibenzyl-2-phenylimidazoline.

Specific examples of phosphorus-containing compounds include phosphites such as triethylphosphite, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphate, triisobutylene, diethyl-n-butylphosphate and diethylphenylphosphine.

Specific examples of oxygen-containing compounds include:

2,6-substituted tetrahydrofuran represented by formulas

< / BR>
2,5-substituted tetrahydrofuran, represented by the formula

< / BR>
The catalyst for polymerization of olefins corresponding to the present invention, may be used or in the process of liquid-phase polymerization such as suspension polymerization, or gas phase polymerization.

Olefin capable of participating in polymerization include ethylene and olefins containing from 3 to 20 carbon atoms, such as propylene, 1-butene, 1-penten, 1-hexene, 4-methyl-1-penten, 1-octene, 1-mission 1-dodecen, 1-tetradecene, 1-hexadecene, 1-Oilcan-1,2,3,4,4 a, 5,8,8 a-octahydronaphthalene. You can also use styrene, vinylcyclohexane, dieny etc.

When the polymerization is carried out in the liquid phase, can be used the same inert hydrocarbon solvents, which were discussed when discussing prepolymerisation, and depending on the reaction conditions as solvents for the polymerization reaction can be used as liquid olefins.

In the polymerization of olefins using the catalyst for polymerization of olefins corresponding to the present invention, the solid titanium catalyst component (A) (or prepolymerisation component of the catalyst) is usually used in an amount of from 0.001 to 0.5 mmol, preferably 0.005 to 0.1 mmol in terms of titanium atoms, per 1 liter of the polymerization volume. On the other hand, catalyst component (B), which alyuminiiorganicheskikh connection is used usually in an amount of from 1 to 2000 mol, preferably from 5 to 500 mol, in terms of metal atoms, per 1 mol of titanium atoms in the solid titanium catalyst component (A) (or prepolymerized catalyst component in the polymerization system. In addition, during polymerization, if necessary, apply a donor is the metal atom alyuminiiorganicheskikh component of the catalyst.

The molecular weight of the resulting polymer can be adjusted by adding in the polymerization of hydrogen, and thus it is possible to obtain a polymer having a high flow velocity of the melt (P).

In the present invention, the olefins will polimerizuet, usually at a temperature of from 20 to 200oC, preferably from 50 to 150oC, typically at a pressure of from atmospheric to 100 kg/cm2, preferably 2 to 50 kg/cm2.

According to the method of the present invention, the polymerization can be carried out in a periodic, properities or continuous process. In addition, the polymerization can be carried out in two or more stages, in which the reaction conditions are different from each other.

Homopolymerization or copolymerization of olefins using the above catalyst for polymerization of olefins gives polymers with a characteristic viscosity () from 0.01 to 100 DL/g, preferably from 0.1 to 50 DL/g

Thus obtained polymer optionally may be mixed with various additives, such as stabilizers, substances that increase the resistance to atmospheric agents, antistatics, antiadhesive, sizing, paradisiacal olefins, corresponding to the present invention may also contain other suitable for the polymerization of olefins ingredients, other than those mentioned above.

Advantages of the claimed invention

The catalyst for polymerization of olefins corresponding to the present invention has an excellent polymerization activity.

When using the catalyst for polymerization of olefins corresponding to the present invention, can be obtained from /from/polymers of olefins with homogeneous particle size value less dust, high bulk density and high stereoregularity.

Examples

The present invention will now be described in more detail using the following examples, but it should be understood that the invention is in no way limited to these examples.

Example 1

Preparation of solid titanium catalyst component (A)

Mix is 95.2 g of anhydrous magnesium chloride, 422 ml of decane and 390,6 g 2-ethylhexanol alcohol, is heated at 130oC for 2 hours to obtain a homogeneous solution (a solution of compounds of magnesium). Then to the resulting homogeneous solution was added 31.1 g of 2-isopentyl-2-isopropyl-anutie components.

The resulting homogeneous solution (polyester solution of magnesium compounds) is cooled to room temperature and then 75 g of a homogeneous solution is added dropwise to 200 ml of titanium tetrachloride kept at -20oC for one hour.

Upon completion of the addition the temperature of the resulting liquid mixture (magnesium-titanium solution) was raised to 110oC for 4 hours.

When the temperature of the liquid mixture reaches 110oC, it added of 4.04 g of 2-isopentyl-2-isopropyl-1,3-dimethoxypropane, then the resulting mixture was stirred at the same temperature for 2 hours to carry out the component contact.

After the reaction mixture was hot filtered to extract the hard part. The hard part is suspended in 275 ml of titanium tetrachloride and heated at 110oC for 2 hours to make further contact (reaction). After completion of this process the hard part is again extracted by hot filtration. Learnt the hard part is thoroughly washed with decane and hexane at 110oC, until, while in the washing solution will be determined by the loose coupling of titanium.

Thus get t and dry, to verify the composition of the catalyst. The scan found that the solid titanium catalyst component (A) contains 2.2 wt.% titanium, 15 wt.%tons of magnesium, 60 wt.% chlorine, 17.3 wt.% 2-isopentyl-2-isopropyl-1,3-dimethoxypropane, 5.4 weight. % decane and 0.2 wt.% 2-ethyl-hexanol (2-ethylhexyloxy).

Polymerization

In an autoclave with an inner volume of 2 liters load 750 ml of purified n-hexane, and then at 60oC in an atmosphere of propylene load 0.75 mmol of triethylaluminum, of 0.075 mmol of cyclohexyltrichlorosilane and 0,0075 mmol in terms of titanium atoms, of the solid titanium catalyst component (A).

Then injected into the autoclave of 200 ml of hydrogen, and the temperature in the autoclave was raised to 70oC, at which carry out the polymerization of propylene in 2 hours. The pressure in the polymerization process support at the level of 7 kg/cm2-G.

Upon completion of the polymerization, the slurry containing the formed solid substance was filtered to separate a white solid from the liquid-phase part. The solid is dried, yielding a white solid powder polymer. The output is 318,6 g of dry. Extraction of the polymer with boiling heptane balance is 98,91%, CTP attribuut and obtain 3.6 g soluble in the solvent of the polymer. Therefore, the catalytic activity is 42500 g PP (in mmol Ti and 1.1.(t-1.1) total product is to 98.4%.

Example 2

Getting prepolymerized catalyst component (B)

400 ml chetyrehraundovy glass reactor equipped with a stirrer, was loaded with 100 ml of purified n-hexane, 3 mmol of triethylaluminum and 1.0 mmol in terms of titanium atoms, of the solid titanium catalyst component (A) obtained in example 1 in a nitrogen atmosphere. In the reactor serves propylene with a velocity of 3.2 l/h for one hour and carry out the polymerization at 20oC.

Upon completion of the propylene feed to the reactor is rinsed with nitrogen and washed twice, removing the supernatant and introducing the purified n-hexane. After that, the product is suspended in purified n-hexane and transferred into the flask for catalyst where it is and keep as prepolymerized catalyst component (B).

Polymerization

In an autoclave with an inner volume of 2 liters load 750 ml of purified n-hexane, and then at 60oC in an atmosphere of propylene load 0.75 mmol of triethylaluminum, 0.75 mmol of cyclohexyltrichlorosilane and 0,0075 mmol in terms of titanium atoms prepolymerized catalyst component is C, at this temperature, carry out polymerization for 2 hours. The pressure in the polymerization process support at the level of 7 kg/cm2- G.

Upon completion of the polymerization, the slurry containing the resulting solid product was filtered to separate a white solid from the liquid-phase part. The solid is dried, yielding a white powdery solid polymer. The output is 398 g of dry. Extraction of the polymer with boiling heptane residue is 99.0%, P is 4.0 DG/min and the apparent bulk density is 0.42 g/ml

On the other hand, the liquid-phase portion of the concentrate and get 1.2 g soluble in the solvent of the polymer. Therefore, the catalyst activity is 53100 g PP (in mmol Ti, and 1.1.(t.1.1) the whole product is 98,7%.

Example 3

Preparation of solid titanium catalyst component (C)

Repeat the procedure to obtain a solid titanium catalyst component (A) of example 1 except that add 0,81 g 2-isopentyl-2-isopropyl-1,3-dimethoxypropane to the magnesium-titanium solution at 110oC to obtain a solid titanium catalyst component (C). The results of the analysis of the composition of the solid titanium component catera 1 except using the solid titanium catalyst component (C). The results are presented in table 1.

Example 4

Prepolymerisation solid titanium catalyst component (C)

Repeat the procedure prepolymerisation of example 2, except that use solid titanium catalyst component (C) to obtain prepolymerized catalyst (D).

Polymerization

Repeat the procedure of polymerization example 2, except that use prepolymerized catalyst (D). The results are presented in table 1.

Example 5

Preparation of solid titanium catalyst component (E)

Repeat the procedure to obtain a solid titanium catalyst component (A) of example 1 except that the temperature rise from -20 to 110oC hold for 2 hours, and the magnesium-titanium solution at 110oC add 0,81 g 2-isopentyl-2-isopropyl-1,3-dimethoxypropane to obtain a solid titanium catalyst component (E). The results of the analysis of the composition of the solid titanium catalyst component (E) are presented in table 2.

Polymerization

Repeat the procedure of polymerization example 1 except tor the>Example 6

Preparation of solid titanium catalyst component (F)

Repeat the procedure to obtain a solid titanium catalyst component (A) of example 1 except that the solution of magnesium chloride added 24,9 g 2-isopentyl-2-isopropyl-1,3-dimethoxypropane and magnesium-titanium solution at 110oC type of 1.62 g of 2-isopentyl-2-isopropyl-1,3-dimethoxypropane to obtain a solid titanium catalyst component (F). The results of the analysis of the composition of the solid titanium catalyst component (F) are presented in table 2.

Polymerization

Repeat the procedure of polymerization example 1 except that use solid titanium catalyst component (F). The results are presented in table 1.

Example 7

Preparation of solid titanium catalyst component (G)

Repeat the procedure to obtain a solid titanium catalyst component (A) of example 1 except that the solution of magnesium chloride type of 24.0 g of 2-isopentyl-2-isopropyl-1,3-dimethoxypropane and magnesium-titanium solution at 110oC type of 1.62 g of 2-isopentyl-2-isopropyl-1,3-dimethoxypropane to obtain a solid titanium catalyst component (G). Results azazia

Repeat the procedure of polymerization example 1 except that use solid titanium catalyst component (G). The results are presented in table 1.

Comparative example 1

[Preparation of solid titanium catalyst component (H)]

Repeat the procedure to obtain a solid titanium catalyst component (A) of example 1 except that the solution of magnesium chloride instead of 2-isopentyl-2-isopropyl-1,3-dimethoxypropane type of 21.3 g of phthalic anhydride and magnesium-titanium solution at 110oC instead of 2-isopentyl-2-isopropyl-1,3-dimethoxypropane add 5,22 g diisobutylphthalate to obtain a solid titanium catalyst component (H).

Polymerization

Repeat the procedure of polymerization example 1 except that use solid titanium catalyst component (H). The results are presented in table 1.

Example 8

Preparation of solid titanium catalyst component (1)

Mix is 95.2 g of anhydrous magnesium chloride, 305 ml of decane and 1600 ml of tetrahydrofuran and heated at boiling temperature under reflux until a homogeneous solution (a solution of compounds of magnesium). Then to the resulting g is boiling under reflux for one hour, to get in touch all of the above components.

The resulting homogeneous solution (polyester solution compounds of magnesium) is cooled to room temperature and then 75 ml of the homogeneous solution is added dropwise to 200 ml of titanium tetrachloride kept at -20oC for one hour.

After the addition the temperature of the resulting liquid mixture (magnesium-titanium solution) was raised to 60oC for 3 hours.

When the temperature of the liquid mixture reaches 60oC, there was added 2,02 g 2-isopentyl-2-isopropyl-1,3-dimethoxypropane, then the resulting mixture was stirred at the same temperature for 2 hours to carry out contact of the reactants.

After that, the hard part is then removed from the hot reaction mixture by filtration. The hard part is suspended in 275 ml of titanium tetrachloride and heated at 110oC for 2 hours to make further contact (reaction). Upon completion of this process the hard part is again extracted by hot filtration.

Learnt the hard part is again suspended in 275 ml of titanium tetrachloride and heated to 110oC for 2 hours. After end roshenko washed with decane and hexane at 110oC as long, while in the washing solution no longer be determined by a loose coupling of titanium.

Thus obtained solid titanium catalyst component (1).

The results of the analysis of the composition of the solid titanium component (1) are presented in table 4.

Polymerization

Repeat the procedure of polymerization example 1 except that use solid titanium catalyst component (1). The results are presented in table 3.

Example 9

[Preparation of solid titanium catalyst component (J)]

Mix 62,0 g of anhydrous magnesium chloride, 469 ml of decane and 469 ml tetraethoxysilane and heated at 130oC for 2 hours to obtain a homogeneous solution (a solution of compounds of magnesium). Then to the resulting homogeneous solution was added 20.2 g of 2-isopentyl-2-isopropyl-1,3-dimethoxypropane, and the resulting homogeneous solution is stirred at 130oC for one hour to bring into contact the above mentioned components.

The resulting homogeneous solution (polyester solution compounds of magnesium) is cooled to room temperature and then 115 ml of the homogeneous solution is added dropwise to 200 ml tetrachloride resulting liquid mixture (magnesium-titanium solution) is increased to 110oC for 4 hours.

When the temperature of the liquid reaction mixture reaches 110oC, it added of 4.04 g of 2-isopentyl-2-isopropyl-1,3-dimethoxypropane, then the resulting mixture was stirred at the same temperature for 2 hours to make contact.

After completion of this process the hard part is then removed from the hot reaction mixture by filtration. The hard part is suspended in 275 ml of titanium tetrachloride and heated at 110oC for 2 hours to make further contact (reaction). At the end of this contact, the hard part is again extracted by hot filtration. Learnt the hard part is thoroughly washed with decane and hexane at 110oC as long, while in the washing solution is no longer free to decide titanium compound.

Thus obtained solid titanium catalyst component (J).

The results of determining the composition of the solid titanium catalyst component (J) is presented in table 4.

[Polymerization]

Repeat the procedure of polymerization example 1 except that use solid titanium catalyst component (J). The results are presented in table 3.o
C for 2 hours to obtain a homogeneous solution (a solution of compounds of magnesium). Then to the resulting homogeneous solution was added 20.2 g of 2-isopentyl-2-isopropyl-1,3-dimethoxypropane and stirred at 130oC for one hour to bring into contact the above mentioned components.

The resulting homogeneous solution (polyester solution compounds of magnesium) is cooled to room temperature, and then 115 ml of the homogeneous solution are added dropwise to 200 ml of titanium tetrachloride kept at -20oC for one hour.

Upon completion of the addition the temperature of the obtained liquid mixture (magnesium-titanium solution) was raised to 110oC for 4 hours.

When the temperature of the liquid mixture reaches 110oC, it added of 4.04 g of 2-isopentyl-2-isopropyl-1,3-dimethoxypropane, then the resulting mixture is stirred at this temperature for 2 hours to carry out contact of all components.

After contact, the hard part is then removed from the hot reaction mixture by filtration. The hard part is suspended in 275 ml of te. the donkey that the hard part is again extracted by hot filtration. Learnt the hard part is thoroughly washed with decane and hexane at 110oC as long, while in the washing solution is no longer free to decide the connection titanium.

Thus obtained solid titanium catalyst component (K).

Results on the composition of the solid titanium catalyst component (K) is presented in table 4.

[Polymerization]

Repeat the procedure of polymerization example 1 except that use solid titanium catalyst component (K). The results are presented in table 3.

Comparative example 2

[Preparation of solid titanium catalyst component (L)]

Repeat the procedure to obtain a solid titanium catalyst component of example 8 except that instead of 2-isopentyl-2-isopropyl-1,3-dimethoxypropane to the solution of magnesium chloride type of 21.3 g of phthalic anhydride and instead of 2-isopentyl-2-isopropyl-1,3-dimethoxypropane to the magnesium-titanium solution at 110oC add 2,61 diisobutylphthalate and get a solid titanium catalyst component (L).

The results of the analysis of the composition of terdag the procedure of polymerization example 1 except using the solid titanium catalyst component (L). The results are presented in table 3.

Comparative example 3

[Preparation of solid titanium catalyst component (M)]

Repeat the procedure for obtaining the solid titanium component of the catalyst of example 9 except that the solution of magnesium chloride instead of 2-isopentyl-2-isopropyl-1,3-dimethoxypropane add to 11.8 g of phthalic anhydride, magnesium-titanium solution at 110oC add instead of 2-isopentyl-2-isopropyl-1,3-dimethoxypropane 3,39 g diisobutylphthalate and get a solid titanium catalyst component (M).

The results of the analysis of the composition of the solid titanium catalyst component (M) are presented in table 4.

[Polymerization]

Repeat the procedure of polymerization example 1 except that use solid titanium catalyst component (M). The results are presented in table 3.

Comparative example 4

[Preparation of solid titanium catalyst component (N)]

Repeat the procedure for obtaining the solid titanium component of the catalyst of example 10 except that the solution of magnesium chloride 2-isopentyl-2-isopropyl-1,3-dimethoxy propyl-1,3-dimethoxypropane add 3,39 g diisobutylphthalate and get a solid titanium catalyst component (N).

The results of the analysis of the composition of the solid titanium catalyst component (N) is presented in table 4.

[Polymerization]

Repeat the procedure of polymerization example 1 except that use solid titanium component. catalyst (N). The results are presented in table 3.2

1. The solid titanium catalyst component for the polymerization of olefins, comprising titanium, magnesium and halogen, and representing the product of the interaction gallogermanate compounds, electron-donating compounds and liquid compounds of titanium, characterized in that it is obtained by the method containing the following steps: (i) enter into contact gallogermanate connection with electron-donor compound which is selected from the group consisting of alcohol, simple ester and ether complex, and each of them is present in amount from 1 to 40 moles per mole gallogermanate connection in the hydrocarbon solvent in an amount of from 1 to 30 moles per mole gallogermanate connection with obtaining a solution of a magnesium compound; (ii) enter into contact with a solution of magnesium compounds with electron-donating compound having at least two ether linkages, due to the many Atmos carbon silicon or phosphorus, in the amount of from 0.01 to 1.0 mole per mole gallogermanate connection; (iii) enter into contact with the resulting solution with a liquid titanium compound in an amount of from 2 to 100 gram atoms per gram-atom of magnesium in the solution of the polyester, and the specified electron-donating compound to obtain a solution of the magnesium compound is different from the specified connection stage ii), to obtain the solid product, the next, a specific atomic absorption spectroscopy or gas chromatography, wt.%: a) magnesium 5 - 35, b) titanium 0.3 to 10, (C) halogen 30 - 75, d) compound having at least two ether linkages provided by a particular set of atoms, and the specified set of atoms includes at least one selected from the group consisting of carbon, silicon and phosphorus, 0.5 to 30 wt.%; (e) a hydrocarbon of 0.5 - 20 wt. % f) an electron donor other than the compound (d), 0.05 to 7 wt.%.

2. Component of the catalyst under item 1, characterized in that the stage iii gives a solution of titanium compound, followed by contacting the specified solution with electron-donor compound different from stage ii), in the amount of from 0.01 to 1.0 mole per mole gallogermanate connection with obtaining enie (f), other than the compound (d) selected from the group consisting of alcohol esters, including esters of metal-containing acids, and ethers, other than compounds having at least two ether linkages provided by a particular set of atoms.

4. The way to obtain a solid titanium catalyst component for polymerization of olefins, as defined under item 1, characterized in that it contains the following stages: (i) enter into contact gallogermanate connection with electron-donor compound which is selected from the group consisting of alcohol, simple ester and ether complex, and each of them is present in amount from 1 to 40 moles per mole gallogermanate compounds in a hydrocarbon solvent in an amount of from 1 to 30 moles per mole gallogermanate connection with obtaining a solution of a magnesium compound; (ii) enter into contact with a solution of magnesium compound with an electron-donor compound, having at least two ether linkages provided by a particular set of atoms, and the specified set of atoms includes at least one selected from the group consisting of carbon atoms, silicon or phosphorus, in the amount of from 0.01 to 1.0 mole per mole of halog the m-atoms per gram-atom of magnesium in the solution of the polyester, moreover, the specified electron-donating compound to obtain a solution of the magnesium compound is different from the specified connection with the stage ii.

5. The method according to p. 4, wherein the alcohol is 2-ethylhexanol.

6. The way to obtain a solid titanium catalyst component for polymerization of olefins, as defined under item 1, characterized in that it contains the following stages: (i) enter into contact gallogermanate connection with electron-donor compound which is selected from the group consisting of alcohol, simple ester and ether complex, and each of them is present in amount from 1 to 40 moles per mole gallogermanate compounds in a hydrocarbon solvent in an amount of from 1 to 30 moles per mole gallogermanate connection with obtaining magnesium compound; (ii) enter into contact with a solution of magnesium compounds with electron-donating compound having, at least two ether linkages provided by a particular set of atoms, and the specified set of atoms includes at least one selected from the group consisting of carbon atoms, silicon or phosphorus, in the amount of from 0.01 to 1.0 mole per mole gallogermanate connection; (iii) enter into contact received is of ifira, obtaining a solution of titanium-magnesium compounds; enter into contact with a solution of titanium-magnesium compounds with electron-donor compound in an amount of from 0.01 to 1.0 mole of mole gallogermanate compounds with electron-donating compound to obtain a solution of the magnesium compound is different from the specified connection with the stage ii.

7. The method according to p. 6, wherein the alcohol is 2-ethylhexanol.

8. The catalyst for polymerization of olefins, comprising: I) a solid titanium catalyst component having a composition defined by PP.1 to 3; (II) alyuminiiorganicheskikh compound component of the catalyst.

9. The catalyst p. 8, characterized in that it contains also electrondonor connection.

10. The catalyst for polymerization of olefins, comprising: (I) terpolymerization component of catalyst obtained by terpolymerization of olefin in the presence of the solid titanium catalyst component, defined by PP. 1 to 3; (II) alyuminiiorganicheskikh compound component of the catalyst and/or (III) an electron donor.

11. The method of polymerization of-olefins, wherein the process is conducted in the presence of a catalyst for polymerization of olefins.08.92 - on PP.4 - 7.

 

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