JPS63223008A - Polymerization of olefin - Google Patents

Abstract

PURPOSE:To produce a highly stereoregular polymer in high yield, by (co)- polymerizing an olefin in the presence of a catalyst formed from a specific solid Ti catalyst, organoaluminum compound catalyst and organosilicon com pound catalyst components. CONSTITUTION:An olefin is (co)polymerized in the presence of a catalyst formed from (A) a solid Ti catalyst component, formed by bringing an Mg compound (e.g. dimethylmagnesium or magnesium chloride) into contact with a Ti compound [e.g. TiCl4 or Ti(OCH3)2Cl2] and a polyfunctional carboxylic acid ester (e.g. succinic acid diester or diethyl adipate) and containing Mg, Ti, a halogen and the polyfunctional carboxylic acid ester is essential components, (B) an organoaluminum compound catalyst component (e.g. triethylaluminum) and (C) an organosilicon compound catalyst component expressed by the formula (R<1> and R<2> are >=3C straight-chain hydrocarbon; R<3> is hydrocarbon) (e.g. di-n- propyldimethoxysilane).

Description

Detailed Description of the Invention [Industrial Application Field] The present invention is directed to the production of olefin polymers (hereinafter, olefin copolymers) by olefin polymerization (hereinafter, the use may also include olefin copolymers). (which may be used including coalescence). In particular, the present invention relates to a method for producing an olefin polymer that can yield a highly stereoregular polymer in high yield when applied to the polymerization of an α-olefin having 3 or more carbon atoms. Furthermore, in the polymerization of α-olefins having 3 or more carbon atoms, even if the melt flow rate of the polymer is changed using a molecular weight regulator such as hydrogen during polymerization, the stereoregularity of the polymer is not significantly reduced. Regarding possible methods. The present invention also relates to a method for polymerizing olefins which has the advantage that there is very little decrease in activity with the passage of polymerization time.

(Prior art) There have already been many proposals regarding methods for producing solid catalyst components containing magnesium, titanium, halogen, and electron donors as essential components.
- It is also known that when utilized in the polymerization of olefins, it is possible to obtain highly stereoregular polymers with high catalytic activity.

However, many of them require further improvement in terms of activity, stereoregularity, etc. of the polymer.

For example, in order to obtain high-quality olefin polymers without post-polymerization treatment, the production ratio of stereoregular polymers must be extremely high, and the polymer yield of transition metal polymers must be sufficiently high. must not.

Some of the conventionally proposed technologies can be said to be at an acceptable level in terms of the above points, depending on the type of target polymer, but there are some issues regarding the residual halogen content in the polymer, which is related to rusting in molding machines. From this point of view, there are only a few that can be said to have sufficient performance, and most of them cause considerable decreases in yield and stereoregularity index when producing polymers with a high melt flow rate. It has the following drawbacks.

The applicant has proposed a number of methods aimed at improving the shortcomings of the prior art in the stereoregular polymerization of α-olefins. For example, JP-A-58-83006
No. 58-138705, Japanese Patent Application Laid-open No. 1982-138705
-138706, JP 58-138707, JP 58-138708, JP 58-1
Publication No. 38709, Japanese Patent Application Publication No. 138710/1983,
JP-A-58-138715, etc. discloses (A) a highly active titanium catalyst component containing magnesium, titanium, halogen, and an electron donor as essential components, [B] an organometallic compound catalyst component, and (C) an organosilicon compound. A method has already been proposed in which olefins are polymerized or copolymerized in the presence of a catalyst formed from catalyst components.

All of these methods are polymerization methods in which the catalyst has extremely high polymerization activity and excellent stereoregularity, and have solved the above-mentioned drawbacks of the prior art.

[Problem that the invention seeks to solve]

The present invention aims to provide a method for polymerizing olefins that has excellent polymerization activity and excellent stereoregularity, and as a result of studying an olefin polymerization catalyst that has excellent polymerization activity and excellent stereoregularity, (A) Magnesium,
By using a catalyst formed from a solid titanium catalyst component containing titanium, a halogen, and a polyhydric carboxylic acid ester as essential components, (B) an organoaluminum compound catalyst component, and (C) a specific organosilicon compound catalyst component, the above-mentioned The inventors have discovered that the object can be achieved and have arrived at the present invention.

An object of the present invention is to provide an olefin polymerization catalyst that uses an organosilicon compound catalyst component as a promoter component and has excellent polymerization activity and stereoregularity.

Another object of the present invention is to form a polymer with excellent particle size, particle size distribution, particle shape, bulk specific gravity, etc., and to form such a polymer with high catalytic performance and also over the course of polymerization time. The object of the present invention is to provide a method for polymerizing olefins in which the accompanying decrease in activity is extremely small.

Another object of the present invention is to form a polymer with excellent particle size, particle size distribution, particle shape, bulk specific gravity, etc., and furthermore, such excellent polymer has high catalytic performance and also has a good polymerization time. It is an object of the present invention to provide a method for polymerizing olefins in which there is extremely little decrease in activity due to olefin polymerization.

Another object of the present invention is to provide a polymer with low stereoregularity (a small amount of hydrogen) when attempting to obtain a polymer with a high melt flow rate by coexisting a molecular weight regulator, such as hydrogen, in the polymerization system. In addition to the advantage that the melt flow rate can be adjusted by using a molecular weight regulator such as hydrogen, it is an object of the present invention to provide an olefin polymerization method in which catalyst activity is rather improved by the use of a molecular weight regulator such as hydrogen. The aim is to provide an improved method for polymerizing olefins.

All of these objects of the present invention can be achieved by employing the configuration described below, and the present invention has been completed.

The above objects and many other objects and advantages of the present invention will become more apparent from the following description.

[Means for Solving the Problems] and [Operation] According to the present invention, (A.) Magnesium, titanium, halogen, and A solid titanium catalyst component containing a monovalent carboxylic acid ester as an essential component, [B] an organoaluminum compound catalyst component, and (C
) General formula (1) SiR'R"(OR')z (
T) In the presence of a catalyst formed from an organosilicon compound catalyst component represented by [wherein R1 and R2 represent a linear hydrocarbon group having 3 or more carbon atoms, and R3 represents a hydrocarbon group] Furthermore, there is provided a method for polymerizing olefins, which comprises polymerizing or copolymerizing olefins.

The titanium catalyst component (A) used in the present invention is magnesium,
A highly active catalyst component containing titanium, halogen, and polyvalent carboxylic acid ester as essential components.

This titanium catalyst component (A) contains magnesium halide with a smaller microcrystal size than commercially available magnesium halides, and usually has a specific surface area of about 50 po/g or more, preferably about 60 to about 1000 rr? /g.

More preferably, it is about 100 to about 800 rrf/g, and its composition is not substantially changed by washing with hexane at room temperature. Furthermore, when a diluent such as an inorganic or organic compound such as a silicon compound, an aluminum compound, or a polyolefin is used, high performance is exhibited even if the specific surface area is smaller than the above-mentioned specific surface area. The titanium catalyst component (A)
, the halogen/titanium (atomic ratio) is about 4 to about 200, particularly about 5 to about 100, and the electron donor/titanium (molar ratio) is about 0.1 to about 10, especially about 0.2 to about 100. 6. Magnesium/titanium (atomic ratio) is preferably about 1 to about 100, particularly about 2 to about 50. Component (A) may also contain other electron donors, metals, elements, functional groups, etc.

Such a titanium catalyst component (A) can be obtained, for example, by mutual contact of a magnesium compound (or magnesium metal), an electron donor and a titanium compound, or optionally with other reactants, such as silicon, phosphorus, aluminium, etc. Compounds of can be used.

As a method for producing such titanium catalyst component (A),
For example, JP 50-108385, JP 50-126
No. 590, No. 51-20297, No. 51-28189
No. 51-64586, No. 51-92885, No. 51-136625, No. 52-87489, No. 52
-100596, 52-100596, 52-
No. 147688, No. 52-104593, No. 53-2
No. 580, No. 53-40093, No. 53-40094
No. 55-135102, No. 56-135103, No. 56-811, No. 56-11908, No. 56-
No. 18606, No. 5B-83006, No. 5B-138
No. 705, No. 5B-138706, No. 58-1387
No. 07, No. 5B-138708, No. 58-13870
No. 9, No. 58-138710, No. 58-138715
No. 60-23404, No. 61-21109, No. 61-37802, No. 61-37803, No. 55-
It can be manufactured according to the methods disclosed in various publications such as No. 152710. Several examples of methods for producing these titanium catalyst components (A) will be briefly described below.

(11. Grinding or not grinding a magnesium compound or a complex compound of a magnesium compound and an electron donor in the presence or absence of an electron donor, a grinding aid, etc.)
The solid obtained with or without pretreatment with an electron donor and/or a reaction aid such as an organoaluminum compound or a halogen-containing silicon compound is reacted with a titanium compound which forms a liquid phase under the reaction conditions. However, the above electron donor is used at least once.

(2) A liquid magnesium compound having no reducing ability and a liquid titanium compound are reacted in the presence of an electron donor to precipitate a solid titanium complex.

(3) React the material obtained in (2) with a titanium compound.

(4) React the material obtained in (11 or (2)) with an electron donor and a titanium compound.

(5) A complex compound of a magnesium compound or a magnesium compound and an electron donor is ground in the presence or absence of an electron donor, a grinding aid, etc., and in the presence of a titanium compound, and then the complex compound of the electron donor and/or The solid obtained with or without pretreatment with a reaction aid such as an organoaluminum compound or a halogen-containing silicon compound is treated with a halogen or a halogen compound or an aromatic hydrocarbon. However, the above electron donor is used at least once.

(6) Treating the compound obtained in (1) to (4) above with a halogen, a halogen compound, or an aromatic hydrocarbon.

(7) Contacting the reaction product of metal oxide, dihydrocarbylmagnesium, and halogen-containing alcohol with polyhydric carboxylic acid ester and titanium compound.

(8) A magnesium compound such as a magnesium salt of an organic acid, anexoxymagnesium, or aryloxymagnesium is reacted with a polyhydric carboxylic acid ester, a titanium compound, and/or a halogen-containing hydrocarbon.

Among these preparation methods, catalysts using liquid titanium halide or catalysts using halogenated hydrocarbons after or during use of a titanium compound are preferred.

Electron donors that can be a component of the highly active titanium catalyst component (A) of the present invention are esters of polyhydric carboxylic acids. Suitable polyhydric carboxylic acid esters include (where R1 is a substituted or unsubstituted hydrocarbon group, R2, R
5, R6 is hydrogen or a substituted or unsubstituted hydrocarbon group, R3
, R4 is hydrogen or a substituted or unsubstituted hydrocarbon group, and preferably at least one of them is a substituted or unsubstituted hydrocarbon group. Further, R'' and R4 may be connected to each other.The hydrocarbon group substituted here includes N, 0
, containing different atoms such as S, such as C-0-C, C0
OR, C0OH, 0)1.5O3H.

It has groups such as -C-N-C- and NH.

) can be exemplified.

Particularly preferred among these are diesters of dicarboxylic acids in which at least one of R1 and R2 is an alkyl group having 2 or more carbon atoms.

Specific examples of preferable polyvalent carboxylic acid esters include diethyl succinate, dibutyl succinate, diethyl methylsuccinate, diisobutyl α-methylglutarate, dibutylmethyl malonate, diethyl malonate, diethyl ethylmalonate, diethyl isopropylmalonate. , butyl diethyl malonate, phenyl diethyl malonate, diethyl malonate, allyl diethyl malonate, diisobutyl diethyl malonate, di-n-butyl diethyl malonate, dimethyl maleate, monooctyl maleate, diisooctyl maleate, diisobutyl maleate, butyl Diisobutyl maleate, diethyl butyl maleate - diisopropyl β-methylglutarate, diallyl ethylsuccinate, di-2-ethylhexyl fumarate, diethyl itaconate, diisobutyl itaconate,
Aliphatic polycarboxylic acid esters such as diisooctyl citraconate and dimethyl citraconate, aliphatic polycarboxylic acid esters such as diethyl 1,2-cyclohexanecarboxylate, diisobutyl 1,2-cyclohexanecarboxylate, diethyl tetrahydrophthalate, and diethyl nadic acid. acid ester, monoethyl phthalate, dimethyl phthalate,
Methyl ethyl phthalate, monoisobutyl phthalate, diethyl phthalate, ethyl isobutyl phthalate, mono-normal butyl phthalate, ethyl normal-butyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, phthalate diisobutyl acid, di-n-hebutyl phthalate, di-2-ethylhexyl phthalate, didecyl phthalate, benzylbutyl phthalate, diphenyl phthalate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate, dibutyl trimellitate Examples thereof include aromatic polycarboxylic acid esters such as Aromatic polycarboxylic acid esters, and heterocyclic polycarboxylic acid esters such as 3,4-furandicarboxylic acid.

Other examples of polycarboxylic acid esters that can be maintained in the titanium catalyst component include diethyl adipate,
Diisobutyl adipate, diisopropyl sebacate,
Mention may be made of esters of long-chain dicarboxylic acids such as di-n-butyl sebacate, n-octyl sebacate, and di-2-ethylhexyl sebacate.

Among these polyhydric carboxylic acid esters, preferred are:
It has the skeleton of the above-mentioned general formula, and is more preferably an ester of phthalic acid, maleic acid, substituted malonic acid, etc., and an alcohol having 2 or more carbon atoms, and particularly preferably an ester of phthalic acid and an alcohol having 2 or more carbon atoms. It is a diester of

When supporting these electron donors, it is not necessarily necessary to use them as starting materials, but by using compounds that can be converted into these in the process of preparing the titanium catalyst component and converting them into these compounds at the stage of preparation. Good too.

Although other electron donors may coexist in the titanium catalyst component, their coexistence in too large a quantity will have an adverse effect, so they should be kept to a small amount.

In the present invention, the magnesium compound used to prepare the solid titanium catalyst component (A) is a magnesium compound that may or may not have reducing ability. Examples of the former include magnesium compounds that have magnesium-carbon bonds and magnesium-hydrogen bonds, such as dimethylmagnesium,
Diethylmagnesium, dipropylmagnesium, dibutylmagnesium, cyamylmagnesium, didecylmagnesium, didecylmagnesium, ethylmagnesium chloride, propylmagnesium chloride, butylmagnesium chloride, hexylmagnesium chloride, amylmagnesium chloride, butylethoxymagnesium, ethylbutylmagnesium, Examples include butylmagnesium hydride. These magnesium compounds can be used, for example, in the form of a complex compound with organoaluminum or the like, and may be in a liquid state or a solid state. On the other hand, magnesium compounds without reducing ability include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride, methoxymagnesium chloride, ethoxymagnesium chloride, isobuboxymagnesium chloride, butoxymagnesium chloride, and octoxymagnesium chloride. Alkoxymagnesium halides such as magnesium chloride, phenoxymagnesium chloride, alkoxymagnesium halides such as methylphenoxymagnesium chloride, alkoxymagnesium such as ethoxymagnesium, isoprooxymagnesium, butoxymagnesium, n-octoxymagnesium, 2-ethylhexoxymagnesium Examples include magnesium, phenoxymagnesium, allyloxymagnesium such as dimethylphenoxymagnesium, and magnesium carboxylates such as magnesium laurate and magnesium stearate. In addition, these magnesium compounds without reducing ability may be derived from the above-mentioned magnesium compounds having reducing ability or may be derived during the preparation of the catalyst component. For example, a magnesium compound having reducing ability may be used as a polysiloxane compound. ,
Examples include a method of converting it into a magnesium compound without reducing ability by contacting it with a compound such as a halogen-containing silane compound, a halogen-containing aluminum compound, an ester, or an alcohol. Further, the magnesium compound may be a complex compound with another metal, a composite compound, or a mixture with another metal compound, or may be a mixture of two or more of these compounds. Among these, preferred magnesium compounds are those without reducing ability, and particularly preferred are halogen-containing magnesium compounds, especially magnesium chloride, alkoxymagnesium chloride, and allyloxymagnesium chloride.

In the present invention, there are various titanium compounds used for preparing the solid titanium catalyst component (A), but usually Ti(
A tetravalent titanium compound represented by OR)gX*-g (R is a hydrocarbon group, X is a halogen, 0≦g≦4) is suitable. More specifically, TtC14, TiBr4, T
Tetrahalogenated titanium such as i1n, Ti(QC)I
s) CI-+, Ti(OCzH+)C1s, Ti(
On-C4HJC1z, Ti (OCJ3) Brl, Ti
(OisoC*H*) Trihalogenated alkoxytitanium with Brs, Ti(OCHz)zChlTi (
OCJs) zclz, Ti(On-CdlJ gcl
z, Ti(OCJs)Brt.

dihalogenated alkoxytitanium, such as Ti(QC)i
3) scl s Ti (OCJs) + CI, Ti (O
Monohalogenated trialkoxytitanium such as n-CJq)3C11Ti(OCJs) Jr, Ti(OCL)t
, Ti(OCzHs)4, Ti(On-CJJ4
Examples include tetraalkoxytitanium such as. Among these, preferred are halogen-containing titanium compounds, particularly titanium tetrahalide, and particularly preferred is titanium tetrachloride. These titanium compounds may be used alone or in the form of a mixture.

Alternatively, it may be used after being diluted with a hydrocarbon or halogenated hydrocarbon.

In the preparation of the titanium catalyst component (A), a titanium compound, a magnesium compound, and an electron donor to be supported, as well as an electron donor that may be used as necessary, such as an alcohol, a phenol, a monocarboxylic acid ester, a silicon compound, The amount of the aluminum compound etc. to be used varies depending on the preparation method and cannot be absolutely specified, but for example, the ratio is about 0.01 to 5 mol of the electron donor to be supported and 0.01 to 500 mol of the titanium compound per 1 mol of the magnesium compound. be able to.

In the present invention, the following titanium catalyst components [A],
Olefin polymerization or copolymerization is carried out using a combined catalyst of an organoaluminum compound catalyst component (B) and an organosilicon compound catalyst component (C).

The above component [B] includes: (i) an organoaluminum compound having at least one Al-carbon bond in the molecule, for example, a compound of the general formula % (where R1 and Rz usually have 1 to 1 carbon atom); 15, preferably 1 to 4 hydrocarbon groups, which may be the same or different from each other.X is halogen, -1 is O
<va≦3, O≦,≦31. is 0≦2≦3.9 is 0≦9
≦3, and +7+, +9=3)
Organoaluminum compounds represented by (ii) general formula % formula % (where P is L1% Na5K, R1 is the same as above) and aluminum alkylated compounds of Group Ⅰ metals, etc. can be mentioned.

Examples of the organoaluminum compounds belonging to (i) above include the following. General formula 8 formula%) (Here, R1 and RX are the same as above., is preferably a number of 1.5≦0≦3.), General formula 8 formula% (Here, R1 is the same as above. .X is halogen 5. is preferably 0<s, <3), general formula 8% (where R1 is the same as above, preferably 2≦, <3
It is. ), general formula % formula %) (where R1 and R1 are the same as above, X is halogen,
0〈, ≦3, Ofan < 3, O≦9〈3, i+n
+Q”3) can be exemplified.

Among the aluminum compounds belonging to (i), more specifically, trialkylaluminum such as triethylaluminum and tributylaluminium, alkenylaluminum such as triisoprenylaluminum, dialkylaluminum alkoxide such as diethylaluminum ethoxide, dibutylaluminum butoxy, and ethyl In addition to alkylaluminum sesquialkoxides such as aluminum sesquiethoxide and butylaluminum sesquibutoxide, R'! , SAβ(OR2). , S
Partially alkoxylated alkyl aluminum halides, such as diethylaluminum chloride, dibutyl aluminum chloride, diethyl aluminum bromide, ethyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquichloride, etc., with an average composition of Partially halogenated alkyl aluminum hydrides such as alkyl aluminum sesquihalides like bromide, alkyl aluminum cybarides like ethyl aluminum dichloride, propyl aluminum dichloride, butyl aluminum dibromide etc., diethylaluminum hydride, dibutyl aluminum hydride Partially hydrogenated alkyl aluminum such as dialkyl aluminum hydride, ethyl aluminum dihydride, alkyl aluminum dihydride such as probyl aluminum dihydride, ethyl aluminum ethoxy chloride, butyl aluminum butoxy chloride, ethyl aluminum ethoxy promide etc. is a partially alkoxylated and halogenated alkyl aluminum.

Examples of compounds belonging to (ii) above include LiA ll (
Examples include CJs) a, LiA It (C?Hls) a, etc.

Moreover, as a compound similar to (i), an organic aluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom may be used. Examples of such compounds include (Czlls) zA I OA J (CtHs)
z, (C4Ha) zA I OA ll (C4L)
! , (Cz)Is) tA It NA I (CJs
) t -CJs Methylaluminoxane and the like can be exemplified.

Among these, it is particularly preferable to use trialkylaluminum and the above-mentioned alkyl aluminum in which two or more aluminums are combined.

The organosilicon compound catalyst component (Q) used by the method of the present invention has the general formula CI) SiR'R"(OR3)z (I) [wherein R
1 and R2 represent a straight chain hydrocarbon group having 3 or more carbon atoms, and R3 represents a hydrocarbon group]. In the above general formula (1), R1 and R2 are n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-decyl group, n- dodecyl group, n-tetradecyl group, n-hexadecyl group, n-octadecyl group, n
Examples include -eicosyl group, and R3 includes methyl group, ethyl group, propyl group, isopropyl group,
Alkyl groups such as butyl and hexyl groups, cycloalkyl groups such as cyclopentyl, cyclohexyl and cyclooctyl groups, aralkyl groups such as phenyl, tolyl and ethylphenyl groups, aralkyl groups such as benzyl, cumyl and phenethyl groups. Examples include groups.

Among these, it is preferable to use an organosilicon compound in which R1 and R2 are straight chain alkyl groups having 3 to 6 carbon atoms, and R1 is an alkyl group and (is a methyl group or an ethyl group).

Specifically, the organosilicon compounds include dilorpropyldimethoxysilane, dibutyldimethoxysilane, dilopentyldimethoxysilane, dihexyldimethoxysilane, dirowoctyldimethoxysilane, and di-n-
Decyldimethoxysilane, dilordodecyldimethoxysilane, di-n-tetradecyldimethoxysilane, dilorhexadecyldimethoxysilane, zirouoctadecyldimethoxysilane, ziroueicosyldimethoxysilane, ziroupropyljethoxysilane, dibutyljethoxysilane, ziroupentyljethoxy Silane, Zyrowoctyljethoxysilane, Di-n-decyljethoxysilane, Di-n-dodecyljethoxysilane, Zyrowtetradecyljethoxysilane, Zyrowhexadecyljethoxysilane, Moro-octadecyljethoxysilane, Zyroweicosyljethoxysilane Silane, di-probil dibutoxysilane, di-n-butyl dipropoxysilane, di-pentyl dipropoxysilane, di-n-probil diisobutoxysilane, cytopropyl dibutoxysilane, dibutyl dibutoxysilane, dihexyl dibutoxysilane, di-n-propyldicyclohexyloxysilane, dibutyldicyclohexyloxysilane, dilorpropyldicyclooctyloxysilane, dilorpropyldiphenoxysilane, dibutyldiphenoxysilane, dilopentyldiphenoxysilane, dihexyldiphenoxy Examples include silane, zillopropylditolyloxysilane, di-n-brobyldibenzyloxysilane, and zillopropyldicumyloxysilane.

The olefins used in the polymerization include ethylene, phlopylene, 1-butene, 4-methyl-1-pentene, and -octene, and these can be subjected to not only homopolymerization but also random copolymerization and block copolymerization. In copolymerization, polyunsaturated compounds such as conjugated dienes and non-diconjugated dienes can be selected as copolymerization components. Among these olefins, propylene or 1-butene is homopolymerized or a mixture of these olefins and other olefins, and propylene or 1-butene is the main component (for example, 50 mol % or more, preferably 70 mol %). It is preferable to apply the method of the present invention to the polymerization or copolymerization of mixed olefins, in which

In the method of the present invention, if the olefin is prepolymerized in the presence of the catalyst and then the olefin is polymerized, the polymerization activity and stereoregularity are further improved, especially in the powder of the resulting polymer. It has a spherical shape, excellent uniformity, and high bulk density, and is suitable for slurry polymerization.

- It is suitable because it has excellent properties and is easy to handle as a powder or slurry.

The prepolymerization is performed by adding the highly active titanium catalyst component (A) in the coexistence of at least a portion of the organoaluminum compound catalyst component (B), and adding about 0.1 to about 500 g of the highly active titanium catalyst component (A) per 1 g of the component (A).
Preferably, 0.3 to about 300 g of olefin is prepolymerized. At this time, part or all of the organosilicon compound catalyst component (C) may be present. The coexisting amount of the organoaluminum compound catalyst component (B) may be sufficient to polymerize the above amount of olefin per 1 g of component (A).
A proportion of, for example, about 0.1 to about 100 mol, especially about 0.5 to about 50 mol, per atom is preferred.

The prepolymerization is preferably carried out under mild conditions in an inert hydrocarbon medium or in liquid monomers.

Inert hydrocarbon media used for this purpose include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, kerosene, and alicyclics such as cyclopentane, cyclohexane, and methylcyclopentane. Examples include aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as ethylene chloride and chlorobenzene, and mixtures thereof. Among these inert hydrocarbon media, it is particularly preferable to use aliphatic hydrocarbons. The prepolymerization treatment can be carried out batchwise or continuously. Further, the concentration of the catalyst in the system can be considerably higher than that in the main polymerization.

The concentration of the highly active titanium catalyst component (A) in the prepolymerization treatment ranges, for example, from about 0.01 to about 200 mmol, preferably from about 0.05 to about 100 mmol, in terms of titanium atoms, per inert hydrocarbon medium IE. It is better to The temperature in the prepolymerization process is such that the prepolymer produced is substantially insoluble in the medium, and is usually about -2
A range of 0 to about +100°C, more preferably about -20 to about +80°C, especially 0 to about +40°C is preferred. The treatment can be carried out by feeding a predetermined amount of olefin to a catalyst suspension in an inert solvent. The olefin used for this purpose may be the same as or different from the olefin used in the main polymerization, and may be selected from those listed above, but preferably ethylene and olefins having 3 to 10 carbon atoms. The α-olefins are preferably selected to produce highly crystalline polymers, with propylene, 4-methyl-1-pentene, 1-butene and the like being particularly preferred. During prepolymerization, a molecular weight regulator such as hydrogen may be present, but at least 135°C
The intrinsic viscosity [η] measured in decalin is 0.2 dl/
It is advisable to limit the amount to such a level that it is possible to produce a prepolymer of not less than 1.5 dl/g, preferably about 0.5 to about 10 dl/g.

The amount of prepolymerization is approximately 0.1 per Ig of titanium catalyst component (d).
from about 500 g, preferably from about 0.3 to about 300 g. Even if the amount of prepolymerization is too large, the effect will not increase accordingly, it will be inefficient, and in some cases, it may cause fish eyes when the olefin polymer is formed into a film etc. Therefore, it is preferable to adjust the amount of prepolymerization within the above range.

Olefin main polymerization is carried out by using the prepolymerized catalyst together with the organoaluminum compound catalyst component (B) and the organosilicon compound catalyst component (C), if any, which were not used in the prepolymerization treatment. .

In the process of the invention, the polymerization of the olefin is carried out in the gas phase or in the liquid phase, for example in the form of a slurry. In slurry polymerization, an inert hydrocarbon may be used as a liquid medium,
The olefin itself can also be used as a solvent. The amount of the catalyst component (A) to be used is, for example, about 0.005 to about 0.5 millimeters, particularly about 1 to about 0.01 to about 0.5 millimeters in terms of Ti atoms per polymerization volume IIl. Also, the amount of organic aluminum urem compound catalyst component (B) to be used is, for example, about 1 to about 1 mole of metal atoms in component B) per mol of titanium atom in component (A) in the polymerization system. 2000 mol, preferably about 5 to about 500 mol, and (C)
The component is about 0.001 to about 10 mol, preferably about 0.01 to about 2 mol, particularly preferably about 0.05 mol, in terms of Si atoms in component (C) per mol of metal atom in component (B). Preferably, the amount is from about 1 mole to about 1 mole.

These respective catalyst components (A), (B), and (C) may be brought into contact with each other during polymerization, or may be brought into contact before polymerization.

In this contacting before polymerization, only an arbitrary component may be freely selected and brought into contact, or a component or a portion of each component may be brought into contact with the component. Furthermore, each component may be brought into contact with each other before polymerization under an inert gas atmosphere or an olefin atmosphere.

The olefin polymerization temperature is preferably from about 20 to about 200
C, more preferably about 50 to about 180 C, and the pressure is from normal pressure to about 100 kg/cri, preferably about 2 to about 50 kg/cri. Polymerization can be carried out in any of the batch, semi-continuous and continuous methods. Furthermore, it is also possible to carry out the polymerization in two or more stages under different reaction conditions.

In the present invention, when applied to the stereoregular polymerization of α-olefins having 3 or more carbon atoms, the present invention is capable of producing a polymer with a high stereoregularity index with high catalytic efficiency. Therefore, even when attempting to obtain a polymer with a high melt flow rate by using hydrogen in the polymerization of olefins, there is a characteristic that the stereoregularity index does not decrease and the activity does not decrease.Furthermore, it has a high activity. In relation to this, the polymer yield per unit solid catalyst component is superior to the conventional proposal at the level of obtaining polymers with the same stereoregularity index, so catalyst residues in the polymer, especially halogen-containing Not only can the amount be reduced and the catalyst removal operation can be omitted, but also the tendency of rusting of the mold during molding can be significantly suppressed.

〔Example〕

Next, the present invention will be explained in more detail with reference to examples.

Example 1 [Preparation of solid Ti catalyst component (A)] 7.14 g (75 mmol) of anhydrous magnesium chloride
, 37.5-decane and 35.1 d (225 mmol) of 2-ethylhexyl alcohol were heated at 130°C for 2 hours to form a homogeneous solution, and then 167 g (11.3 mmol) of phthalic anhydride was added to this solution. 1
Stirring and mixing is continued for an additional hour at 30°C to dissolve phthalic anhydride into the homogeneous solution. After the homogeneous solution thus obtained was cooled to room temperature, the entire amount was dropped over 1 hour into titanium tetrachloride 200+d (1.8 mol) maintained at -20°C. After charging, the temperature of this mixed liquid was raised to 110°C over 4 hours, and when it reached 110°C, 5.03 mff1 (18
, 8 mmol) and then kept stirring at the same temperature for 2 hours. After the completion of the 2-hour reaction, a solid portion is collected by hot filtration, and after resuspending the solid portion in a 275-barrel Ttel, a heating reaction is performed again at 110° C. for 2 hours.

After the reaction was completed, the solid portion was collected again by hot filtration and heated to 110°C.
Wash thoroughly with decane and hexane until no free titanium compound is detected in the washing solution.

Solid Ti catalyst component (A) synthesized by the above production method
is stored as a hexane slurry, and a portion of this is dried for the purpose of examining the catalyst composition.

The composition of the solid Ti catalyst component (A) thus obtained was 2.5% by weight of titanium, 58% by weight of chlorine, and 1% by weight of magnesium.
8% by weight and diisobutyl phthalate) 13.8% by weight.

[Prepolymerization]

After charging 200% of purified hexane into a 4001R1 glass reactor purged with nitrogen, 20% of triethylaluminum was added.
M1lol, Ziropropyldimethoxysilane 4mmo
1 and the Ti catalyst component (A) in terms of titanium atoms.
After inserting 1 mmol of Ti catalyst component (A), propylene was supplied at a rate of 5.9 N J/hour over 1 hour.
2.8 g of propylene was polymerized per g. After the prepolymerization, the liquid part was removed by filtration, and the separated solid part was reslurried in decane.

[Overlapping]

500g of propylene was charged into an autoclave with an internal volume of 21, and 0.6mm of triethylaluminum was heated at 60°C.
ol, Ziropropyldimethoxysilane 0.06+++
mol and the prepolymerized catalyst component (A) were charged in an amount of 0.006 n+mol in terms of titanium atoms, and after further charging hydrogen 2E, the temperature was raised to 70° C. and propylene polymerization was carried out for 40 minutes. The total polymer yield after drying was 302 g, the extraction residue with boiling rhoheptane was 98.1%, and the MFR was 19.
It was 8g/min. Therefore, the polymerization activity at this time is 50
+300g-pp/mmol-Ti.

Example 2 In the prepolymerization of Example 1, the amount of triethylaluminum was changed from 20 mmol to 5 mmol, and no diropropyldimethoxysilane was added.
An experiment was conducted in the same manner as in Example 1.

The results are shown in Table 1.

Example 3 [Preparation of solid catalyst component (A)] A high-speed stirring device (manufactured by Tokushu Kika Kogyo) with an internal volume of 21 was heated to sufficient N.
After 2 substitutions, purified kerosene 700-1 commercially available MgCjl
z, 24.2 g of ethanol, and 3 g of Emazol 320 (trade name, manufactured by Kao Atlas Co., Ltd., sorbitan distearate)), and the system was heated to 120°C while stirring.
The mixture was stirred at 800 rpm for 30 minutes. -1 in advance using a Teflon tube with an inner diameter of 5fi under high-speed stirring.
The refined kerosene 11 cooled to 0° C. was transferred to a 21 glass flask (equipped with a stirrer). The produced solid was collected by filtration and thoroughly washed with hexane to obtain a carrier.

After 7.5 g of the carrier was suspended in 150 g of titanium tetrachloride at room temperature, 1.3 g of diisobutyl phthalate was added, and the yarn was heated to 120°C. After stirring and mixing at 120°C for 2 hours, the solid portion was collected by filtration, suspended again in 150-titanium tetrachloride, and stirring and mixing was performed again at 130°C for 2 hours. Furthermore, a reaction solid substance is collected from the reaction product by filtration,
A solid catalyst component (A) was obtained by washing with a sufficient amount of purified hexane. The components were 2.2% by weight of titanium, 63% by weight of chlorine, 20% by weight of magnesium, and 5.0% by weight of diisobutyl phthalate.

[Prepolymerization]

After charging 200 all of purified hexane into a 400 d glass reactor purged with nitrogen, 200 all of triethylaluminum was added.
mnol, 4 mmof cytopropyldimethoxysilane, and the Ti catalyst component (A) 2 mmol in terms of titanium atom.
1, propylene was fed over 1 hour at a rate of 5.9 N1/hour, and 2.8 g of propylene was polymerized per Ig of Ti catalyst component (A). After the prepolymerization, the liquid part was removed by filtration, and the separated solid part was reslurried in decane.

[Propylene polymerization]

Polymerization of propylene was carried out in the same manner as in Example 1.

Example 4 Example 1 except that dibutyldimethoxysilane used in Example 1 was replaced with dibutyldimethoxysilane.
The experiment was conducted in a similar manner. The results are shown in Table 1.

Example 5 An experiment was carried out in the same manner as in Example 1, except that the zillopropyldimethoxysilane used in Example 1 was replaced with zillohexyldimethoxysilane. The results are shown in Table 1.

[Brief explanation of drawings]

FIG. 1 is a flowchart showing one example of the preparation of a catalyst for olefin polymerization according to the present invention.

Claims (1)

[Claims] (1) [A] A solid titanium catalyst component containing as essential components magnesium, titanium, halogen, and polyvalent carboxylic acid ester formed by contacting a magnesium compound, a titanium compound, and a polyvalent carboxylic acid ester, [ B] Organoaluminum compound catalyst component, and [C] General formula [I] SiR^1R^2 (OR^3)_
2 [I] An organosilicon compound catalyst component represented by [wherein R^1 and R^2 represent a linear hydrocarbon group having 3 or more carbon atoms, and R^3 represents a hydrocarbon group]; A method for polymerizing olefins, which comprises polymerizing or copolymerizing olefins in the presence of a catalyst formed from.