JP2537506B2 - Olefin Polymerization Method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention provides an olefin polymer (hereinafter, referred to as olefin) by polymerization of olefin (hereinafter, it may be used to include a copolymer of olefin). A copolymer may be used inclusively). In particular,
When applied to the polymerization of α-olefin having 3 or more carbon atoms,
The present invention relates to a method for producing an olefin polymer capable of obtaining a highly stereoregular polymer in high yield. Furthermore, in the polymerization of α-olefins having 3 or more carbon atoms, olefin polymerization in which the stereoregularity of the polymer is less reduced even when the melt flow rate of the polymer is changed by using a molecular weight modifier such as hydrogen during the polymerization. Regarding possible methods. The present invention also relates to a method for polymerizing olefin, which has an advantage that the activity is hardly decreased with the passage of polymerization time.

[Conventional technology]

There have already been many proposals for a method for producing a solid catalyst component containing magnesium, titanium, a halogen and an electron donor as essential components, and when the solid catalyst component is used for polymerization of α-olefin having 3 or more carbon atoms, It is also known that highly stereoregular polymers can be obtained with high catalytic activity. However, many of them are desired to be further improved in activity and stereoregularity of polymers.

For example, in order to obtain a high quality olefin polymer without treatment after the polymerization, the production ratio of the stereoregular polymer is very high, and the polymer yield per transition metal is not sufficiently large. Don't The technologies of the various proposals hitherto can be said to be at a satisfactory level from the above viewpoint depending on the type of the target polymer, but the residual halogen content in the polymer relating to rusting of the molding machine In terms of
Few things can be said to have sufficient performance. Moreover, most of them have a drawback that when producing a polymer having a large methotre flow rate, the yield and the stereoregularity index decrease not a little.

The Applicant has proposed a number of methods aimed at ameliorating the drawbacks of the prior art in the stereoregular polymerization of α-olefins. For example, JP-A-58-83006, JP-A-58-138705, JP-A-58-138706, JP-A-58-138707, JP-A-58-138708, and JP-A-58-138708. JP-A-58-138709, JP-A-58-138710, JP-A-58-138715 and the like disclose a highly active titanium catalyst component containing [A] magnesium, titanium, halogen and an electron donor as essential components, A method for polymerizing or copolymerizing olefin in the presence of a catalyst formed from [B] an organometallic compound catalyst component and [C] an organosilicon compound catalyst component has been already proposed. All of these methods are polymerization methods which are remarkably excellent in the polymerization activity of the catalyst and are excellent in stereoregularity, and have solved the above-mentioned drawbacks of the prior art.

[Problems to be solved by the invention]

The present invention is to provide a method for polymerizing olefins having excellent polymerization activity and excellent stereoregularity, and as a result of studying an olefin polymerization catalyst having extremely excellent polymerization activity and stereoregularity, [A] a catalyst formed from a solid titanium catalyst component containing magnesium, titanium, halogen, and a polycarboxylic acid ester as essential components, [B] an organoaluminum compound catalyst component, and [C] a specific organosilicon compound catalyst component. The inventors have found that the above objects can be achieved by using them, and have reached the present invention.

An object of the present invention is to provide an olefin polymerization catalyst having an organosilicon compound catalyst component as a cocatalyst component and having excellent polymerization activity and stereoregularity.

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

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

Another object of the present invention is to use a small amount of hydrogen with a small stereoregularity in the case of obtaining a polymer having a large melt flow rate by allowing a molecular weight modifier such as hydrogen to coexist in the polymerization system during polymerization. In addition to the advantage that the melt flow rate can be controlled by the method described above, it is intended to provide an olefin polymerization method in which the catalytic activity is improved by utilizing a molecular weight modifier such as hydrogen. Yet another object of the present invention is to provide an improved process for olefin polymerization.

All of these objects of the present invention can be achieved by adopting the configurations 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 Problems] and [Operation] According to the present invention, [A] magnesium, titanium, halogen and a compound formed by bringing a magnesium compound, a titanium compound and a polycarboxylic acid ester into contact with each other. Solid titanium catalyst component containing polyvalent carboxylic acid ester as an essential component, [B] organoaluminum compound catalyst component, and [C] general formula [I] SiR ¹ R ² (OR ³ ) ₂ [I] [wherein R ¹ and R ² represent a straight-chain hydrocarbon group having 3 or more carbon atoms, and R ³ represents a hydrocarbon group], in the presence of a catalyst formed from an organosilicon compound catalyst component There is provided a method for polymerizing olefin, which comprises polymerizing or copolymerizing.

The titanium catalyst component [A] used in the present invention is a highly active catalyst component containing magnesium, titanium, halogen and a polycarboxylic acid ester as essential components. This titanium catalyst component [A] contains magnesium halide having a small crystallite size as compared with a commercially available magnesium halide, and usually has a specific surface area of about 50 m ² / g or more, preferably about 60 to about 10 m ² / g.
00 m ² / g, more preferably about 100 to about 800 m ² / g, and the composition thereof is not substantially changed by washing with hexane at room temperature. Also, inorganic or organic compounds,
For example, when a diluent such as a silicon compound, an aluminum compound, or polyolefin is used, high performance is exhibited even if the specific surface area is smaller than that described above. In the titanium catalyst component [A], the halogen / titanium (atomic ratio) is about 4 to about 20.
0, especially about 5 to about 100, electron donor / titanium (molar ratio) of about 0.1 to about 10, particularly about 0.2 to about 6, magnesium / titanium (atomic ratio) of about 1 to about 10
0, especially about 2 to about 50 are preferable. The component [A] may also contain other electron donors, metals, elements, functional groups and the like.

Such 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 in some cases, another reaction agent such as silicon, Compounds such as phosphorus and aluminum can be used.

Examples of the method for producing the titanium catalyst component [A] include, for example, JP-A-50-108385, JP-A-50-126590, and JP-A-50-126590.
Nos. 51-20297, 51-28189, 51-64586, 51-9
2885, 51-136625, 52-87489, 52-10059
No. 6, No. 52-100596, No. 52-147688, No. 52-104593
No. 53-2580, No. 53-40093, No. 53-40094, No.
55-135102, 56-135103, 56-811, 56-1
1908, 56-18606, 58-83006, 58-138705
No. 58, No. 58-138706, No. 58-138707, No. 58-138708
No. 58, No. 58-138709, No. 58-138710, No. 58-138715
No. 60, No. 60-23404, No. 61-21109, No. 61-37802,
It can be produced according to the method disclosed in each of the publications such as 61-37803 and 55-152710. Several examples of the method for producing the titanium catalyst component [A] will be briefly described below.

(1) An electron donor and / or an organoaluminum compound is crushed or not crushed with or without 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 crushing aid, and the like. It is pretreated with a reaction aid such as a halogen-containing silicon compound or is reacted with a titanium compound that forms a liquid phase under the reaction conditions with the solid obtained without pretreatment. However, the electron donor is used at least once.

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

(3) The titanium compound is reacted with the product obtained in (2).

(4) An electron donor and a titanium compound are reacted with the product obtained in (1) or (2).

(5) A magnesium compound or a complex compound of a magnesium compound and an electron donor is pulverized in the presence or absence of an electron donor, a pulverization aid or the like, and in the presence of a titanium compound to obtain an electron donor and / or an organic compound. Pretreatment with a reaction aid such as an aluminum compound or a halogen containing silicon compound, or the solid obtained without pretreatment is treated with halogen or a halogen compound or an aromatic hydrocarbon. However, the electron donor is used at least once.

(6) The compound obtained in (1) to (4) is treated with halogen, a halogen compound or an aromatic hydrocarbon.

(7) A contact reaction product of a metal oxide, dihydrocarbyl magnesium and a halogen-containing alcohol is contacted with a polycarboxylic acid ester and a titanium compound.

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

Among these preparation methods, a catalyst using a liquid titanium halide or a catalyst using a halogenated hydrocarbon after or when using a titanium compound is preferable.

The electron donor that can be a constituent of the highly active titanium catalyst component [A] of the present invention is a polyvalent carboxylic acid ester. Preferred as these polycarboxylic acid esters are: (Here, R ¹ is a substituted or unsubstituted hydrocarbon group, R ² , R ⁵ , R ⁶
Is hydrogen or a substituted or unsubstituted hydrocarbon group, and R ³ and R ⁴ are hydrogen or a substituted or unsubstituted hydrocarbon group, and preferably at least one of them is a substituted or unsubstituted hydrocarbon group. R ³ and R ⁴ may be connected to each other. Here, the substituted hydrocarbon group includes a heteroatom such as N, O, S, and is, for example, C—O—C, COOR, COOH, OH, SO
_It has a group such as ₃ H, —C—N—C—, and NH ₂ . ) Can be exemplified.

Particularly preferred among these are diesters of dicarboxylic acids in which at least one of R ¹ and R ² is an alkyl group having 2 or more carbon atoms.

Specific examples of preferred polycarboxylic acid esters include succinic acid diester, dibutyl succinate, diethyl methyl succinate, diisobutyl α-methyl glutarate, dibutyl methyl malonate, diethyl malonate, diethyl ethyl malonate, diethyl isopropyl malonate. , Diethyl butylmalonate, diethyl phenylmalonate, diethyl diethylmalonate, diethyl allylmalonate, diethyl diisobutylmalonate, diethyl dinormal butylmalonate, dimethyl maleate, monooctyl maleate, diisooctyl maleate, diisobutyl maleate, butyl maleate Acid diisobutyl, diethyl butyl maleate, β-methyl glutarate diisopropyl, ethyl succinate diaryl, di-2-ethylhexyl fumarate, itaconic acid Aliphatic polycarboxylic acid esters such as diethyl, diisobutyl itaconate, diisooctyl citracone, dimethyl citracone, 1,2-
Aliphatic polycarboxylic acid esters such as diethyl cyclohexanecarboxylate, diisobutyl 1,2-cyclohexanecarboxylate, diethyl tetrahydrophthalate, diethyl nadicuate, monoethyl phthalate, dimethyl phthalate, methylethyl phthalate, monoisobutyl phthalate,
Diethyl phthalate, ethyl isobutyl phthalate, mononormal butyl phthalate, ethyl normal butyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-n-heptyl phthalate, Aromatic polycarboxylic acid esters such as di-2-ethylhexyl phthalate, didecyl phthalate, benzylbutyl phthalate, diphenyl phthalate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate, dibutyl trimellitate, 3,4 Mention may be made of heterocyclic polycarboxylic acid esters such as furandicarboxylic acid.

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

Among these polycarboxylic acid esters, those having a skeleton of the above-mentioned general formula are preferred, and more preferred are esters of phthalic acid, maleic acid, substituted malonic acid, etc. with an alcohol having 2 or more carbon atoms. And a diester of phthalic acid and an alcohol having 2 or more carbon atoms.

When carrying these electron donors, it is not always necessary to use them as starting materials, and it is necessary to use compounds that can be changed to these during the preparation process of the titanium catalyst component and convert them into these compounds at the stage of the preparation. Good.

Other electron donors may coexist in the titanium catalyst component, but if they coexist in too large an amount, it will have an adverse effect and should be suppressed to a small amount.

In the present invention, the magnesium compound used for preparing the solid titanium catalyst component [A] is a magnesium compound with or without reducing ability. Examples of the former are magnesium compounds having a magnesium-carbon bond or a magnesium-hydrogen bond, such as dimethylmagnesium, diethylmagnesium, dipropylmagnesium,
Examples thereof include dibutyl magnesium, diamyl magnesium, dihexyl magnesium, didecyl magnesium, ethyl magnesium chloride, propyl magnesium chloride, butyl magnesium chloride, hexyl magnesium chloride, amyl magnesium chloride, butyl ethoxy magnesium, ethyl butyl magnesium, and butyl magnesium hydride. These magnesium compounds can be used in the form of a complex compound with, for example, organoaluminum, and may be in a liquid state or a solid state. On the other hand, magnesium compounds having no reducing ability include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide and magnesium fluoride, methoxymagnesium chloride, ethoxymagnesium chloride, isopropoxymagnesium chloride, butoxymagnesium chloride, octoxychloride. Alkoxy magnesium halides such as magnesium chloride, phenoxy magnesium chloride, alkoxy magnesium halides such as methyl phenoxy magnesium chloride, ethoxy magnesium,
Isopropoxymagnesium, butoxymagnesium,
Carboxylates of magnesium such as alkoxymagnesium such as n-octoxymagnesium, 2-ethylhexoxymagnesium, allyloxymagnesium such as phenoxymagnesium, dimethylphenoxymagnesium, magnesium laurate, magnesium stearate And the like. Further, the magnesium compound having no reducing ability may be one derived from the above-mentioned magnesium compound having reducing ability or one derived at the time of preparation of the catalyst component,
For example, a method of changing a magnesium compound having a reducing ability to a magnesium compound having no reducing ability by bringing it into contact with a compound such as a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an ester or an alcohol. The magnesium compound may be a complex compound with another metal, a complex compound, or a mixture with another metal compound. Further, a mixture of two or more of these compounds may be used. Among these, preferred magnesium compounds are compounds having no 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].
(OR) gX ₄ -g (R is a hydrocarbon group, X is a halogen, 0 ≦
A tetravalent titanium compound represented by g ≦ 4) is preferable.
More specifically, titanium tetrahalides such as TiCl ₄ , TiBr ₄ , and Til ₄ , Ti (OCH ₃ ) Cl ₃ , Ti (OC ₂ H ₃ ) Cl ₃ , Ti (O
Tri-halogenated alkoxy titanium such as n-C ₄ H ₉ ) Cl ₃ , Ti (OC ₂ H ₃ ) Br ₃ and Ti (OisoC ₄ H ₉ ) Br ₃ Ti (OCH ₃ ) ₂ C
l ₂ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ , Ti (On-C ₄ H ₉ ) ₂ Cl ₂ , Ti (OC
₂ H ₅ ) Br ₂ , etc., dihalogenated alkoxy titanium, Ti
_{(OCH 3) 3 Cl, Ti} (OC 2 H 5) 3 Cl, Ti (On-C 4 H 9) 3 Cl, Ti
Examples of monohalogenated trialkoxy titanium such as (OC ₂ H ₅ ) ₃ Br Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , and tetraalkoxy titanium such as Ti (On-C ₄ H ₉ ) ₄ can do. Of these, preferred are halogen-containing titanium compounds, particularly titanium tetrahalides, and particularly preferred is titanium tetrachloride. These titanium compounds may be used alone or in the form of a mixture. Alternatively, it may be diluted with a hydrocarbon or a halogenated hydrocarbon before use.

In the preparation of the titanium catalyst component [A], a titanium compound,
The amount of the magnesium compound, the electron donor to be supported, and the electron donor that may be optionally used, such as alcohol, phenol, monocarboxylic acid ester, silicon compound and aluminum compound, depends on the preparation method. Although it cannot be specified unconditionally, for example, the ratio can be 0.01 to 5 mol of the electron donor to be supported and 0.01 to 500 mol of the titanium compound per mol of the magnesium compound.

In the present invention, olefin polymerization or copolymerization is carried out using a combination catalyst of the following titanium catalyst component [A], organoaluminum compound catalyst component [B] and organosilicon compound catalyst component [C].

Examples of the component [B] include (i) an organoaluminum compound having at least one Al-carbon bond in the molecule, for example, a general formula R ¹ _m Al (OR ² ) _n H _p X _q (where R ¹ and R ² usually have 1 to 15 carbon atoms
Hydrocarbon groups, including one, preferably one to four, may be the same or different from each other. X is halogen, _m is 0 <
_m ≦ 3, 0 ≦ _n ≦ 3, _p is 0 ≦ _p ≦ 3, _q is 0 ≦ _q ≦ 3
And an organic aluminum compound represented by the formula _m + _n + _p + _q = 3), (ii) the general formula M ¹ AlR ¹ ₄ (wherein M ¹ is Li, Na or K). , R ¹ is the same as the above) and a complex alkyl compound of a Group I metal and aluminum.

Examples of the organoaluminum compound belonging to (i) above include the following. Formula _{^{R 1 m Al (OR 2)}} 3-m ( wherein like. _M and R ¹ and R ² above is preferably 1.
5 ≦ _m ≦ 3. ), The general formula R ¹ _m AlX _3-m (wherein R ¹ is the same as above, X is a halogen, and _m is preferably 0 < _m <3), and the general formula R ¹ _m AlH _3-m ( Here, R ¹ is the same as above, and _m is preferably 2 ≦ _m <3.
Is. ), The general formula R ¹ _m Al (OR ² ) _n X _q (wherein R ¹ and R ² are the same as above. X is halogen, 0
<In _{m ≦ 3,0 ≦ n <3,0 ≦} q <3, m + n + q = 3
And the like can be exemplified.

Among the aluminum compounds belonging to (i), more specifically, trialkylaluminums such as triethylaluminum and tributylaluminum, alkenylaluminums such as triisoprenylaluminum, dialkylaluminum alkoxides such as diethylaluminum ethoxide and dibutylaluminum butoxy. In addition to alkylaluminum sesquialkoxides such as ethyl aluminum sesquiethoxide, butylaluminum sesquibutoxide, partially alkoxylated alkylaluminum having an average composition represented by R ¹ _2.5 Al (OR ² ) _0.5 , diethylaluminum Chloride,
Dibutyl aluminum chloride, dialkyl aluminum halides such as diethyl aluminum bromide, ethyl aluminum sesquichloride, butyl aluminum sesquichloride, alkyl aluminum sesquihalides such as ethyl aluminum sesquibromide, ethyl aluminum dichloride, propyl aluminum dichloride, butyl aluminum dibromide, etc. Partially halogenated alkyl aluminum such as alkyl aluminum dihalide, dialkyl aluminum hydride such as diethyl aluminum hydride, dibutyl aluminum hydride, partial aluminum aluminum hydride such as ethyl aluminum dihydride, propyl aluminum dihydride etc. Alkyl aluminum, hydrogenated to Chill aluminum ethoxy chloride, butyl aluminum butoxide cycloalkyl chloride, partially alkoxylated and halogenated alkylaluminum such as ethylaluminum ethoxy bromide.

Examples of the compound belonging to (ii) above include LiAl (C
_{2 H 5) 4, LiAl (} C 7 H 15) 4 etc. can be exemplified.

Further, a compound similar to (i) may be an organoaluminum compound in which two or more aluminum atoms are bound via an oxygen atom or a nitrogen atom. Examples of such compounds include (C ₂ H ₅ ) ₂ AlOAl (C ₂ H ₅ ) ₂ , (C ₄ H ₈ ) ₂ AlOAl (C ₄ H ₈ ) ₂ , Examples include methylaluminoxane.

Among these, it is particularly preferable to use trialkylaluminum or alkylaluminum in which two or more aluminums described above are bonded.

The organosilicon compound catalyst component (c) used according to the method of the present invention has a general formula [I] SiR ¹ R ² (OR ³ ) ₂ [I] [wherein R ¹ and R ² are the number of carbon atoms. Represents a straight-chain hydrocarbon group of 3 or more, and R ³ represents a hydrocarbon group]. As R ¹ and R ² in the above general formula [I], n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-pephtyl group, n-octyl group, n-decyl group, n-dodecyl group, n-tetradecyl group, n-hexadecyl group, n-octadecyl group, n
-Eicosyl group and the like can be exemplified, and as R ³ , a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an alkyl group such as a hexyl group, a cyclopentyl group, a cyclohexyl group, a cycloalkyl such as a cyclooctyl group. Examples thereof include an aralkyl group such as a group, a phenyl group, a tolyl group, and an ethylphenyl group, an aralkyl group such as a benzyl group, a cumyl group, and a phenethyl group. Among these, it is preferable to use an organosilicon compound in which R ¹ and R ² are linear alkyl groups having 3 to 6 carbon atoms and R ³ is an alkyl group, particularly a methyl group or an ethyl group. Specific examples of the organosilicon compound include di-n-propyldimethoxysilane, di-n-butyldimethoxysilane, di-n-pentyldimethoxysilane, di-n-hexyldimethoxysilane, di-n-octyldimethoxysilane and di-n-decyldimethoxy. Silane, di-n-dodecyldimethoxysilane, di-n-tetradecyldimethoxysilane, di-n-hexadecyldimethoxysilane, di-n-octadecyldimethoxysilane, di-n-eicosyldimethoxysilane, di-n-propyldiethoxysilane, di-n -Butyldiethoxysilane, di-n-pentyldiethoxysilane, di-n-octyldiethoxysilane, di-n-decyldiethoxysilane, di-n-dodecyldiethoxysilane, di-n-tetradecyldiethoxysilane, di-n- Hexadecyldiethoxysilane, di-n-o Tadecyldiethoxysilane, di-n-eicosyldiethoxysilane, di-n-propylpropoxysilane, di-n-butyldipropoxysilane, di-n-pentyldipropoxysilane, di-n-propyldiisopropoxysilane, di-n- Propyldibutoxysilane, di-n-butylbutoxysilane, di-n-hexyldibutoxysilane, di-n-propyldicyclohexyloxysilane, di-n-butyldicyclohexyloxysilane, di-n-propyldicyclooctyloxysilane, di-n-propyl Diphenoxysilane, di-n-butyldiphenoxysilane, di-n-pentyldiphenoxysilane, di-n-hexyldiphenoxysilane, di-n-propylditolyloxysilane, di-n-propyldibenzyloxysilane, Di-n-propyldicumyloxysilane, etc. It can be exemplified.

The olefins used for the polymerization include ethylene, furopyrene, 1-butene, 4-methyl-1-pentene, 1-octene and the like, and these can be used for not only homopolymerization but also random copolymerization and block copolymerization. Upon copolymerization, polyunsaturated compounds such as conjugated dienes and non-diconjugated dienes can be selected as the copolymerization component. Among these olefins, homopolymerization of propylene or 1-butene or a mixed component of these olefins and other olefins containing propylene or 1-butene as the main component (for example, 50 mol% or more, preferably 70% or more). It is preferred to apply the method of the present invention to the polymerization or copolymerization of mixed olefins in molar ratios of at least 1).

In the method of the present invention, when the olefin is polymerized after the olefin is preliminarily polymerized in the presence of the catalyst prior to the polymerization of the olefin, the polymerization activity and the stereoregularity are further improved. It is preferable because it has a spherical shape and is excellent in uniformity, has a high bulk density, and in the case of slurry polymerization, has excellent slurry properties and handleability of powder or slurry.

In the prepolymerization, the highly active titanium catalyst component (A) is present in the presence of at least a part of the organoaluminum compound catalyst component (B) in an amount of about 0.1 to about 500 g, preferably 0.3 to about 300 g per 1 g of the component (A). Olefin is preliminarily polymerized. At this time, part or all of the organosilicon compound catalyst component (C) may coexist. The coexisting amount of the organoaluminum compound catalyst component (B) may be an amount sufficient to polymerize the above amount of olefin per 1 g of the component (A). For example, per 1 atom of titanium in the high activity titanium catalyst component (A), A ratio of about 0.1 to about 100 mol, particularly about 0.5 to about 50 mol is preferred.

The prepolymerization is preferably carried out in an inert hydrocarbon medium or in a liquid monomer under mild conditions. Inert hydrocarbon media used for this purpose include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene, and cycloaliphatic rings such as cyclopentane, cyclohexane and methylcyclopentane. Examples thereof include aromatic hydrocarbons such as group hydrocarbons, benzene, toluene and xylene, halogenated hydrocarbons such as ethylene chloride and chlorobenzene, and mixtures thereof. Of these inert hydrocarbon media, it is particularly preferred to use aliphatic hydrocarbons. The prepolymerization treatment can be carried out batchwise or continuously. It is also possible to carry out at a much higher concentration than the concentration of the catalyst in the system in the main polymerization.

The concentration of the highly active titanium catalyst component (A) in the prepolymerization treatment is, for example, 0.01 to about 200 mmol, preferably about 0.05, in terms of titanium atom per inert hydrocarbon medium.
The preferred range is from about 100 millimolar. The temperature in the prepolymerization process is the temperature at which the resulting prepolymer is substantially insoluble in the medium and is usually about -20 to about +100.
C., more preferably about -20 to about + 80.degree. C., especially 0 to about + 40.degree. The treatment can be carried out by supplying 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 can be selected from those exemplified above, for example, ethylene and C3-10 are preferable. It should be chosen so as to produce a highly crystalline polymer from α-olefin, with propylene, 4-methyl-1-pentene, 1-butene and the like being especially preferred. In the prepolymerization, a molecular regulator such as hydrogen may coexist, but the intrinsic viscosity [η] measured in decalin of at least 135 ° C is 0.2 dl / g or more, preferably about 0.5 to about 10 dl / g.
It is preferable to limit the amount so that the prepolymer can be produced.

The amount of prepolymerization is about 0.1 to about 500 g, preferably about 0.3 to about 300 g per 1 g of the titanium catalyst component (d). Even if the amount of prepolymerization is too large, the effect does not increase with it, and the efficiency is poor, and in some cases, when the olefin polymer is formed into a film, it may cause the occurrence of fisheye. Therefore, the amount of prepolymerization is preferably adjusted within the above range.

Organoaluminum compound catalyst component (B) which has not been used in the prepolymerization treatment of the catalyst obtained by the prepolymerization treatment.
When the organosilicon compound catalyst component (C) is present, the olefin main polymerization is carried out by using it together with these catalysts.

In the process of the present invention, the olefin polymerization is carried out in the gas phase or in the liquid phase, for example in the form of a slurry. In the slurry polymerization, an inert hydrocarbon may be used as a liquid medium, or olefin may be used as a solvent. The amount of the catalyst component (A) used is, for example, a polymerization volume of 1
The amount of the catalyst component (B) of the organoaluminum compound used is, for example, titanium in the component (A) in the polymerization system. (B) for 1 mol of atom
The amount of the metal atom in the component is about 1 to about 2000 mol, preferably about 5 to about 500 mol, and the amount of the component (C) is about 1 mol of the metal atom in the component (B). The amount is preferably about 0.001 to about 10 mol, preferably about 0.01 to about 2 mol, and particularly preferably about 0.05 to about 1 mol in terms of atom.

These catalyst components (A), (B) and (C) may be brought into contact with each other during the polymerization or may be brought into contact before the polymerization.
In the contact before the polymerization, only arbitrary two members may be freely selected and contacted, or a part of each component may be contacted with two or three members. Further, the contact of each component before the polymerization may be carried out in an inert gas atmosphere or in an olefin atmosphere.

The olefin polymerization temperature is preferably from about 20 to about 200
℃, more preferably about 50 to about 180 ℃, the pressure is normal pressure to about 100 kg / cm ² , preferably about 2 to about 50 kg / cm
^It is preferable to carry out under a pressurized condition of about ² . The polymerization can be performed by any of a batch system, a semi-continuous system, and a continuous system. Further, the polymerization can be carried out in two or more different stages under different reaction conditions.

In the present invention, a polymer having a high stereoregularity index can be produced with high catalyst efficiency, particularly when applied to stereoregular polymerization of α-olefin having 3 or more carbon atoms.
When the present invention is adopted, there is a feature that even when an attempt is made to obtain a polymer having a high melt flow rate by using hydrogen in the polymerization of olefin, the stereoregularity index and the activity are not lowered. In relation to higher activity, the polymer yield per unit solid catalyst component is superior to the conventional proposals at the level of obtaining a polymer with the same stereoregularity index, so that It is possible to reduce the content of the catalyst residue, particularly the halogen content, and it is possible to omit the catalyst removal operation, and it is possible to significantly suppress the rusting tendency of the mold during molding.

〔Example〕

 Next, an example will be described in more detail.

Example 1 [Preparation of solid Ti catalyst component [A]] 7.14 g (75 mmol) of anhydrous magnesium chloride and 37.5 m of decane
l and 2-ethylhexyl alcohol 35.1ml (225mmo
l) is heated at 130 ° C for 2 hours to form a uniform solution,
1.67 g (11.3 mmol) of phthalic anhydride is added to this solution, and the mixture is stirred and mixed at 130 ° C. for 1 hour to dissolve phthalic anhydride in the homogeneous solution. The homogeneous solution thus obtained is cooled to room temperature and then added dropwise to 200 ml (1.8 mmol) of titanium tetrachloride kept at -20 ° C over 1 hour. After the completion of charging, the temperature of this mixed solution was raised to 110 ° C. over 4 hours, and when it reached 110 ° C., 5.03 ml (18.8 mmol) of diisobutyl phthalate was added, and the mixture was kept stirring at the same temperature for 2 hours. To do. After completion of the reaction for 2 hours, a solid portion was collected by hot filtration, and the solid portion was resuspended in 275 ml of TiCl ₄ and then heated again at 110 ° C. for 2 hours.
After the completion of the reaction, the solid part is again collected by hot filtration and thoroughly washed with decane and hexane at 110 ° C. until no free titanium compound is detected in the washing liquid. The solid Ti catalyst component [A] synthesized by the above-mentioned production method is stored as a hexane slurry, and a part thereof is dried for the purpose of examining the catalyst composition. The solid Ti catalyst component [A] thus obtained had a composition of 2.5% by weight of titanium, 58% by weight of chlorine, 18% by weight of magnesium and 13.8% by weight of diisobutyl phthalate.

[Preliminary polymerization]

After charging 200 ml of purified hexane into a 400 ml glass reactor purged with nitrogen, 20 mmol of triethylaluminum, 4 mmol of di-n-propyldimethoxysilane and 2 mmol of the Ti catalyst component [A] in terms of titanium atom were added, and then 5.9N
Propylene was fed at a rate of 1 hour / hour over 1 hour to polymerize 2.8 g of propylene per 1 g of the Ti catalyst component [A]. After the preliminary polymerization, the liquid part was removed by filtration, and the separated solid part was reslurried in decane.

(Conjugation)

An autoclave having an inner volume of 2 was charged with 500 g of propylene, and at 60 ° C., 0.6 mmol of triethylene aluminum, 0.06 mmol of di-n-propylenedimethoxysilane, and 0.006 mmol of the prepolymerized catalyst component [A] in terms of titanium atom.
After charging, and further charging hydrogen 2, the temperature was raised to 70 ° C. and propylene polymerization was carried out for 40 minutes. The total polymer yield after drying is 302g
And the extraction residual rate by boiling n-heptane is 98.1%, MFR
Was 19.8 g / min. Therefore, the polymerization activity at this time is 50,30.
It is 0 g-pp / mmol-Ti.

Example 2 In the prepolymerization of Example 1, the same procedure as in Example 1 was carried out except that the amount of triethylaluminum was changed from 20 mmol to 6 mol and di-n-propyldimethoxysilane was not added. The results are shown in Table 1.

Example 3 [Preparation of solid catalyst component (A)] A high-speed stirrer (made by Tokushu Kika Kogyo) having an inner volume of 2 was sufficiently used
After substituting with N ₂ , 700 ml of refined kerosene, 10 g of commercially available MgCl ₂ , 24.2 g of ethanol and ₃ g of trade name Emazole 320 (Kao Atlas, sorbitan distearate) were added, and the system was heated under stirring to 120 ° C. And stirred at 800 rpm for 30 minutes. Under high-speed stirring, a Teflon Cide tube having an inner diameter of 5 mm was used to transfer to a 2 glass flask (with a stirrer) filled with purified kerosene 1 that had been cooled to −10 ° C. in advance. The produced solid was collected by filtration and sufficiently washed with hexane to obtain a carrier.

After suspending 7.5 g of the carrier in 150 ml of titanium tetrachloride at room temperature, 1.3 ml of diisobutyl phthalate was added and the system was added to 120 ml.
The temperature was raised to ° C. After stirring and mixing at 120 ° C. for 2 hours, the solid portion was collected by filtration, suspended again in 150 ml of titanium tetrachloride, and again stirred and mixed at 130 ° C. for 2 hours. Further, the reaction solid was collected from the reaction product by filtration and washed with a sufficient amount of purified hexane to obtain a solid catalyst component (A). The components are, in terms of atoms, 2.2% by weight of titanium, 63% by weight of chlorine, 20% by weight of magnesium, 5.0% of diisobutyl phthalate.
% By weight.

[Preliminary polymerization]

After charging 200 ml of purified hexane into a nitrogen-substituted 400 ml glass reactor, 20 mmol of triethylaluminum, 4 mmol of di-n-propylenemethoxysilane and 2 mmol of the Ti catalyst component [A] in terms of titanium atom were charged, and then 5.9 N
Propylene was fed at a rate of 1 hour / hour over 1 hour to polymerize 2.8 g of propylene per 1 g of the Ti catalyst component [A]. After the preliminary polymerization, 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 An experiment was conducted in the same manner as in Example 1 except that di-n-propyldimethoxysilane used in Example 1 was replaced with di-n-butyldimethoxysilane. The results are shown in Table 1.

Example 5 An experiment was performed in the same manner as in Example 1 except that di-n-propyldimethoxysilane used in Example 1 was replaced with di-n-hexyldimethoxysilane. The results are shown in Table 1.

Comparative Example 1 An experiment was conducted in the same manner as in Example 1 except that the di-n-propyldimethoxysilane used in Example 1 was replaced with diisobutyldiisobutoxysilane. The results are shown in Table 1.

Comparative Example 2 An experiment was performed in the same manner as in Example 1 except that n-propyldimethoxysilane used in Example 1 was replaced with dimethyldiphenoxysilane. The results are shown in Table 1.

Comparative Example 3 An experiment was conducted in the same manner as in Example 1 except that dimethyldimethoxysilane was used instead of n-propyldimethoxysilane used in Example 1. The results are shown in Table 1.

Comparative Example 4 An experiment was performed in the same manner as in Example 1 except that dimethyldiethoxysilane was used instead of n-propyldimethoxysilane used in Example 1. The results are shown in Table 1.

[Brief description of drawings]

FIG. 1 is a flow chart showing one example of the preparation of a catalyst in the polymerization of olefin of the present invention.

Claims (1)

(57) [Claims] 1. A solid titanium catalyst component containing [A] magnesium compound, titanium compound and polyvalent carboxylic acid ester as essential components which are formed by contacting magnesium, titanium, halogen and polyvalent carboxylic acid ester. , [B] an organoaluminum compound catalyst component, and [C] a general formula [I] SiR ¹ R ² (OR ³ ) ₂ [I] [wherein, R ¹ and R ² are linear chains having 3 or more carbon atoms. A hydrocarbon group and R ³ represents a hydrocarbon group], wherein the olefin is polymerized or copolymerized in the presence of a catalyst formed from an organosilicon compound catalyst component represented by: .