JP4508173B2 - Olefin polymerization catalyst component, olefin polymerization catalyst, olefin polymer production method, and organosilicon compound use method - Google Patents

Description

  The present invention relates to an olefin polymerization catalyst component comprising a specific organosilicon compound, a method for using the organosilicon compound, an olefin polymerization catalyst using the same, and a method for producing an olefin polymer. More specifically, when used as a catalyst component for α-olefin polymerization, it is excellent in catalytic activity and stereoregular polymerization ability, and even when hydrogen is used for molecular weight control, a polymer having very little amorphous polymer is obtained. The present invention relates to a catalyst component for olefin polymerization comprising a suitable organosilicon compound.

  As a method for producing an α-olefin polymer such as propylene and butene-1, it is well known to use a so-called Ziegler-Natta catalyst obtained by contacting a titanium-based solid catalyst component with an organoaluminum compound.

  When the α-olefin polymer is produced, an amorphous polymer is usually produced as a by-product in addition to the highly stereoregular α-olefin polymer having high industrial utility value. This amorphous polymer has little industrial utility value, and has a great adverse effect on the mechanical properties when the α-olefin polymer is processed into an injection molded product, film, fiber, or other processed product. In addition, the production of the amorphous polymer causes a loss of raw material monomers, and at the same time, a production facility for removing the amorphous polymer is required, which causes a great disadvantage from an industrial viewpoint. Accordingly, it is desirable that the catalyst for producing the α-olefin polymer does not produce such an amorphous polymer at all or is extremely small.

  By using in combination with a supported solid catalyst component obtained by supporting tetravalent titanium halide on magnesium halide particles, an organoaluminum compound as a co-catalyst, and an organosilicon compound as a polymerization third component, a certain amount of α- It is known that high stereoregularity and high activity polymerization of olefins can be realized (JP 57-63310 A, JP 58-83006 A, JP 61-78803 A).

  In addition, a solid product obtained by reacting an organomagnesium compound and a silicon halide compound in the presence of an ether compound, an ester compound, a solid catalyst component treated with titanium tetrachloride, an organoaluminum compound as a cocatalyst, a third polymerization It is known that a certain degree of high stereoregularity and high activity polymerization of α-olefin can be realized even in combination with an electron donating compound as a component (Japanese Patent Laid-Open Nos. 54-112983 and 56-30407). Publication).

  Specific examples of the organosilicon compound as the third component of polymerization used in these catalysts are tetraethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, and compounds having a cyclohexyl group.

  Furthermore, a polymerization example using an alkoxysilane having a cyclopentyl group having a substituent at a specific position is disclosed (JP-A-8-59730). Further, examples using an alkoxysilane having a cyclopropyl group and dicycloalkyl dialkoxysilane having two cycloalkyl groups having 2 or more different carbon atoms are also disclosed (Japanese Patent Laid-Open Nos. 10-147610 and 10). -147611). Furthermore, an example in which a silicon compound having a cyclic hydrocarbon group and a branched hydrocarbon group and having two different alkoxy groups is used is also disclosed (Japanese Patent Laid-Open No. 11-35620).

  However, in any case, although there is a level at which the non-extraction and non-decalcification process can be realized to some extent, further improvement is desired. Specifically, in order to improve the quality of the α-olefin polymer, it is desired to realize further highly stereoregular polymerization and to further increase the activity. In particular, in applications where high rigidity of the polymer is desired, such as in the field of injection molding, a high stereoregular polymer directly produces high-rigidity quality. The emergence of catalysts having the following is urgently desired.

  Furthermore, recently, high-speed processability is also required, and there is a demand for a catalyst that has a small amount of by-produced amorphous polymer and can easily adjust the molecular weight of the α-olefin polymer. Particularly in such a field, since a polymer having a lower molecular weight has better flowability at the time of melt processing, it is desirable that an amorphous polymer is few and a low molecular weight polymer can be produced.

  Under such circumstances, the problem to be solved by the present invention, that is, the object of the present invention, is an olefin composed of an organosilicon compound that is highly active and sufficiently high in the degree of stereoregular polymerization such that removal of the amorphous polymer is unnecessary. The object is to provide a polymerization catalyst component, a catalyst for olefin polymerization, a method for producing an olefin polymer, and a method for using the organosilicon compound. Moreover, the further object of this invention includes making it easy to adjust the molecular weight of a polymer.

（式中、ｎは１または２であり、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵およびＲ⁶はそれぞれ独立に水素原子、ハロゲン原子または炭化水素基であり、互いに結合して環をなしていてもよく、Ｒ⁷は炭化水素基である。ｎ＝２のとき、それぞれ２つあるＲ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵およびＲ⁶はそれぞれ同一であっても異なっていてもよい。） That is, the present invention relates to a magnesium atom, a titanium atom, a halogen atom, and an electron donating compound obtained by supporting a titanium compound (vii) and an electron donating compound (ii) on a magnesium compound (vi) having no reducing ability. It is obtained by contacting a catalyst component (C) for olefin polymerization comprising a solid catalyst component (A), an organoaluminum compound (B), and an organosilicon compound represented by the following general formula (1). The present invention relates to an olefin polymerization catalyst characterized by being produced, and a method for producing an olefin polymer characterized by polymerizing an olefin in the presence of the olefin polymerization catalyst.

(In the formula, n is 1 or 2, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, a halogen atom or a hydrocarbon group, R ⁷ is a hydrocarbon group, and when n = 2, each two R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be the same May be different.)

  As described above, according to the present invention, a catalyst component for olefin polymerization comprising an organosilicon compound that is highly active and capable of undergoing stereoregular polymerization that is sufficiently high that removal of the amorphous polymer is unnecessary, for olefin polymerization Provided are a catalyst, a method for producing an olefin polymer, and a method for using the organosilicon compound. In addition, according to the present invention, the industrial value of the polymer can be adjusted without reducing the stereoregularity of the polymer.

Hereinafter, the present invention will be described in more detail.
In the present invention, the term “polymerization” may be used to mean not only homopolymerization but also copolymerization, and the term “polymer” includes not only homopolymers but also copolymers. Sometimes used in meaning.

（式中、ｎは１または２であり、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵およびＲ⁶はそれぞれ独立に水素原子、ハロゲン原子または炭化水素基であり、互いに結合して環をなしていてもよく、Ｒ⁷は炭化水素基である。ｎ＝２のとき、それぞれ２つあるＲ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵およびＲ⁶はそれぞれ同一であっても異なっていてもよい。） The organosilicon compound used as a catalyst component for olefin polymerization in the present invention is an organosilicon compound represented by the following general formula (1).

(In the formula, n is 1 or 2, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, a halogen atom or a hydrocarbon group, R ⁷ is a hydrocarbon group, and when n = 2, each two R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be the same May be different.)

In the general formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are preferably each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or the number of carbon atoms. A cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, more preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a carbon atom. A cycloalkyl group having 3 to 10 carbon atoms, more preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms, and particularly preferably a hydrogen atom.

In the above general formula (1), R ⁷ is a hydrocarbon group, preferably an alkyl group having 1 to 20 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.

Specific examples of such an organosilicon compound include those having one cyclobutyl group (that is, those in which n is 1).
Cyclobutyltrimethoxysilane, 2-methylcyclobutyltrimethoxysilane, 3-methylcyclobutyltrimethoxysilane, 2-ethylcyclobutyltrimethoxysilane, 3-ethylcyclobutyltrimethoxysilane, 2-propylcyclobutyltrimethoxysilane 3-propylcyclobutyltrimethoxysilane, 2-butylcyclobutyltrimethoxysilane, 3-butylcyclobutyltrimethoxysilane, 2-phenylcyclobutyltrimethoxysilane, 3-phenylcyclobutyltrimethoxysilane, cyclobutyltriethoxy Silane, 2-methylcyclobutyltriethoxysilane, 3-methylcyclobutyltriethoxysilane, 2-ethylcyclobutyltriethoxysilane, 3-ethylcyclobutyltriethoxysilane, 2-propyl Pyrcyclobutyltriethoxysilane, 3-propylcyclobutyltriethoxysilane, 2-butylcyclobutyltriethoxysilane, 3-butylcyclobutyltriethoxysilane, 2-phenylcyclobutyltriethoxysilane, 3-phenylcyclobutyltriethoxy Such as silane.

Specific examples of compounds having two cyclobutyl groups (that is, n is 2) include the following compounds.
Dicyclobutyldimethoxysilane, di (2-methylcyclobutyl) dimethoxysilane, di (3-methylcyclobutyl) dimethoxysilane, bis (2,3-dimethylcyclobutyl) dimethoxysilane, bis (2,2-dimethylcyclobutyl) ) Dimethoxysilane, bis (3,3-dimethylcyclobutyl) dimethoxysilane, bis (2,4-dimethylcyclobutyl) dimethoxysilane, di (2-ethylcyclobutyl) dimethoxysilane, di (3-ethylcyclobutyl) dimethoxy Silane, bis (2,3-diethylcyclobutyl) dimethoxysilane, bis (2,2-diethylcyclobutyl) dimethoxysilane, bis (3,3-diethylcyclobutyl) dimethoxysilane, bis (2,4-diethylcyclobutyl) ) Dimethoxysilane, cyclobutyl (2- Tilcyclobutyl) dimethoxysilane, cyclobutyl (3-methylcyclobutyl) dimethoxysilane, cyclobutyl (4-methylcyclobutyl) dimethoxysilane, cyclobutyl (2-phenylcyclobutyl) dimethoxysilane, cyclobutyl (3-phenylcyclobutyl) dimethoxysilane , Cyclobutyl (4-phenylcyclobutyl) dimethoxysilane, cyclobutyl (2-ethylcyclobutyl) dimethoxysilane, cyclobutyl (3-ethylcyclobutyl) dimethoxysilane, cyclobutyl (4-ethylcyclobutyl) dimethoxysilane, 2-methylcyclobutyl (2-ethylcyclobutyl) dimethoxysilane, 3-methylcyclobutyl (3-ethylcyclobutyl) dimethoxysilane, 4-methylcyclobutyl (4-ethylcyclobutyl) E) Dimethoxysilane, cyclobutyl (2-fluorocyclobutyl) dimethoxysilane, cyclobutyl (3-fluorocyclobutyl) dimethoxysilane, cyclobutyl (4-fluorocyclobutyl) dimethoxysilane, cyclobutyl (2-chlorocyclobutyl) dimethoxysilane, cyclobutyl (3-chlorocyclobutyl) dimethoxysilane, cyclobutyl (4-chlorocyclobutyl) dimethoxysilane, dicyclobutyldiethoxysilane, di (2-methylcyclobutyl) diethoxysilane, di (3-methylcyclobutyl) diethoxy Silane, bis (2,3-dimethylcyclobutyl) diethoxysilane, bis (2,2-dimethylcyclobutyl) diethoxysilane, bis (3,3-dimethylcyclobutyl) diethoxysilane, bis (2,4- The Methylcyclobutyl) diethoxysilane, di (2-ethylcyclobutyl) diethoxysilane, di (3-ethylcyclobutyl) diethoxysilane, bis (2,3-diethylcyclobutyl) diethoxysilane, bis (2, 2-diethylcyclobutyl) diethoxysilane, bis (3,3-diethylcyclobutyl) diethoxysilane, bis (2,4-diethylcyclobutyl) diethoxysilane, cyclobutyl (2-methylcyclobutyl) diethoxysilane, Cyclobutyl (3-methylcyclobutyl) diethoxysilane, cyclobutyl (4-methylcyclobutyl) diethoxysilane, cyclobutyl (2-ethylcyclobutyl) diethoxysilane, cyclobutyl (3-ethylcyclobutyl) diethoxysilane, cyclobutyl ( 4-ethylcyclobutyl) di Toxisilane, 2-methylcyclobutyl (2-ethylcyclobutyl) diethoxysilane, 3-methylcyclobutyl (3-ethylcyclobutyl) diethoxysilane, 4-methylcyclobutyl (4-ethylcyclobutyl) diethoxysilane, Cyclobutyl (2-phenylcyclobutyl) diethoxysilane, cyclobutyl (3-phenylcyclobutyl) diethoxysilane, cyclobutyl (4-phenylcyclobutyl) diethoxysilane, cyclobutyl (2-fluorocyclobutyl) diethoxysilane, cyclobutyl ( 3-fluorocyclobutyl) diethoxysilane, cyclobutyl (4-fluorocyclobutyl) diethoxysilane, cyclobutyl (2-chlorocyclobutyl) diethoxysilane, cyclobutyl (3-chlorocyclobutyl) diethoxy Run, cyclobutyl (4-chloro-cyclobutyl) such as diethoxy silane and the like.

Moreover, the organosilane compound which has the group which any ^{one of} R < ¹ > -R < ⁶ > couple | bonded with the cyclobutyl group couple | bonded together and formed the polycycle with the cyclobutyl group is also mentioned.
For example, (bicyclo [2.1.0] -2-pentyl) trimethoxysilane, (bicyclo [2.2.0] -2-hexyl) trimethoxysilane, (bicyclo [3.2.0] -6- (Heptyl) trimethoxysilane, (bicyclo [4.2.0] -7-octyl) trimethoxysilane, (bicyclo [5.2.0] -8-nonanyl) trimethoxysilane, (bicyclo [6.2.0] ] -9-decanyl) trimethoxysilane, di (bicyclo [2.1.0] -2-pentyl) dimethoxysilane, di (bicyclo [2.2.0] -2-hexyl) dimethoxysilane, di (bicyclo [ 3.2.0] -6-heptyl) dimethoxysilane, di (bicyclo [4.2.0] -7-octyl) dimethoxysilane, di (bicyclo [5.2.0] -8-nonanyl) dimethoxysilane Di (bicyclo [6.2.0] -9-decanyl) dimethoxysilane, (bicyclo [2.1.0] -2-pentyl) triethoxysilane, (bicyclo [2.2.0] -2-hexyl) Triethoxysilane, (bicyclo [3.2.0] -6-heptyl) triethoxysilane, (bicyclo [4.2.0] -7-octyl) triethoxysilane, (bicyclo [5.2.0]- 8-nonanyl) triethoxysilane, (bicyclo [6.2.0] -9-decanyl) triethoxysilane, di (bicyclo [2.1.0] -2-pentyl) diethoxysilane, di (bicyclo [2 .2.0] -2-hexyl) diethoxysilane, di (bicyclo [3.2.0] -6-heptyl) diethoxysilane, di (bicyclo [4.2.0] -7-octyl) diethoxy Silane, Di ( Cyclo [5.2.0] -8-nonanyl) diethoxysilane, di (bicyclo [6.2.0] -9-decanyl) diethoxysilane and the like.

  In the general formula (1), n is 1 or 2, and preferably n is 2. More preferably, the organosilicon compound represented by the general formula (1) is di (substituted) cyclobutyldimethoxysilane or di (substituted) cyclobutyldiethoxysilane. Particularly preferred is di (substituted) cyclobutyldimethoxysilane, and most preferred is dicyclobutyldimethoxysilane.

  Such an organosilicon compound can be produced according to a known technique (Japanese Patent Laid-Open Nos. 8-157482 and 9-12584) or can be obtained from the manufacturer of such a compound.

[Olefin polymerization catalyst]
Examples of the olefin polymerization catalyst comprising the olefin polymerization catalyst component comprising such an organosilicon compound include a solid catalyst component (A) containing a magnesium atom, a titanium atom, a halogen atom and an electron donating compound, and an organoaluminum compound (B ), And an olefin polymerization catalyst using the olefin polymerization catalyst component (C) composed of the above organosilicon compound.

  The solid catalyst component (A) contains a magnesium atom, a titanium atom, a halogen atom, and an electron donating compound as essential components. However, the adjustment method is not limited as long as these components are contained. It can adjust by making it contact by the method of this.

For example, in the presence of an organosilicon compound (i) having a Si—O bond, the general formula Ti (OR ⁸ ) _a X _4-a (wherein R ⁸ represents a hydrocarbon group having 1 to 20 carbon atoms). , X represents a halogen atom, a represents a number satisfying 0 <a ≦ 4), and a trivalent titanium atom obtained by reducing a titanium compound (iii) with an organomagnesium compound (iv) After obtaining the solid product to be contained, a solid component obtained by treating the solid product with a halogen compound (v) of a metal of Group 4 to 6 of the periodic table, or a magnesium compound having no reducing ability (vi ) Is a solid component obtained by supporting titanium compound (vii) and electron donating compound (ii). As the solid catalyst component (A) used in the olefin polymerization catalyst of the present invention, the former solid component is preferably used. When the titanium compound (iii) is reduced with the organomagnesium compound (iv) in the presence of the organosilicon compound (i), it is preferable that an electron donating compound (ii) is further coexisted. These will be described in more detail below.

Organosilicon compound (i)
Examples of the organosilicon compound (i) having a Si—O bond include silicate esters, and are represented by the general formula R ⁹ _b Si (OR ¹⁰ ) _4-b (where R ⁹ and R ¹⁰ are the number of carbon atoms, respectively) A linear, branched or alicyclic alkyl group having 1 to 20 carbon atoms, an aryl group having 1 to 20 carbon atoms, or an aralkyl group having 1 to 20 carbon atoms, which may be the same or different. And b is a number satisfying 0 ≦ b <4). Preferred is an organosilicon compound with b = 0, and more preferred is an organosilicon compound in which R ¹⁰ is a linear alkyl group.

Specific examples include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraphenoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, butyltrimethoxysilane, isobutyltrimethoxysilane, tert-butyltrimethoxysilane, isopropyltrimethoxysilane. Methoxysilane, cyclohexyltrimethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, dipropyldimethoxysilane, propylmethyldimethoxysilane, diisopropyldimethoxysilane, dibutyldimethoxysilane, diisobutyldimethoxysilane, di- tert-butyldimethoxysilane, butylmethyldimethoxysilane, butylethyldimethoxysilane tert-butylmethyldimethoxysilane, isobutylisopropyldimethoxysilane, tert-butylisopropyldimethoxysilane, hexylmethyldimethoxysilane, hexylethyldimethoxysilane, dodecylmethyldimethoxysilane, dicyclopentyldimethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylethyldimethoxysilane, cyclopentyl Isopropyldimethoxysilane, cyclopentylisobutyldimethoxysilane, cyclopentyl-tert-butyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylisopropyldimethoxysilane, cyclohexylisobutyldimethoxysilane, Cyclohexyl-tert-butyldimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylphenyldimethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, phenylisopropyldimethoxysilane, phenylisobutyldimethoxysilane, phenyl-tert-butyldimethoxysilane, phenylcyclopentyldimethoxysilane, Vinylmethyldimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, butyltriethoxysilane, isobutyltriethoxysilane, tert-butyltriethoxysilane, isopropyltriethoxysilane, cyclohexyltriethoxysilane, phenyltriethoxysilane, vinyltriethoxy Silane, dimethyldiethoxysilane Run, diethyldiethoxysilane, dipropyldiethoxysilane, propylmethyldiethoxysilane, diisopropyldiethoxysilane, dibutyldiethoxysilane, diisobutyldiethoxysilane, di-tert-butyldiethoxysilane, butylmethyldiethoxysilane, butyl Ethyldiethoxysilane, tert-butylmethyldiethoxysilane, hexylmethyldiethoxysilane, hexylethyldiethoxysilane, dodecylmethyldiethoxysilane, dicyclopentyldiethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyl Diethoxysilane, diphenyldiethoxysilane, phenylmethyldiethoxysilane, vinylmethyldiethoxysilane, ethyltriisopropyl Examples include xyloxysilane, vinyltributoxysilane, phenyltri-tert-butoxysilane, 2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, trimethylphenoxysilane, methyltriallyloxysilane, and the like. it can. Among these, tetraalkoxysilane is preferable, and tetra-n-butoxysilane is particularly preferable.

Electron-donating compound (ii)
Examples of the electron donating compound (ii) include oxygenated electrons such as diethers, ketones, aldehydes, carboxylic acids, esters of organic acids or inorganic acids, acid amides of organic acids or inorganic acids, acid anhydrides, and the like. Nitrogen-containing electron-donating compounds such as donor compounds, ammonia, amines, nitriles, isocyanates and the like can be mentioned. Of these electron donating compounds, carboxylic acid esters or diethers are preferably used.

  Examples of the carboxylic acid esters include mono- and polyvalent carboxylic acid esters, and examples thereof include saturated aliphatic carboxylic acid esters, unsaturated aliphatic carboxylic acid esters, alicyclic carboxylic acid esters, and aromatic carboxylic acid esters. There may be mentioned acid esters. Specific examples include methyl acetate, ethyl acetate, phenyl acetate, methyl propionate, ethyl propionate, ethyl butyrate, ethyl valerate, ethyl acrylate, methyl methacrylate, ethyl benzoate, butyl benzoate, methyl toluate, toluyl Ethyl acetate, ethyl anisate, diethyl succinate, dibutyl succinate, diethyl malonate, dibutyl malonate, dimethyl maleate, dibutyl maleate, diethyl itaconate, dibutyl itaconate, monoethyl phthalate, dimethyl phthalate, methyl phthalate Examples thereof include ethyl, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-n-octyl phthalate, and diphenyl phthalate.

  Of these carboxylic acid esters, unsaturated aliphatic carboxylic acid esters such as methacrylic acid esters and maleic acid esters or aromatic carboxylic acid esters such as benzoic acid esters and phthalic acid esters are preferably used. Particularly preferred are aromatic polycarboxylic esters, and most preferred are phthalates.

（但し、Ｒ¹¹〜Ｒ¹⁴はそれぞれ独立に、炭素原子数１〜２０の直鎖状、分岐状もしくは脂環式のアルキル基、炭素原子数１〜２０のアリール基、または炭素原子数１〜２０のアラルキル基であり、Ｒ¹²および／またはＲ¹³は水素原子であってもよい。）で表されるジエーテル化合物である。 Preferred examples of diethers are preferably those of the general formula

(However, R ^{11 to} R ¹⁴ are each independently a linear, branched or alicyclic alkyl group having 1 to 20 carbon atoms, an aryl group having 1 to 20 carbon atoms, or 1 to 1 carbon atoms. 20 is an aralkyl group, and R ¹² and / or R ¹³ may be a hydrogen atom.)

  Specific examples include 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane, 2-isopropyl-2-3,7-dimethyloctyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclohexylmethyl-1,3-dimethoxypropane, 2 , 2-dicyclohexyl-1,3-dimethoxypropane, 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3- Dimethoxypropane, 2-isopropyl-2-cyclohexyl-1,3-dimethoxy Examples include propane, 2-isopropyl-2-cyclopentyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2-heptyl-2-pentyl-1,3-dimethoxypropane, and the like. it can.

Preferably, R ^{11 to} R ¹⁴ are each independently an alkyl group, more preferably R ¹² and R ¹³ are each independently a branched or alicyclic alkyl group, and R ¹¹ and R ¹⁴ are each independently And diethers represented by the above general formula, which are linear alkyl groups.
The electron donating compound (ii) may be a single compound or a plurality of types may be used simultaneously.

Titanium compound (iii)
General formula Ti (OR ⁸ ) _a X _4-a (wherein R ⁸ is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen atom, and a is a number satisfying 0 <a ≦ 4. A liquid titanium compound is preferably used as the titanium compound (iii) represented by

Specifically, Ti (OCH ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (OC ₃ H ₇ ) Cl ₃ , Ti (On-C ₄ H ₉ ) Cl ₃ , Ti (OC _{2 H 5) Br 3, Ti} (O-iso-C 4 H 9) trihalide alkoxy titanium Br _{3 etc., Ti (OCH 3) 2 Cl} 2, Ti (OC 2 H 5) 2 Cl 2, Ti ( _{OC 3 H 7) 2 Cl 2} , Ti (O-n-C 4 H 9) 2 Cl 2, Ti (OC 2 H 5) 2 Br 2, Ti (O-iso-C 4 H 9) 2 Br 2 , etc. Dihalogenated dialkoxytitanium, Ti (OCH ₃ ) ₃ Cl, Ti (OC ₂ H ₅ ) ₃ Cl, Ti (OC ₃ H ₇ ) ₃ Cl, Ti (On-C ₄ H ₉ ) ₃ Cl, Ti Halogenated trialkoxytitanium such as (OC ₂ H ₅ ) ₃ Br and Ti (O-iso-C ₄ H ₉ ) ₃ Br, Ti (OCH ₃ ) ₄ , Ti (OC _{2 H 5) 4, Ti (OC} 3 H 7) 4, Ti (O-n-C 4 H 9) 4, Ti (OC 2 H 5) 4, Ti (O-iso-C 4 H 9) 4 , etc. Examples thereof include tetraalkoxy titanium.

Among these, tetraalkoxy titanium is particularly preferably used. Two or more kinds of these titanium compounds may be mixed and used at an arbitrary ratio, or may be used in combination with a tetrahalogenated titanium compound such as TiCl ₄ . The titanium compound may be diluted with a hydrocarbon, a halogenated hydrocarbon or an aromatic hydrocarbon.

Organomagnesium compound (iv)
As the organomagnesium compound (iv), any type of organomagnesium compound having an Mg-carbon bond can be used. Among organomagnesium compounds, a Grignard compound represented by R ¹⁵ MgX (wherein R ¹⁵ represents an alkyl group having 1 to 8 carbon atoms, an aryl group, or an aralkyl group, and X represents a halogen atom), or R A compound represented by ¹⁶ R ¹⁷ Mg (wherein R ¹⁶ and R ¹⁷ each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group or an aralkyl group) is preferably used. Here, R ¹⁵ , R ¹⁶ and R ¹⁷ may be the same or different, and are methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, amyl group, isoamyl group, n -An hexyl group, an n-octyl group, a 2-ethylhexyl group, a phenyl group, a benzyl group or the like, an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group.

Specifically, as the Grignard compound, methylmagnesium chloride, erythrmagnesium chloride, ethylmagnesium bromide, ethylmagnesium iodide, propylmagnesium chloride, propylmagnesium bromide, butylmagnesium chloride, butylmagnesium bromide, sec-butylmagnesium chloride, sec- Examples of compounds represented by R ¹⁶ R ¹⁷ Mg include butyl magnesium bromide, tert-butyl magnesium chloride, tert-butyl magnesium bromide, amyl magnesium chloride, isoamyl magnesium chloride, hexyl magnesium chloride, phenyl magnesium chloride, and phenyl magnesium bromide. , Dimethylmagnesium, Examples include ethyl magnesium, dipropyl magnesium, diisopropyl magnesium, dibutyl magnesium, di-sec-butyl magnesium, di-tert-butyl magnesium, butyl-sec-butyl magnesium, diamyl magnesium, dihexyl magnesium, diphenyl magnesium, and butyl ethyl magnesium. It is done.
Of these, Grignard compounds are more preferably used.

  As the organic magnesium compound synthesis solvent, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether, diamyl ether, diisoamyl ether, dihexyl ether, dioctyl ether, diphenyl ether, dibenzyl ether, phenetole, anisole, Ether solvents such as tetrahydrofuran and tetrahydropyran can be used. Further, a hydrocarbon solvent such as hexane, heptane, octane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, or a mixed solvent of an ether solvent and a hydrocarbon solvent may be used.

The organomagnesium compound is preferably used in the form of an ether solution. In this case, the ether compound is more preferably an ether compound containing 6 or more carbon atoms in the molecule or an ether compound having a cyclic structure. Used for. In particular, it is preferable to use a Grignard compound represented by R ¹⁵ MgX in the state of an ether solution.

  Moreover, the hydrocarbon soluble complex of said organomagnesium compound and organometallic compound can also be used. Examples of such an organometallic compound include Li, Be, B, Al, or Zn organometal.

Group 4-6 metal halides of the periodic table (v)
Examples of Periodic Table Group 4-6 metals include Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, and W. The halogen compound (v) of Group 4 to 6 metal of the periodic table is preferably a halogen compound of at least one transition metal selected from Ti, Zr and Hf. In particular, a tetravalent titanium halogen compound is preferably used. Such a tetravalent titanium halogen compound has the general formula Ti (OR ¹⁸ ) _m X _4-m (where R ¹⁸ is a hydrocarbon group having 1 to 20 carbon atoms, and X is a halogen atom) , M is a number satisfying 0 ≦ m <4.) A preferred compound is a titanium halide compound represented by the following formula. R ¹⁸ is preferably an alkyl group having 1 to 8 carbon atoms.

  Specific examples of such compounds include titanium tetrachloride, titanium tetrabromide, titanium tetraiodide tetrahalides, methoxytrichlorotitanium, ethoxytrichlorotitanium, butoxytrichlorotitanium, ethoxytribromotitanium, isobutoxytri Trihalogenated alkoxytitanium such as bromotitanium, dimethoxydichlorotitanium, diethoxydichlorotitanium, dibutoxydichlorotitanium, dihalogenated dialkoxytitanium such as diethoxydibromotitanium, trimethoxychlorotitanium, triethoxychlorotitanium, tributoxychlorotitanium And monohalogenated trialkoxytitanium such as triethoxybromotitanium.

  Among these, titanium tetrahalide is preferable, and titanium tetrachloride is particularly preferable. These titanium compounds may be used alone or in combination of two or more. The titanium compound may be diluted with a hydrocarbon, a halogenated hydrocarbon or an aromatic hydrocarbon.

Magnesium compound having no reducing ability (vi)
The magnesium compound (vi) having no reducing ability is preferably magnesium halide such as magnesium chloride, magnesium bromide, magnesium iodide, magnesium fluoride, methoxy magnesium chloride, ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride. Alkoxymagnesium halides such as octoxymagnesium chloride, aryloxymagnesium halides such as phenoxymagnesium chloride, methylphenoxymagnesium chloride and butoxyphenoxymagnesium chloride, alkoxymagnesiums such as methoxymagnesium, ethoxymagnesium, isopropoxymagnesium, butoxymagnesium , Phenoxymagnesium, methylphenoxymagnesium, Aryloxy magnesium such as butoxy phenoxy magnesium or magnesium laurate, a carboxylic acid salt such as magnesium stearate.

  In addition, a hydrocarbon-soluble complex with an organometallic compound can also be used as the organomagnesium compound having no reducing ability. Examples of such an organometallic compound include Li, Be, B, Al, or Zn organometal.

Titanium compound (vii)
The titanium compound (vii) has a general formula Ti (OR ¹⁹ ) _k X _4-k (where R ¹⁹ is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen atom, and k is 0 ≦ and a titanium halide compound represented by the following formula: k <4. Specifically, titanium tetrahalides such as TiCl ₄ , TiBr ₄ , and TiI ₄ , Ti (OCH ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (OC ₃ H ₇ ) Cl ₃ , Ti ( _{O-n-C 4 H 9} ) Cl 3, Ti (OC 2 H 5) Br 3, Ti (O-iso-C 4 H 9) trihalide alkoxy titanium Br ₃ etc., Ti (OCH _{3) 2} Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ , Ti (OC ₃ H ₇ ) ₂ Cl ₂ , Ti (On-C ₄ H ₉ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Br ₂ , Dihalogenated dialkoxytitanium such as Ti (O-iso-C ₄ H ₉ ) ₂ Br ₂ , Ti (OCH ₃ ) ₃ Cl, Ti (OC ₂ H ₅ ) ₃ Cl, Ti (OC ₃ H ₇ ) ₃ Cl, _{Ti (O-n-C 4} H 9) 3 Cl, Ti (OC 2 H 5) 3 Br, Ti (O-iso-C 4 H 9) of ₃ Br etc. Ha Gen tri alkoxy titanium, and the like.

Of these, titanium tetrahalide is preferable, and TiCl ₄ is most preferable. These titanium compounds may be used by mixing a plurality of types at an arbitrary ratio. Further, the titanium compound may be diluted with a hydrocarbon, a halogenated hydrocarbon, or an aromatic hydrocarbon.

Preparation of solid catalyst component (A) The solid catalyst component (A) is usually adjusted in an inert gas atmosphere such as nitrogen or argon.

In the presence of an organosilicon compound (i) having an Si—O bond and an electron donating compound (ii), the general formula Ti (OR ⁸ ) _a X _4-a (wherein R ⁸ has 1 to 1 carbon atoms) 20 hydrocarbon groups, X represents a halogen atom, and a represents a number satisfying 0 <a ≦ 4), and is obtained by reducing a titanium compound (iii) with an organomagnesium compound (iv). As a method for obtaining a solid product containing a trivalent titanium atom and then treating the solid product with a halogen compound (v) of a group 4-6 metal in the periodic table, (i) and A method in which (iii) is added to the mixture of (ii), (iv) is contacted, and then treated in (v);
A method of adding (ii) to a mixture of (i) and (iii), then contacting (iv) and then treating with (v);
A method of adding (i) to a mixture of (ii) and (iii), then contacting (iv) and then treating with (v);
A method of adding a mixture of (ii) and (iii) to (i), then contacting (iv) and then treating with (v);
A method of adding a mixture of (i) and (iii) to (ii), then contacting (iv) and then treating with (v);
A method of adding a mixture of (i) and (ii) to (iii), then contacting (iv) and then treating with (v);
Any of these may be used. Among these, the method of adding (iii) to the mixture of (i) and (ii), bringing (iv) into contact with the mixture, and then treating with (v) is preferable from the viewpoint of catalytic activity.

The temperature during the reduction reaction is usually in the temperature range of -50 ° C to 70 ° C, preferably -30 ° C to 50 ° C, particularly preferably -25 ° C to 35 ° C. If the temperature is high, the particle properties may deteriorate.
The treatment temperature in (v) is usually in the temperature range of −50 ° C. to 200 ° C., preferably 30 ° C. to 150 ° C., particularly preferably 60 ° C. to 130 ° C. If the contact temperature is high, the particle properties may deteriorate.

Examples of the method for supporting the titanium compound (vii) and the electron donating compound (ii) on the magnesium compound (vi) having no reducing ability include the following methods.
For example, it can be obtained by bringing a magnesium compound liquid in a liquid state comprising a magnesium compound (vi) having no reducing ability, an electron donating compound (ii), and a hydrocarbon solvent into contact with the titanium compound (vii).

  The contact temperature is usually −70 ° C. to 200 ° C., preferably −50 ° C. to 150 ° C., particularly preferably −30 ° C. to 130 ° C.

  Moreover, when preparing these solid catalyst components, it is also possible to coexist a porous substance such as an inorganic oxide or an organic polymer and impregnate the porous substance with the solid product. As such a porous substance, those having a pore volume of 0.3 ml / g or more and an average particle diameter of 5 to 300 μm at a pore radius of 20 to 200 nm are preferable.

Examples of the porous inorganic oxide include SiO ₂ , Al ₂ O ₃ , MgO, TiO ₂ , ZrO ₂ , SiO ₂ · Al ₂ O ₃ composite oxide, MgO · Al ₂ O ₃ composite oxide, MgO · SiO ₂ · Al ₂ O ₃ composite oxide can be used. Examples of the porous organic polymer include polystyrene, styrene-divinylbenzene copolymer, styrene-N, N′-alkylene dimethacrylamide copolymer, styrene-ethylene glycol dimethacrylate copolymer, polyethyl acrylate, acrylic Acid methyl-divinylbenzene copolymer, ethyl acrylate-divinylbenzene copolymer, polymethyl methacrylate, methyl methacrylate-divinylbenzene copolymer, polyethylene glycol dimethacrylate, polyacrylonitrile, acrylonitrile-divinylbenzene copolymer, Polyvinyl chloride, polyvinyl pyrrolidine, polyvinyl pyridine, ethyl vinyl benzene-divinyl benzene copolymer, polyethylene, ethylene-methyl acrylate copolymer, polypropylene Examples thereof include polymers of restyrene type, polyacrylic acid ester type, polyacrylonitrile type, polyvinyl chloride type, and polyolefin type. Among these porous _{materials, SiO 2, Al 2 O 3} , or a styrene - divinylbenzene copolymer are preferably used.

  The amount of the electron donating compound (ii) used in the preparation of the solid catalyst component is usually (ii) / (iv) = 0.0001 to 1, preferably in the molar ratio of (ii) to the organomagnesium compound (iv). Is in the range of 0.0005 to 0.6, particularly preferably 0.001 to 0.1. The amount of the organomagnesium compound (iv) used is usually (i) / (iv) = 0.1 to 10, preferably 0.2 to the molar ratio with the organosilicon compound (i) having a Si—O bond. 5.0, particularly preferably in the range of 0.5 to 2.0. The used amount of the titanium compound (iii) is usually (iii) / (i) = 0.001 to 10, preferably 0.01 to 5, particularly preferably 0.00 in terms of a molar ratio with the organosilicon compound (i). It is the range of 02-2. The usage-amount of the halogen compound (v) of a periodic table group 4-6 metal is 10-10000 normally with respect to the titanium atom in the solid product containing a trivalent titanium atom, Preferably it is 30-5000. Especially preferably, it is the range of 100-3000. In addition, when the magnesium compound (vi) is used, the amount used is usually (ii) / (vi) = 0.01 to 10, preferably 0.1 to 0.1 in terms of a molar ratio with the electron donating compound (ii). The amount of titanium compound (vii) used is usually in the molar ratio of (vii) / (vi) = 0.01 to 1000, preferably 0.1 to 200.

  The obtained solid catalyst component is preferably washed with a hydrocarbon solvent at 0 to 150 ° C. (more preferably 60 to 130 ° C.). As this hydrocarbon solvent, an aliphatic hydrocarbon or an aromatic hydrocarbon solvent is preferably used. Particularly preferably, toluene is used.

(B) Organoaluminum compound The organoaluminum compound used in the present invention has at least one Al-carbon bond in the molecule. A typical one is shown in the following general formula.
R ²⁰ _r AlY _3-r
R ²¹ R ²² Al—O—AlR ²³ R ²⁴
(Wherein R ^{20 to} R ²⁴ represent a hydrocarbon group having 1 to 20 carbon atoms, Y represents a halogen atom, a hydrogen atom or an alkoxy group, and r is a number satisfying 2 ≦ r ≦ 3. .) Specific examples of organoaluminum compounds include trialkylaluminum such as triethylaluminum, triisobutylaluminum, and trihexylaluminum, dialkylaluminum hydride such as diethylaluminum hydride and diisobutylaluminum hydride, dialkylaluminum halide such as diethylaluminum chloride, and triethyl. Mixtures of trialkylaluminum and dialkylaluminum halides, such as a mixture of aluminum and diethylaluminum chloride, tetraethyldialumoxane, tetrabutyldialumoxane, etc. An example is rualkylalumoxane.

  Of these organoaluminum compounds, trialkylaluminum, a mixture of trialkylaluminum and dialkylaluminum halide, or alkylalumoxane is preferred, and triethylaluminum, triisobutylaluminum, a mixture of triethylaluminum and diethylaluminum chloride, or tetraethyldialumonium. Xane is preferred.

[Olefin polymerization method]
The method for producing an olefin polymer of the present invention is a method for producing an olefin polymer in which an olefin is polymerized in the presence of the above-mentioned catalyst for olefin polymerization. The present invention is particularly suitably applied to a method for producing an isotactic α-olefin polymer.

  The α-olefin herein is an α-olefin having 3 or more carbon atoms, and specific examples thereof include propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, decene-1, Linear monoolefins such as, branched monoolefins such as 3-methylbutene-1, 3-methylpentene-1, 4-methylpentene-1, and vinylcyclohexane. One type of these α-olefins may be used, or two or more types may be used in combination. Among these α-olefins, it is preferable to carry out homopolymerization using propylene or butene-1, or to carry out copolymerization using a mixed olefin containing propylene or butene-1 as a main component. It is particularly preferable to carry out homopolymerization or to carry out copolymerization using a mixed olefin mainly composed of propylene (for example, propylene and ethylene, propylene and butene-1). In the copolymerization in the present invention, two or more kinds of olefins selected from ethylene and the above α-olefin can be mixed and used. Furthermore, a compound having a polyunsaturated bond such as a conjugated diene or a non-conjugated diene can be used for the copolymerization. And hetero block copolymerization which superposes | polymerizes in 2 steps or more can also be performed easily.

  The method for supplying each catalyst component to the polymerization tank is not particularly limited except that the catalyst component is supplied in an inert gas such as nitrogen or argon in the absence of moisture.

  The olefin polymerization catalyst component (C) comprising the solid catalyst component (A), the organoaluminum compound (B), and the organosilicon compound described above may be supplied separately, or either of them may be contacted in advance. You may supply.

  In the present invention, it is possible to carry out olefin polymerization in the presence of the above-mentioned catalyst, but prepolymerization described below may be carried out before such polymerization (main polymerization).

  The prepolymerization is preferably carried out in a slurry state by supplying a small amount of olefin in the presence of the solid catalyst component (A) and the organoaluminum compound (B). Examples of the solvent used for the slurry include inert hydrocarbons such as propane, butane, isobutane, pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, and toluene. Further, when slurrying, a liquid olefin can be used instead of a part or all of the inert hydrocarbon solvent.

  The amount of the organoaluminum compound used in the prepolymerization can be selected in a wide range such as 0.5 to 700 mol per 1 mol of titanium atom in the solid catalyst component, preferably 0.8 to 500 mol, 200 moles are particularly preferred.

  The amount of olefin to be prepolymerized is usually 0.01 to 1000 g, preferably 0.05 to 500 g, particularly preferably 0.1 to 200 g, per 1 g of the solid catalyst component.

The slurry concentration during the prepolymerization is preferably 1 to 500 g-solid catalyst component / liter-solvent, and more preferably 3 to 300 g-solid catalyst component / liter-solvent. The prepolymerization temperature is preferably -20 to 100 ° C, particularly preferably 0 to 80 ° C. The partial pressure of the olefin in the gas phase portion in the prepolymerization is preferably 0.01~20kg / cm ^2, especially 0.1 to 10 / cm ² is preferred, the pressure in the prepolymerization, in liquid at a temperature This is not the case for certain olefins. Further, the prepolymerization time is not particularly limited, but usually 2 minutes to 15 hours is preferable.

  As a method of supplying the solid catalyst component (A), the organoaluminum compound (B), and the olefin when carrying out the prepolymerization, the olefin after the solid catalyst component (A) and the organoaluminum compound (B) are brought into contact with each other is used. Any method may be used, such as a method for supplying the organic aluminum compound (B) after the solid catalyst component (A) and the olefin are brought into contact with each other. In addition, as a method for supplying olefin, either a method of sequentially supplying olefin while maintaining the inside of the polymerization tank at a predetermined pressure, or a method of supplying all the predetermined amount of olefin first is used. good. It is also possible to add a chain transfer agent such as hydrogen in order to adjust the molecular weight of the resulting polymer.

  Furthermore, when the solid catalyst component (A) is prepolymerized with a small amount of olefin in the presence of the organoaluminum compound (B), the above component (C) may coexist as necessary. The component (C) used is a part or all of the component (C). The amount used is usually 0.01 to 400 mol, preferably 0.02 to 200 mol, particularly preferably 0.03 to 100 mol, per 1 mol of titanium atoms contained in the solid catalyst component (A). Yes, with respect to the organoaluminum compound (B), it is usually 0.003 to 5 mol, preferably 0.005 to 3 mol, and particularly preferably 0.01 to 2 mol.

  There is no particular limitation on the method for supplying the component (C) during the prepolymerization, and the component (C) may be supplied separately from the organoaluminum compound (A) or may be supplied in contact with the component in advance. Further, the olefin used in the prepolymerization may be the same as or different from the olefin used in the main polymerization.

  An α-olefin polymerization catalyst comprising the solid catalyst component (A), the organoaluminum compound (B) and the component (C) described above, either after the prepolymerization as described above or without performing the prepolymerization. The main polymerization of α-olefin can be carried out in the presence of.

  The amount of the organoaluminum compound used in the main polymerization can be selected in a wide range such as 1 to 1000 mol per 1 mol of titanium atom in the solid catalyst component (A), and the range of 5 to 600 mol is particularly preferable.

  Moreover, said (C) component used at the time of this superposition | polymerization is 0.1-2000 mol normally with respect to 1 mol of titanium atoms contained in a solid catalyst component (A), Preferably 0.3-1000 mol, Especially preferably, it is 0.5-800 mol, and is 0.001-5 mol normally with respect to an organoaluminum compound, Preferably it is 0.005-3 mol, Most preferably, it is 0.01-1 mol.

Although this superposition | polymerization can be implemented over -30-300 degreeC normally, 20-180 degreeC is preferable. Although there is no restriction | limiting in particular about the superposition | polymerization pressure, Generally the pressure of a normal pressure-100 kg / cm < ² >, Preferably about 2-50 kg / cm < ² > is employ | adopted from the point of being industrial and economical. As the polymerization method, either batch type or continuous type is possible. Further, slurry polymerization or solution polymerization using an inert hydrocarbon solvent such as propane, butane, isobutane, pentane, hexane, heptane, and octane, and bulk polymerization or gas phase polymerization using a liquid olefin as a medium at the polymerization temperature are also possible.

  During the main polymerization, a chain transfer agent such as hydrogen can be added to adjust the molecular weight of the polymer. In the present invention, by using a small amount of hydrogen, the molecular weight of the polymer can be lowered while suppressing an increase in the amorphous polymer, and the molecular weight of the polymer is easily controlled.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not specifically limited by the following examples. In the examples, evaluation methods for various physical properties of the polymer are as follows.

(1) CXS: The amount soluble in cold xylene at 20 ° C. was expressed as a percentage (wt%).
In general, the smaller the value of CXS, the smaller the amorphous polymer and the higher the stereoregularity.

(2) Intrinsic viscosity (hereinafter abbreviated as [η]): measured at tetralin solvent at 135 ° C.

(3) Bulk density: Measured according to JIS K-6721-1966.

(4) Composition analysis: Ti content is determined by decomposing solid components with dilute sulfuric acid, adding excess hydrogen peroxide solution, and measuring 410 nm characteristic absorption using Hitachi double beam spectrophotometer U-2001 type. It was determined by a calibration curve. The alkoxy group content was determined by decomposing the solid component with water and then measuring the corresponding alcohol amount using a gas chromatography internal standard method. The electron donor content was determined by gas chromatography internal standard method after decomposing the solid component with water and extracting the soluble component with a saturated hydrocarbon solvent.

[Example 1]
(A) Synthesis of solid catalyst component (A) After replacing a 500 ml flask equipped with a stirrer, a dropping funnel and a thermometer with nitrogen, 31.74 g of MgCl ₂ (manufactured by Aldrich), 167 ml of N-decane, 2- 157 ml of ethylhexyl alcohol was added and stirring was started. This was heated up to 130 degreeC and stirred for 2 hours.
7.54 g of phthalic anhydride was further added thereto, and the mixture was stirred at 130 ° C. for 1 hour. After the reaction, the reaction mixture was cooled to room temperature, and then dropped into 1330 ml of titanium tetrachloride over 2 hours while maintaining -20 ° C. After completion of the dropping, the temperature was slowly raised to room temperature over 1 hour and a half and stirred. After confirming the reaction, the temperature was further raised to 110 ° C. over 2.5 hours, and 17.9 ml of diisobutyl phthalate was added. After stirring at 110 ° C. for 2 hours, solid-liquid separation was performed at the same temperature, and 1330 ml of titanium tetrachloride was again added to the solid component, followed by stirring at 110 ° C. for 2 hours. It was washed 3 times with 200 ml of IPSOLVENT2028 made by Idemitsu Petrochemical Co., Ltd. at the same temperature. Then, it wash | cleaned 3 times by 200 ml of n-hexane, and it dried under reduced pressure at 40 degreeC, and obtained 37.9g of solid catalyst components (A-2). The solid catalyst component contained 1.72% by weight of titanium atoms.

(B) Polymerization of propylene
3. A 3 liter stirred stainless steel autoclave was purged with argon, 2.6 mmol of triethylaluminum, 0.26 mmol of dicyclobutyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.), and the solid catalyst component (A-2) synthesized above. 3 mg was charged, and hydrogen corresponding to a partial pressure of 0.33 kg / cm ² was added. Next, 780 g of liquefied propylene was charged, the temperature of the autoclave was raised to 80 ° C., and polymerization was carried out at 80 ° C. for 1 hour. After the polymerization was completed, unreacted monomers were purged. The produced polymer was dried under reduced pressure at 60 ° C. for 2 hours to obtain polypropylene powder.

[Comparative Example 1]
Polymerization of propylene was carried out in the same manner as in Example 1 (b) except that dicyclopentyldimethoxysilane was used instead of dicyclobutyldimethoxysilane. The results are shown in Table 1.

FIG. 1 is a flowchart for helping understanding of the present invention. This flowchart is a representative example of the embodiment of the present invention, and the present invention is not limited to this.

Claims (3)

Magnesium atom, titanium atom, halogen atom, and electron obtained by supporting titanium halide (vii) and aromatic polyvalent carboxylic acid ester as electron donating compound (ii) on magnesium halide (vi) Contacting the catalyst component (C) for olefin polymerization comprising the solid catalyst component (A), the organoaluminum compound (B), which is a solid component containing a donor compound, and the organosilicon compound represented by the following general formula (1) An olefin polymerization catalyst characterized by being obtained.

(In the formula, n is 2, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, a halogen atom or a hydrocarbon group, and are bonded to each other to form a ring. R ⁷ is a hydrocarbon group, and when n = 2, two R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different, respectively. May be.) The catalyst for olefin polymerization according to claim 1, wherein the catalyst for olefin polymerization is a catalyst for homopolymerization of propylene or butene-1 or a catalyst for copolymerization of mixed olefin mainly composed of propylene or butene-1. . In the presence of an olefin polymerization catalyst according to claim 1 or 2, process for producing an olefin polymer which comprises polymerizing an olefin.

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