JPH11106434A - Propylenic random copolymer and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a propylenic random copolymer low in melting point, excellent in moldability into films, and capable of being molded into the films good in transparency, and excellent in low temperature heat sealability, blocking resistance and slipperiness. SOLUTION: This propylenic random copolymer is obtained by copolymerizing propylene with ethylene and at least one kind of α-olefin selected from α-4-20C olefins in the presence of a Ziegler type catalyst, and contains the halogen- containing residues of the catalyst. The copolymer has a propylene content of 90-99.5 wt.%, a melting point of 110-140 deg.C, a xylene-soluble content of 1-7 wt.% at 20 deg.C, a mol.wt. distribution (Mw/Mn) of 6-10, and a MFR of 0.1-10 g/10 min. And a method for producing the random copolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a propylene random copolymer and a method for producing the same, and more particularly, to producing a film having good transparency, excellent low-temperature heat sealability and excellent blocking resistance. The present invention relates to a low-melting propylene random copolymer excellent in moldability and a method for producing the same.

[0002]

BACKGROUND OF THE INVENTION Crystalline polypropylene has a structure with excellent stereoregularity, a high melting point, heat resistance,
It has excellent properties such as rigidity and transparency, and is used for a wider range of applications than before.

A propylene random copolymer obtained by copolymerizing propylene with another α-olefin is also known. As such a propylene random copolymer, for example, a random copolymer of propylene and ethylene is used. Copolymers, random copolymers of propylene and α-olefins having 4 or more carbon atoms, and ternary random copolymers of propylene, ethylene and α-olefins having 4 or more carbon atoms are known.

In the propylene random copolymer as described above, it is known that as the copolymerization ratio of the monomer to be copolymerized with propylene is increased, the melting point can be lowered and the heat sealing property is improved. I have.

In producing such a propylene-based random copolymer, a catalyst for olefin polymerization comprising a solid titanium catalyst component, an organoaluminum compound and, if necessary, an electron donor has been widely used.

[0006] However, when the copolymerization ratio of α-olefin to be copolymerized with propylene is increased, the composition distribution generally tends to be widened, and the composition distribution is disturbed and the stereoregularity is reduced, so that the homogeneity is reduced. It becomes difficult to obtain a propylene-based random copolymer having a composition. For this reason, in the propylene-based random copolymer, as the composition ratio of the copolymerized monomer increases, the amount of the sticky component during film formation tends to increase, and the blocking resistance tends to deteriorate. Further, the molecular weight distribution (Mw / Mn) was narrowed, and the moldability tended to be reduced.

Further, when a catalyst which requires removal (decalcification) of the catalyst after the polymerization reaction is used as an olefin polymerization catalyst, the decalcification step is required, which increases the production cost of the propylene random copolymer.

In order to solve the above-mentioned problems, the present inventors have intensively studied the production of a propylene-based random copolymer using a so-called non-deashing catalyst which does not require deashing of the catalyst. (1) In addition to a liquid magnesium compound, a liquid titanium compound, and an electron donor, a solid titanium catalyst component obtained by contacting a solid divalent metal halide, and (2) an organoaluminum compound When,
(3) In the presence of an olefin polymerization catalyst comprising a specific electron donor, by copolymerizing propylene and an α-olefin having 4 to 20 carbon atoms, transparency is good and low-temperature heat sealability is improved. It has been found that a low-melting-point propylene-based random copolymer excellent in moldability and capable of producing a film excellent in blocking resistance as well as excellent can be obtained, and [I] (1) the solid titanium catalyst described above. Ingredients, (2) organoaluminum compound, (3)
A specific electron donor, a prepolymerization catalyst obtained by prepolymerizing an olefin, [II] an organoaluminum compound,
[III] By copolymerizing propylene and an α-olefin having 4 to 20 carbon atoms in the presence of an olefin polymerization catalyst comprising a specific electron donor, the transparency is good,
It has been found that a low-melting-point propylene-based random copolymer excellent in moldability can be obtained, which can produce a film having excellent low-temperature heat sealability and excellent blocking resistance, and completed the present invention. Was.

[0009]

An object of the present invention is to solve the problems associated with the prior art as described above, and to produce a film having good transparency, excellent low-temperature heat sealability and excellent blocking resistance. An object of the present invention is to provide a low-melting propylene-based random copolymer excellent in moldability and a method for producing the same.

[0010]

SUMMARY OF THE INVENTION A propylene random copolymer according to the present invention comprises propylene and at least one α-olefin selected from ethylene and an α-olefin having 4 to 20 carbon atoms in the presence of a Ziegler-type catalyst. A propylene-based random copolymer obtained by copolymerization and containing a halogen-containing catalyst residue of the catalyst, wherein the propylene-based random copolymer has (i) a propylene content of 90 to 9
(Ii) a differential scanning calorimeter (DS)
The melting point measured by C) is 110-140 ° C.,
(Iii) the amount of the xylene-soluble component at 20 ° C. is 1 to 7% by weight, and (iv) the molecular weight distribution (Mw / Mn) measured by gel permeation chromatography (GPC) is in the range of 6 to 10. , (V) melt flow rate (JIS K-6758, 230 ° C, load 2.16 kg) is 0.1 to 10 g /
It is characterized by being within a range of 10 minutes.

The method for producing a propylene-based random copolymer according to the present invention comprises: (A) (a) a liquid magnesium compound;
(b) a liquid titanium compound, (c) a solid titanium catalyst component obtained by contacting an electron donor and (d) a solid divalent metal halide, and (B) an organoaluminum compound;
(C) In the presence of an olefin polymerization catalyst comprising an electron donor represented by the following general formula (1) or (2), at least one selected from propylene, ethylene and an α-olefin having 4 to 20 carbon atoms. It is characterized in that it is copolymerized with various α-olefins.

[0012]

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[In the formula (1) or (2), R
¹ represents a hydrocarbon group having 1 to 8 carbon atoms, and R ² represents a hydrocarbon group having ^{2 to} 24 carbon atoms, a hydrocarbon amino group having 2 to 24 carbon atoms, or a hydrocarbon alkoxy group having 1 to 24 carbon atoms. R ³ N represents a polycyclic amino group having 7 or more carbon atoms which forms a skeleton together with a nitrogen atom. Further, another method for producing a propylene-based random copolymer according to the present invention comprises: [I] (A) (a) a liquid magnesium compound, (b) a liquid titanium compound, (c) an electron donor, and (d)
A solid titanium catalyst component obtained by contacting a solid divalent metal halide, (B) an organoaluminum compound, and (C) an electron donor represented by the general formula (1) or (2). In the presence of an olefin polymerization catalyst comprising a prepolymerized catalyst obtained by prepolymerizing an olefin, [II] an organoaluminum compound, and [III] an electron donor represented by the general formula (1) or (2). , Propylene, and at least one α-olefin selected from ethylene and α-olefins having 4 to 20 carbon atoms.

The propylene random copolymer according to the present invention has a wide molecular weight distribution (Mw / Mn) and excellent moldability,
Moreover, a film having good transparency, excellent low-temperature heat sealability, and excellent blocking resistance can be formed.

[0015]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the propylene-based random copolymer according to the present invention and a method for producing the same will be described in detail.

Propylene random copolymer The propylene random copolymer according to the present invention comprises, in the presence of a Ziegler-type catalyst, propylene, at least one kind selected from ethylene and an α-olefin having 4 to 20 carbon atoms. Obtained by copolymerization with α-olefin, and
It contains a halogen-containing catalyst residue of the catalyst.

This Ziegler-type catalyst will be described later in the method for producing a propylene-based random copolymer according to the present invention, but this catalyst does not require a deashing step, and is a so-called non-deashed catalyst.

C4-20 copolymerized with propylene
Specific examples of the α-olefin include propylene,
1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-
Methyl-1-pentene, 4,4-dimethyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene,
Examples thereof include 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene.

Ethylene and the above-mentioned α having 4 to 20 carbon atoms
-The olefins can be used alone or in combination of two or more. Specific examples of the propylene random copolymer according to the present invention include propylene / ethylene random copolymer, propylene / 1-butene random copolymer, propylene / 1-hexene random copolymer, propylene / 1-octene random Copolymer, propylene / ethylene / 1-butene random copolymer, propylene / ethylene / 1-hexene random copolymer, propylene / ethylene / 1-octene random copolymer, propylene / 1-butene / 1-hexene random Copolymers, propylene / 1-butene / 1-octene random copolymer and the like.

The propylene random copolymer according to the present invention may contain a small amount of a vinyl compound or a polyene compound in addition to the above-mentioned α-olefin as long as the object of the present invention is not impaired.

Examples of the vinyl compound include styrene, dimethylstyrenes, allylnaphthalene, allylnorbornane, vinylnaphthalenes, allyltoluenes, allylbenzene, vinylcyclopentane, vinylcyclohexane, vinylcycloheptane, allyltrialkyl Examples include silanes.

Specific examples of the polyene compound include 1,3-butadiene, 1,3-pentadiene, 1,4-pentadiene, 1,3-hexadiene, 1,4-hexadiene, 1,5-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4
-Hexadiene, 6-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 6-ethyl-1,6-octadiene,
6-propyl-1,6-octadiene, 6-butyl-1,6-octadiene, 6-methyl-1,6-nonadiene, 7-methyl-1,6-nonadiene, 6-ethyl-1,6-nonadiene, 7-ethyl-1,6-
Nonadiene, 6-methyl-1,6-decadiene, 7-methyl-1,6
-Diene compounds such as decadiene, 6-methyl-1,6-undecadiene, 1,7-octadiene, 1,9-decadiene, isoprene, butadiene, ethylidene norbornene, vinyl norbornene and dicyclopentadiene. These may be used in combination of two or more.

The (i) propylene content, (ii) melting point, and (iii) 20 of the propylene random copolymer according to the present invention.
Xylene solubles at (° C), (iv) molecular weight distribution (M
w / Mn) and melt flow rate (MFR) are as follows. (I) The propylene-based random copolymer according to the present invention comprises:
Propylene content is 90 to 99.5% by weight, preferably 94 to 97.5% by weight, ethylene content or α-olefin content of 4 to 20 carbon atoms, or ethylene content and 4 to 20 carbon atoms Is 0.5 to 10% by weight, preferably 2.5 to 6% by weight. Propylene content and ethylene content and / or
Alternatively, the total content of the α-olefin having 4 to 20 carbon atoms is 100% by weight. Propylene content is different from other α
-Can be calculated from the olefin content.

The ethylene content in the propylene-based random copolymer can be measured as follows. Here, ethylene having an ethylene content refers to isolated ethylene. Isolated ethylene means an ethylene unit in a portion where three or more ethylene units are continuously polymerized in a polymer chain, and an isolated ethylene content (C
² ) is measured as follows. That is, 0.5 g of a sample is heated for 2 minutes and 30 seconds using a hydraulic molding machine (manufactured by Toho Press Co., Ltd.), degassed at 20 atm, and then pressed at 80 atm for 10 seconds. Subsequently, a film is obtained by pressing at 100 atm for 1 minute using a hydraulic molding machine in which cooling water is circulated. At this time, an iron spacer is used so that the thickness of the obtained film is about 0.3 mm. The obtained film was analyzed using a DS-701G type diffraction grating infrared spectrophotometer manufactured by JASCO Corporation,
The infrared absorption spectrum in the range of 00 to 650 cm ^-1 is measured by transmittance. And around 760 cm ^-1 of the resulting chart, drawing a common tangent of the maximum point in the vicinity of 700 cm ^-1, and baseline. A line perpendicular to the wavenumber line is drawn from the transmittance at the minimum absorption point of 733 cm ^-1 (T%) and the minimum point of absorption at 733 cm ^-1 , and the transmittance (T ₀ %) at the intersection of the perpendicular and the baseline is read. Absorbance at 733 cm ^-1 (D
_{733 = log (T 0 / T} )) is calculated. Next, the content of isolated ethylene (C ² ) is determined from the absorbance (D ₇₃₃ ) of ₇₃₃ cm ⁻¹ and the thickness (L (mm)) of the film used for measurement by the following equation.

Isolated ethylene content (%) = 6.17 × (D ₇₃₃ / L) 1- as a representative of an α-olefin having 4 to 20 carbon atoms
The butene content (C ⁴ ) can be measured as described below.

That is, a film is obtained from 0.5 g of a sample in the same manner as described above. At this time, an iron spacer is used so that the thickness of the obtained film is about 0.3 mm. About the obtained film, A-30 manufactured by JASCO Corporation
800 to 700 using a type 2 diffraction grating infrared spectrophotometer.
The infrared absorption spectrum in the cm ^-1 region is measured by transmittance. Around 775 cm ^{-1 of the} resulting chart and 750 c
A common tangent at the local maximum near m ^-1 is drawn and used as a baseline. The transmittance (T%) at the minimum absorption point of 765 cm ^-1 and 7
A perpendicular line to the wave number line is drawn from the absorption minimum point at 65 cm ⁻¹ , and the transmittance at the intersection of the perpendicular line and the baseline (T ₀ %)
And the absorbance at ₇₆₅ cm ^-1 (D ₇₆₅ = log (T ₀
/ T)). Next, the 1-butene content (C ⁴ ) is determined from the absorbance (D ₇₆₅ ) of 733 cm ⁻¹ and the thickness (L (mm)) of the film used for measurement by the following equation.

1-butene content (%) = 7.77 × (D ₇₆₅ / L) (ii) Melting point (Tm) of the propylene-based random copolymer according to the present invention measured by a differential scanning calorimeter (DSC) )
Is 110 to 140 ° C, preferably 130 to 140 ° C.

The melting point (Tm) is measured by the following method. The measurement is performed using a Perkin-Elmer DSC-7 apparatus in accordance with ASTM-3417-75. That is, the temperature is raised from room temperature to 200 ° C. at 320 ° C./min, kept at 200 ° C. for 10 minutes, and then 3
Cool to 0 ° C. The calorific value curve when the polypropylene crystallizes at the time of this temperature decrease is processed by the analysis program of the DSC-7 type apparatus to determine the temperature at the top of the exothermic peak,
c. Subsequently, after holding at 30 ° C. for 5 minutes, 10
The temperature was raised to 200 ° C at a rate of ° C / min. The endothermic curve when the polypropylene melts at the time of this temperature rise is processed by the analysis program of the DSC-7 type apparatus, and the temperature at the top of the endothermic peak is determined and set as the melting point (Tm). (Iii) The amount of the xylene-soluble component at 20 ° C., which is a measure of the sticky component of the propylene-based random copolymer according to the present invention, is 1 to 7% by weight, preferably 1 to 5% by weight. Since the propylene-based random copolymer having the xylene-soluble component content within the above range has a small sticky component, a film having excellent blocking resistance can be formed. The film formed from the propylene-based random copolymer does not cause blocking not only during film formation but also during storage and use.

The amount of the xylene-soluble component at 20 ° C. is determined by dissolving the propylene-based random copolymer in hot xylene, cooling the mixture to 20 ° C., filtering the solute, concentrating the solute, and measuring the weight of the soluble component. Ask. (Iv), (v) The propylene random copolymer according to the present invention is obtained by gel permeation chromatography (G
PC), the molecular weight distribution (Mw / Mn: Mw = weight average molecular weight, Mn = number average molecular weight) is in the range of 6 to 10, preferably 8 to 10, and the melt flow rate (MFR; ASTM D) 1238, 230 ℃, load 2.16kg).
It is in the range of 1-10 g / 10 min, preferably 1-5. As described above, the propylene random copolymer according to the present invention has a melt flow rate in the above-mentioned range and has a wide molecular weight distribution (Mw / Mn) as described above. Excellent in nature.

The molecular weight distribution (Mw / Mn) was measured using a GPC (Waters 150C type, o-dichlorobenzene solvent, column) using polystyrene as a standard substance.
SHODEX, temperature 145 ° C., concentration 0.05%) and weight average molecular weight (Mw) and number average molecular weight (M
It was evaluated by the ratio of n).

Method for Producing Propylene-Based Random Copolymer The propylene-based random copolymer according to the present invention, having the above-mentioned properties, comprises (A) (a) a liquid magnesium compound, (b) a liquid titanium compound, c) an electron donor and (d)
In the presence of a catalyst for olefin polymerization comprising a solid titanium catalyst component obtained by contacting a solid divalent metal halide, (B) an organoaluminum compound, and (C) a specific electron donor, propylene and At least one selected from ethylene, ethylene and an α-olefin having 4 to 20 carbon atoms
It can be produced by copolymerizing with a kind of α-olefin.

First, the olefin polymerization catalyst (Ziegler type catalyst) will be described. [(A) Solid Titanium Catalyst Component] The (A) solid titanium catalyst component, which is the catalyst component of the olefin polymerization catalyst used in the present invention, includes (a) a liquid magnesium compound, (b) a liquid titanium compound, and (c) A) contacting an electron donor with (d) a solid divalent metal halide.

(A ) Liquid Magnesium Compound In the present invention, (A) the magnesium compound is used as a liquid when preparing the solid titanium catalyst component. The magnesium compound itself may be liquid or solid magnesium compound as long as the compound is in a magnesium compound solution.

As such a magnesium compound,
Examples thereof include a magnesium compound having reducing ability (a-1) and a magnesium compound having no reducing ability (a-2). Examples of the magnesium compound (a-1) having a reducing ability include an organic magnesium compound represented by the following formula.

[0035] MgX in ¹ _n R ¹ _2-n wherein, n = 0 ≦ n <2, R ¹ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl radical, n Is 0, two R ¹ may be the same or different. X ¹ is a halogen atom, a hydrogen atom or an alkoxy group.

As the organomagnesium compound (a-1) having such a reducing ability, specifically, dimethylmagnesium, diethylmagnesium, dipropylmagnesium, dibutylmagnesium, diamilmagnesium, dihexylmagnesium, didecylmagnesium, Dialkyl magnesium compounds such as octyl butyl magnesium and ethyl butyl magnesium, alkyl magnesium halides such as ethyl magnesium chloride, propyl magnesium chloride, butyl magnesium chloride, hexyl magnesium chloride, amyl magnesium chloride, butyl ethoxy magnesium, ethyl butoxy magnesium, octyl butoxy magnesium, etc. Alkyl magnesium alkoxide, butyl magnesium hydride and the like.

The magnesium compound having no reducing ability (a-
Examples of 2) include a magnesium compound represented by the following formula. Mg (OR ²⁾ in _n X _{^{2 2-n}} wherein, n = 0 ≦ n ≦ 2, R ⁵ is 1 to 20 carbon atoms
When n is 2, two R ² may be the same or different. X ² is a halogen atom or a hydrogen atom.

Examples of the magnesium compound (a-2) having no reducing ability include magnesium chloride,
Magnesium halides such as magnesium bromide, magnesium iodide and magnesium fluoride; alkoxymagnesium halides such as methoxymagnesium chloride, ethoxymagnesium chloride, isopropoxymagnesium chloride, butoxymagnesium chloride and octoxymagnesium chloride; phenoxymagnesium chloride; methylphenoxychloride Allyloxy magnesium halide such as magnesium,
Ethoxymagnesium, isopropoxymagnesium,
Butoxymagnesium, n-octoxymagnesium, 2-
Examples thereof include alkoxymagnesium such as ethylhexoxymagnesium, alloxymagnesium such as phenoxymagnesium and dimethylphenoxymagnesium, and magnesium hydride.

The magnesium compound having no reducing ability (a-
2) as further magnesium carboxylate such as magnesium laurate, magnesium stearate,
Magnesium metal can also be used.

The magnesium compound having no reducing ability (a-2) may be a compound derived from the above-mentioned magnesium compound having reducing ability (a-1) or a compound derived at the time of preparing the catalyst component. Good. In order to derive the magnesium compound having no reducing ability (a-2) from the magnesium compound having reducing ability (a-1), for example, a magnesium compound having reducing ability (a-1) is converted into a polysiloxane compound, It may be brought into contact with a halogen-containing silane compound, a halogen-containing aluminum compound, an ester, an alcohol, a halogen-containing compound, or a compound having an OH group or an active carbon-oxygen bond.

The magnesium compounds can be used alone or in combination of two or more. In addition, the magnesium compound having the above reducing ability
(a-1) and a magnesium compound having no reducing ability (a-
2) may form, for example, a complex compound or a double compound with a metal compound such as aluminum, zinc, boron, beryllium, sodium, or potassium as described below as the catalyst component (B), or May be used as a mixture.

As the magnesium compound used for the preparation of the solid titanium catalyst component (A), a magnesium compound other than those described above can be used. In the finally obtained solid titanium catalyst component (A), the halogen-containing magnesium It is preferably present in the form of a compound. Therefore, when a halogen-free magnesium compound is used, it is preferable to carry out a contact reaction with a halogen-containing compound during the preparation.

Among these, a magnesium compound (a-2) having no reducing ability is preferable, and a halogen-containing magnesium compound is particularly preferable. Among these, magnesium chloride, alkoxymagnesium chloride and allyloxymagnesium chloride are preferable.

Among the above magnesium compounds,
When the magnesium compound is a solid, the magnesium compound can be dissolved in an electron donor (ci) to form a liquid.

Examples of the electron donor (ci) include (c) alcohols, phenols, ketones, aldehydes, ethers, amines and the like as described below.
Pyridines and the like can be used.

As the electron donor (ci), tetraethoxytitanium, tetra-n-propoxytitanium, tetra-i-
Metal acid esters such as propoxytitanium, tetrabutoxytitanium, tetrahexoxytitanium, tetrabutoxyzirconium, and tetraethoxyzirconium can also be used.

Among these electron donors (ci), alcohols and metal acid esters are particularly preferably used. To dissolve the solid magnesium compound in the electron donor (ci), the solid magnesium compound and the electron donor (c
-i) and heating as necessary. This contact is usually carried out at 0 to 200 ° C, preferably 2 to 200 ° C.
The reaction can be performed at a temperature of 0 to 180 ° C, more preferably 50 to 150 ° C.

The above-mentioned dissolution is preferably carried out in the presence of a hydrocarbon solvent. As such hydrocarbon solvents, specifically, pentane, hexane, heptane,
Octane, decane, dodecane, tetradecane, aliphatic hydrocarbons such as kerosene, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, cyclooctane, alicyclic hydrocarbons such as cyclohexene, dichloroethane, dichloropropane, trichloroethylene,
Halogenated hydrocarbons such as chlorobenzene, benzene,
Aromatic hydrocarbons such as toluene and xylene are used.

(B) Liquid Titanium Compound In the present invention, a tetravalent titanium compound is particularly preferably used as (b) the liquid titanium compound. Examples of such a tetravalent titanium compound include a compound represented by the following formula.

Ti (OR) _g X _{4-g In the} formula, R is a hydrocarbon group, X is a halogen atom, and 0 ≦ g ≦ 4. Specific examples of such a compound include titanium tetrahalides such as TiCl ₄ , TiBr ₄ , and TiCl ₂ Br ₂ , Ti (OCH ₃ ) Cl ₃ , and Ti (OC
_{2 H 5) Cl 3, Ti} (On-C 4 H 9) Cl 3, Ti (OC 2 H 5) B
_{r 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 (On-C ₄ H ₉ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Br ₂
Such as dihalogenated dialkoxytitanium, Ti (OCH ₃ ) ₃
Cl, Ti (OC ₂ H ₅ ) ₃ Cl, Ti (On-C ₄ H ₉ ) ₃ Cl,
Monohalogenated trialkoxy titanium such as Ti (OC ₂ H ₅ ) ₃ Br, Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (On-
Tetraalkoxy titanium such as C ₄ H ₉ ) ₄ , Ti (O-iso-C ₄ H ₉ ) ₄ , and Ti (O-2-ethylhexyl) ₄ .

Of these, titanium tetrahalides are preferred, and titanium tetrachloride is particularly preferred. These titanium compounds can be used alone or in combination of two or more. The liquid titanium compound (b) may be used after being diluted with a hydrocarbon, a halogenated hydrocarbon, or an aromatic hydrocarbon.

(C) Electron Donor (A) The (c) electron donor used for preparing the solid titanium catalyst component includes alcohols, phenols, ketones, aldehydes, carboxylic acids, organic acid halides, and the like. Examples include esters, ethers, acid amides, acid anhydrides, ammonia, amines, nitriles, hydroxy ethers, isocyanates, nitrogen-containing cyclic compounds, and oxygen-containing cyclic compounds of organic acids or inorganic acids. More specifically, methanol, ethanol, propanol, butanol, pentanol, hexanol, 2-ethylhexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol, isopropyl benzyl C1-C18 alcohols such as alcohols, trichloromethanol,
C1-C18 halogen-containing alcohols such as trichloroethanol and trichlorohexanol, and carbon atoms which may have a lower alkyl group such as phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol and naphthol 6-20 ketones having 3-15 carbon atoms such as phenols, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, benzoquinone, carbon numbers such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, naphthaldehyde, etc. 2 to 15 aldehydes, methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, butyric acid Chill, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate Phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, ethyl anisate,
Organic acid esters having 2 to 30 carbon atoms such as ethyl ethoxybenzoate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethyl carbonate, dimethyl carbonate, acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid chloride, etc. C2 to C15 acid halides, methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, etc., C2 to C20 ethers, acetic acid N, N-dimethylamide, benzoic acid Acid amides such as acid N, N-diethylamide, toluic acid N, N-dimethylamide, methylamine, ethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine, tributylamine, tribenzylamine, tetramethylenediamine Amines such as hexamethylenediamine, nitriles such as acetonitrile, benzonitrile and trinitrile, hydroxy ethers such as 1-butoxyethanol, 2-butoxyethanol and 2-butoxypropanol, acetic anhydride, phthalic anhydride, benzoic anhydride, etc. Acid anhydrides, pyrroles, methylpyrroles, pyrroles such as dimethylpyrrole, pyrroline; pyrrolidine; indole; pyridine, methylpyridine, ethylpyridine,
Pyridines such as propylpyridine, dimethylpyridine, ethylmethylpyridine, trimethylpyridine, phenylpyridine, benzylpyridine and pyridine chloride; nitrogen-containing cyclic compounds such as piperidines, quinolines and isoquinolines; tetrahydrofuran; 1,4-cineole; And cyclic oxygenated compounds such as 8,8-cineole, pinolfuran, methylfuran, dimethylfuran, diphenylfuran, benzofuran, coumaran, phthalane, tetrahydropyran, pyran, and ditedropyran.

As the organic acid ester, a polycarboxylic acid ester having a skeleton represented by the following general formula can be mentioned as a particularly preferred example.

[0054]

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In the above formula, R ¹ is a substituted or unsubstituted hydrocarbon group, and R ² , R ⁵ and R ⁶ are a hydrogen atom or a substituted or unsubstituted hydrocarbon group, and R ³ and R ⁴ are , A hydrogen atom 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 to form a cyclic structure. When the hydrocarbon groups R ^{1 to} R ⁶ are substituted, the substituent contains a different atom such as N, O, S, and is, for example, C—O—C, COOR, COO.
It has groups such as H, OH, SO ₃ H, —C—N—C—, and NH ₂ .

Specific examples of such polycarboxylic acid esters include diethyl succinate, dibutyl succinate, diethyl methyl succinate, diisobutyl α-methylglutarate, diethyl methyl malonate, diethyl ethyl malonate and isopropyl malonate. Diethyl acrylate, diethyl butylmalonate, diethyl phenylmalonate, diethyl diethylmalonate, diethyl dibutylmalonate, monooctyl maleate, dioctyl maleate, dibutyl maleate, dibutyl butyl maleate, diethyl butyl maleate, β-methyl glutar Aliphatic polycarboxylates such as diisopropyl acrylate, diallyl ethyl succinate, di-2-ethylhexyl fumarate, diethyl itaconate, dioctyl citraconic acid, diethyl 1,2-cyclohexanecarboxylate, 1,2-cyclohexane Diisobutyl hexane carboxylate, diethyl tetrahydrophthalate, alicyclic polycarboxylic acid esters such as diethyl nadic acid, monoethyl phthalate, dimethyl phthalate, methyl ethyl phthalate, monoisobutyl phthalate, diethyl phthalate, ethyl isobutyl phthalate, Di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-n-heptyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, dineopentyl phthalate, phthalic acid Didecyl, benzyl butyl phthalate,
Aromatic polycarboxylic acid esters such as diphenyl phthalate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate, dibutyl trimellitate, and heterocyclic polycarboxylic acid esters such as 3,4-furandicarboxylic acid. No.

Other examples of the polycarboxylic acid ester include diethyl adipate, diisobutyl adipate,
Long chain dicarboxylic acid esters such as diisopropyl sebacate, di-n-butyl sebacate, di-n-octyl sebacate, and di-2-ethylhexyl sebacate can also be mentioned.

In the present invention, (c) as the electron donor,
A polyether compound having two or more ether bonds existing through a plurality of atoms can also be used. Examples of such polyether compounds include compounds in which atoms existing between ether bonds are carbon, silicon, oxygen, nitrogen, phosphorus, boron, sulfur, or two or more selected from these. Among such polyether compounds, a compound in which a relatively bulky substituent is bonded to an atom between ether bonds and a plurality of carbon atoms are contained in an atom existing between two or more ether bonds is preferable. For example, a polyether compound represented by the following formula is preferable.

[0059]

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(Where n is an integer of 2 ≦ n ≦ 10,
R ^{1 to} R ²⁶ are substituents having at least one atom selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron and silicon, and any of R ^{1 to} R ²⁶
Preferably, R ^{1 to} R ²ⁿ may together form a ring other than a benzene ring, and atoms other than carbon may be contained in the main chain. ) Of the polyether compounds represented by such formulas,
3-Diethers are preferably used, and in particular, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-
Isobutyl-1,3-dimethoxypropane, 2-isopropyl
-2-isopentyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane, 2-cyclohexyl-2-isopropyl- 1,3-dimethoxypropane, 2-isopropyl-2-s-butyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2-cyclopentyl-2-isopropyl-1,3-dimethoxy Propane or the like is preferably used.

Further, as the electron donor (c), an electron donor (C) as described later can be used. These electron donors (c) can be used alone or in combination of two or more.

In the present invention, as the electron donor (c), among the above-mentioned compounds, carboxylic acid esters, particularly polyvalent carboxylic acid esters, particularly phthalic acid esters and polyethers are preferably used.

(D) Solid Divalent Metal Halide In the present invention, (d) a solid divalent metal halide is used when preparing the solid titanium catalyst component (A).

As the solid divalent metal halide (d), the composition is MX ₂ (M is a divalent metal atom,
X is a Cl, I or Br atom). Specifically, MgCl ₂ , MnC
l ₂ , FeCl ₂ , CoCl ₂ , NiCl ₂ , CdCl ₂ ,
ZnCl ₂ , ZnBr ₂ , NiBr ₂ , CdBr ₂ , NiI
_{2 and the} like. Among them, MgCl ₂ ,
Is preferable, _{FeCl 2, CoCl 2, NiCl 2} , and more preferred are MgCl _2, FeCl _2, particularly preferred is MgCl _2.

The solid divalent metal halide (d) used in the present invention is an anhydride, and preferably has a crystal structure classified as a cadmium chloride type. The crystal structure classified into the cadmium chloride type is a known crystal structure described in various documents, for example, “Chemical Dictionary 1” (Kyoritsu Shuppan Co., Ltd., first edition, February 1962)
28), "Contemporary Inorganic Chemistry Lectures on Inorganic Chemistry (Part 1)" (Shichiichiro Utsumi, Gihodo Inc., First Edition Showa 4)
Published on July 20, 2000).

(A) Preparation of Solid Titanium Catalyst Component In the present invention, (a) a liquid magnesium compound, (b) a liquid titanium compound, (c) an electron donor, and (d)
The solid titanium catalyst component (A) is prepared by contacting a solid divalent metal halide (hereinafter sometimes simply referred to as a solid compound).

FIG. 1 shows a preferred process for preparing a solid titanium catalyst component and an example of a process for preparing an olefin polymerization catalyst containing the solid titanium catalyst component. When the components (a) to (d) are brought into contact with each other to prepare a solid, a hydrocarbon solvent used when the solid magnesium compound is liquefied to form the liquid magnesium compound (a) is used as needed. be able to. Specific examples of the hydrocarbon solvent are as described above.

When preparing the solid titanium catalyst component (A), in addition to these compounds, an organic compound or an inorganic compound containing silicon, phosphorus, aluminum or the like used as a carrier compound and a reaction aid, etc. Or the like may be used.

Examples of such a carrier compound include Al
₂ O ₃ , SiO ₂ , B ₂ O ₃ , MgO, CaO, TiO ₂ , Zn
Metal oxides such as O, SnO ₂ , BaO, and ThO, and resins such as a styrene-divinylbenzene copolymer are exemplified. Among them, TiO ₂ , Al ₂ O ₃ , SiO ₂ , styrene-divinylbenzene copolymer and the like are preferably used.

The method for preparing the solid titanium catalyst component (A) from each of the above components is not particularly limited, and examples thereof include the following methods. (1) (a) The liquid magnesium compound is brought into contact with an organoaluminum compound to precipitate a solid, or (b) is brought into contact with a liquid titanium compound while precipitating.

In this process, (c) an electron donor and
(d) contacting the solid compound with the contact product at least once. (2) A contact product of an inorganic carrier and (a) a liquid organomagnesium compound, (b) a liquid titanium compound, (c) an electron donor and
(d) contacting the solid compound;

At this time, a contact product of the inorganic carrier and the liquid organic magnesium compound (a) may be brought into contact with a halogen-containing compound and / or an organic aluminum compound in advance. (3) Contacting (a) an inorganic or organic carrier carrying a liquid magnesium compound with (b) a liquid titanium compound.

In this process, (c) the electron donor and
(d) contacting the solid compound with the contact product at least once. (4) A solution containing a magnesium compound and (b) a liquid titanium compound, an inorganic carrier or an organic carrier, and (c) an electron donor and (d) a solid compound are contacted.

(5) After contacting (a) a liquid magnesium compound with (b) a liquid titanium compound, (c) an electron donor and (d) a solid compound. (6) After contacting (a) the liquid magnesium compound with the halogen-containing compound, (b) contacting the liquid titanium compound.

In this process, (c) the electron donor and
(d) using the solid compound at least once. (7) (a) a liquid magnesium compound, (c) an electron donor,
Contacting (d) a solid compound and (b) a liquid titanium compound.

(8) (a) After contacting a liquid magnesium compound with an organoaluminum compound, (b) contacting with a liquid titanium compound. In this contacting step, (c) an electron donor and (d) a solid compound are used at least once.

(9) A liquid magnesium compound having no reducing ability (a-2) is brought into contact with (b) a liquid titanium compound in the presence or absence of (c) an electron donor. In this contacting step, (c) an electron donor and (d) a solid compound are used at least once.

(10) After suspending the (d) solid compound in the (a) liquid magnesium compound, (b) is brought into contact with the liquid titanium compound and then (c) is brought into contact with the electron donor. (11) A solid compound (d) is suspended in a liquid magnesium compound (a), and then a liquid titanium compound (b) is brought into contact.
In this contacting process, (c) an electron donor is used.

(12) The liquid titanium compound (b) in which the (d) solid compound is suspended is brought into contact with the (a) liquid magnesium compound. In this contacting process, (c) an electron donor is used. (13) A liquid titanium compound (b) in which a (d) solid compound is suspended is brought into contact with (a) a liquid magnesium compound, and then (c) an electron donor.

(14) (a) a liquid magnesium compound, and (b)
The liquid titanium compound is brought into contact with (d) a solid compound in the presence of (c) an electron donor. (15) After contacting (a) a liquid magnesium compound, (b) a liquid titanium compound, and (d) a solid compound, (c) contacting with an electron donor.

(16) The reaction products obtained in (1) to (15)
Further, (b) a liquid titanium compound is brought into contact. (17) The reaction product obtained in (1) to (15) is further contacted with (c) an electron donor and (b) a liquid titanium compound.

In the above method, as the organoaluminum compound, an organoaluminum compound described later as (B) the organoaluminum compound is used. In the present invention, (a) ~ (d) when contacting, (a)
The contact between the liquid magnesium compound and the (b) liquid titanium compound is preferably carried out in the presence of the (d) solid compound, in which case (c) the electron donor may be used in any step, but (a) More preferably, the contact between the liquid magnesium compound and (b) the liquid titanium compound is performed in the presence of (d) a solid compound and then (c) an electron donor. Specifically, among the preparation methods described above, (1
The preparation methods of (0) to (17) are preferable, and the preparation method of (13) is particularly preferable.

The contact of each component as described above is usually carried out at -70.
C. to 200.degree. C., preferably -50.degree. C. to 150.degree. C., more preferably -30 to 130.degree. (A) The amount of each component used in preparing the solid titanium catalyst component varies depending on the preparation method and cannot be specified unconditionally. For example, (a) 0 mol of (c) electron donor per 1 mol of liquid magnesium compound 0.01 to 10 mol, preferably 0.1 to 5 mol, (b) the liquid titanium compound is 0.0
The solid compound (d) can be used in an amount of 1 to 1000 mol, preferably 0.1 to 200 mol, and the solid compound (d) in an amount of 0.5 to 150 mol, preferably 1 to 100 mol.

In the present invention, an olefin polymerization catalyst can be formed using the solid titanium catalyst component (A) thus obtained as it is. It is preferable to use after washing with a solvent at 200 ° C.

Examples of the solvent include aliphatic hydrocarbon solvents such as hexane, heptane, octane, nonane, decane and cetane, non-halogenated aromatic hydrocarbon solvents such as toluene, xylene and benzene, chlorobenzene, o-dichlorobenzene. And halogen-containing aromatic hydrocarbon solvents such as m-dichlorobenzene, trichlorobenzene, α, α, α-trichlorotoluene, o-chlorotoluene, benzal chloride and 2-chlorobenzyl chloride. Of these, aliphatic hydrocarbon solvents and halogen-containing aromatic hydrocarbon solvents are preferably used.

(A) When washing the solid titanium catalyst component, the hydrocarbon solvent is usually used in an amount of 1 to 1 per gram of the solid.
It can be used in an amount of 0000 ml, preferably 5 to 5000 ml, more preferably 10 to 1000 ml.

This washing is preferably performed until the hexane washing at room temperature does not remove titanium. The solid titanium catalyst component (A) obtained as described above comprises titanium in an amount of 0.1 to 10% by weight, preferably 0.5 to 5% by weight, and magnesium and halogen in a total amount of 55 to 94%. It is desirable to contain (c) an electron donor in an amount of 5 to 35% by weight, preferably 7.5 to 30% by weight in an amount of 9.9% by weight, preferably 65 to 92% by weight. (D) Magnesium chloride (M
When metal chlorides other than gCl ₂ ) are used,
(d) It is desirable to contain the metal derived from the solid compound in an amount of 0.05 to 10% by weight, preferably 0.1 to 5% by weight.

When the solid titanium catalyst component (A) obtained as described above is used as a catalyst component for olefin polymerization, olefins can be polymerized with extremely high activity and polyolefins having high stereoregularity can be produced. can do.

[(B) Organoaluminum Compound] In the present invention, when forming a catalyst for olefin polymerization, (B) together with (A) the solid titanium catalyst component as described above,
An organic aluminum compound is used. Specific examples of the organoaluminum compound (B) include an organoaluminum compound, a complex alkyl compound of a metal of Group I of the periodic table with aluminum, and the like.

Such an organoaluminum compound is represented, for example, by the following formula. During R ^a _n AlX _3-n (wherein, R ^a is a hydrocarbon group having 1 to 12 carbon atoms, X
Is a halogen atom or a hydrogen atom, and n is 1 to 3. R ^a is a hydrocarbon group having 1 to 12 carbon atoms such as an alkyl group, a cycloalkyl group or an aryl group, and specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an isobutyl group, Examples include a pentyl group, a hexyl group, an octyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group and a tolyl group.

Specific examples of such an organoaluminum compound include trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri-2-ethylhexylaluminum, and isoprenylaluminum. Alkenylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dialkylaluminum halide such as dimethylaluminum bromide, methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride, etc. Ethyl aluminum Alkylaluminum sesquihalide such as Kiburomido, methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, alkyl aluminum dihalides such as ethyl aluminum dibromide, diethyl aluminum hydride, alkyl aluminum hydride such as diisobutylaluminum hydride and the like.

Further, as the organoaluminum compound, a compound represented by the following formula can also be mentioned. In R ^a _n AlY _3-n the above formulas, R ^a is as defined above, Y is -OR
^b group, -OSiR ^c ₃ group, -OAlR ^d ₂ group, -NR ^e ₂ group,
—SiR ^f ₃ or —N (R ^g ) AlR ^h ₂ ;
Is 1-2, R ^b , R ^c , R ^d and R ^h are a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group and the like, ^Re is a hydrogen atom,
Examples include a methyl group, an ethyl group, an isopropyl group, a phenyl group, and a trimethylsilyl group, and R ^f and R ^g are a methyl group, an ethyl group, and the like.

Specific examples of such an organoaluminum compound include the following compounds. _{^{(i) R a n Al (}} OR b) 3-n dimethylaluminum methoxide, diethylaluminum ethoxide and diisobutylaluminum methoxide. _{^{(ii) R a n Al (}} OSiR c) 3-n (Et 2 Al (OSiMe 3), (iso-Bu) 2 Al (OSiM
e ₃ ), (iso-Bu) ₂ Al (OSiEt ₃ ) and the like. _{^{(iii) R a n Al (}} OAlR d 2) 3-n Et 2 AlOAlEt 2, (iso-Bu) 2 AlOAl (iso-Bu)
₂ etc. _{^{(iv) R a n Al (}} NR e 2) 3-n Me 2 AlNEt 2, Et 2 AlNHMe, Me 2 AlNHE
t, Et ₂ AlN (Me ₃ Si) ₂ , (iso-Bu) ₂ AlN (M
e ₃ Si) ₂ etc. (v) R ^a _n Al etc. ^{_{(SiR f 3) 3-n}} (iso-Bu) 2 AlSiMe 3, (vi) R a n Al [N (R ^g) -AlR ^h _{2] 3-n} Et ₂ AlN ( Me) -AlEt ₂ (iso-Bu) ₂ AlN (Et) Al (iso-Bu) _{2 and the} like.

In the above formula, Me is a methyl group;
Et is an ethyl group, and iso-Bu is an isobutyl group. Further similar compounds, such as oxygen atoms,
An organoaluminum compound in which two or more aluminum atoms are bonded via a nitrogen atom can also be mentioned. More specifically, (C ₂ H ₅ ) ₂ AlOAl (C ₂ H ₅ ) ₂ , (C ₄ H ₉ ) ₂
AlOAl (C ₄ H ₉ ) ₂ , (C ₂ H ₅ ) ₂ AlN (C
_{2 H 5) Al (C 2} H 5) 2, etc., it may further include aluminoxanes such as methyl aluminoxane.

The complex alkylated product of aluminum and Group I metal of the Periodic Table of the Elements is represented by the following general formula. M ¹ AlR ^j ₄ (M ¹ is Li, Na, K, and R ^j has 1 to 15 carbon atoms.
Is a hydrocarbon group. ) Specifically, LiAl (C ₂ H ₅ )
₄ , LiAl (C ₇ H ₁₅ ) _{4 and the} like.

[0096] Among the above-described (B) an organoaluminum _{^{compound, R a 3 Al, R a}} n Al (OR b) 3-n, R
an organoaluminum compound represented by _{^{a n Al (OAlR d 2)}} 3-n is preferably used.

In the present invention, the above-mentioned organoaluminum compounds (B) can be used alone or in combination of two or more. [(C) Electron Donor] The (C) electron donor used together with (A) the solid titanium catalyst and (B) the organoaluminum when preparing the catalyst for olefin polymerization is represented by the following general formula (1) or ( An organosilicon compound (aminosilane compound) represented by 2).

[0098]

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[In the formula (1) or (2), R
¹ represents a hydrocarbon group having 1 to 8 carbon atoms, and R ² represents a hydrocarbon group having ^{2 to} 24 carbon atoms, a hydrocarbon amino group having 2 to 24 carbon atoms, or a hydrocarbon alkoxy group having 1 to 24 carbon atoms. R ³ N represents a polycyclic amino group having 7 or more carbon atoms which forms a skeleton together with a nitrogen atom].

In these formulas, R ¹ has 1 to 8 carbon atoms.
And an unsaturated or saturated aliphatic hydrocarbon group having 1 to 8 carbon atoms. Specifically, methyl, ethyl, n-propyl, isopropyl, n-
Butyl group, isobutyl group, t-butyl group, sec-butyl group,
Examples include an alkyl group such as an n-pentyl group, an isopentyl group, and an n-hexyl group, and a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group. Among them, a methyl group is particularly preferable.

R ² has 2 to 24 carbon atoms, preferably 2 to 8 carbon atoms.
A hydrocarbon group having 2 to 24, preferably 2 to 8 carbon atoms, or a hydrocarbon group having 1 to 24 carbon atoms, preferably 1 to 8 carbon atoms.
Is a hydrocarbon alkoxy group. Among them, those having 2 to 2 carbon atoms
A hydrocarbon group of 4 or a hydrocarbon amino group having 2 to 24 carbon atoms is preferred.

As the hydrocarbon group having 2 to 24 carbon atoms, specifically, an ethyl group, an n-propyl group, an isopropyl group,
n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, isopentyl group, n-hexyl group, n-
Examples include a heptyl group, n-octyl group, texyl group, cyclopentyl group, cyclohexyl group, phenyl group, benzyl group, and toluyl group. Further, a hydrocarbon group containing a silicon atom such as a trimethylsilylmethyl group and a bistrimethylsilylmethyl group may be mentioned.

Specific examples of the hydrocarbon amino group having 2 to 24 carbon atoms include a dimethylamino group, a methylethylamino group, a diethylamino group, an ethyl n-propylamino group,
Di-n-propylamino group, ethylisopropylamino group,
Examples thereof include a diisopropylamino group, a pyrrolidino group, a piperidino group, and a hexamethyleneimino group.

Specific examples of the hydrocarbon alkoxy group having 1 to 24 carbon atoms include a methoxy group, an isopropoxy group,
t-butoxy group and the like. Among the above, a propyl group such as an n-propyl group and an isopropyl group, a butyl group such as an isobutyl group, and a diethylamino group are preferable.

R ³ N is a polycyclic amino group having 7 or more carbon atoms which forms a skeleton together with a nitrogen atom. The polycyclic amino group may be a saturated polycyclic amino group or a polycyclic amino group in which part or all of the ring is unsaturated. The nitrogen atom of the polycyclic amino group is directly bonded to the silicon atom of the organosilicon compound. That is, the hydrogen atom of the secondary amine R ³ NH is removed and Si and N are chemically bonded. In the general formula (1), two R ³ N
The groups can be the same or different.

As specific examples of R ³ NH, as shown in the following chemical structural formula, perhydroindole, perhydroisoindole, perhydroquinoline, perhydroisoquinoline, perhydrocarbazole, perhydroacridine, perhydrophen Nanthridin, perhydrobenzo (g) quinoline, perhydrobenzo (h) quinoline, perhydrobenzo (f) quinoline, perhydrobenzo (g) isoquinoline, perhydrobenzo (h) isoquinoline, perhydrobenzo (f) isoquinoline , Perhydroacequinoline, perhydroaceisoquinoline, amine compounds such as perhydroiminostilbene, and a part of hydrogen atoms other than nitrogen atoms in the amine compounds were substituted with alkyl groups, phenyl groups, and cycloalkyl groups. Amine compound It can gel.

[0107]

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Further, as shown in the following chemical structural formula, R ³ NH represents 1,2,3,4-tetrahydroquinoline, 1,2,3,
Examples thereof include polycyclic amino compounds in which a part of a ring is unsaturated, such as 4-tetrahydroisoquinoline, and amine compounds in which a part of hydrogen atoms other than a nitrogen atom is substituted with an alkyl group, a phenyl group, or a cycloalkyl group. be able to.

[0109]

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Particularly preferred R ³ NH includes perhydroquinoline, perhydroisoquinoline, 1,2,3,4-tetrahydroquinoline, 1,2,3,4-tetrahydroisoquinoline and derivatives thereof.

Examples of the organosilicon compound (C-1) represented by the general formula (1) include a perhydroquinolino compound represented by the general formula (1-a) and a perhydroisoino compound represented by the general formula (1-b). Quinolino compound, general formula (1-c)
(Perhydroquinolino) (perhydroisoquinolino) compound represented by the formula: 1,2,
3,4-tetrahydroquinolino compound, 1,2,3,4-tetrahydroisoquinolino compound represented by general formula (1-e),
(1,2,3,4-tetrahydroquinolino) (1,2,3,4-tetrahydroisoquinolino) compounds represented by the general formula (1-f) are exemplified.

[0112]

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[0113]

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R in the general formulas (1-a) to (1-f)
⁴ represents a substituent on the saturated ring of R ³ N, and is a hydrogen atom or an unsaturated or saturated aliphatic hydrocarbon group having 1 to 24 carbon atoms. Preferred specific examples of R ⁴ include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, and a sec-butyl group. Further, the number of hydrocarbon groups on the saturated ring of R ³ N may be one or more.

Specific examples of the compound represented by the general formula (1-a) include bis (perhydroquinolino) dimethoxysilane. Also, bis (2-methylperhydroquinolino) dimethoxysilane, bis (3-methylperhydroquinolino) dimethoxysilane, bis (4-
Methyl perhydroquinolino) dimethoxysilane, bis (5-methylperhydroquinolino) dimethoxysilane, bis (6-methylperhydroquinolino) dimethoxysilane,
Bis (7-methylperhydroquinolino) dimethoxysilane, bis (8-methylperhydroquinolino) dimethoxysilane, bis (9-methylperhydroquinolino) dimethoxysilane, and bis (10-methylperhydroquinolino) dimethoxysilane (Methyl-substituted perhydroquinolino) dimethoxysilane compounds.

Further, bis (2,3-dimethylperhydroquinolino) dimethoxysilane, bis (2,4-dimethylperhydroquinolino) dimethoxysilane, bis (2,5-dimethylperhydroquinolino) dimethoxysilane, bis (2 , 6-Dimethylperhydroquinolino) dimethoxysilane, bis (2,
7-dimethylperhydroquinolino) dimethoxysilane, bis (2,8-dimethylperhydroquinolino) dimethoxysilane, bis (2,9-dimethylperhydroquinolino) dimethoxysilane, bis (2,10-dimethylperhydroquinolino)
Dimethoxysilane, bis (3,4-dimethylperhydroquinolino) dimethoxysilane, bis (3,5-dimethylperhydroquinolino) dimethoxysilane, bis (3,6-dimethylperhydroquinolino) dimethoxysilane, bis (3,7 -Dimethylperhydroquinolino) dimethoxysilane, bis (3,
8-dimethylperhydroquinolino) dimethoxysilane, bis (3,9-dimethylperhydroquinolino) dimethoxysilane, bis (3,10-dimethylperhydroquinolino) dimethoxysilane, bis (4,5-dimethylperhydroquinolino)
Dimethoxysilane, bis (4,6-dimethylperhydroquinolino) dimethoxysilane, bis (4,7-dimethylperhydroquinolino) dimethoxysilane, bis (4,8-dimethylperhydroquinolino) dimethoxysilane, bis (4,9 -Dimethylperhydroquinolino) dimethoxysilane, bis (4,
10-dimethylperhydroquinolino) dimethoxysilane,
Bis (5,6-dimethylperhydroquinolino) dimethoxysilane, bis (5,7-dimethylperhydroquinolino) dimethoxysilane, bis (5,8-dimethylperhydroquinolino)
Dimethoxysilane, bis (5,9-dimethylperhydroquinolino) dimethoxysilane, bis (5,10-dimethylperhydroquinolino) dimethoxysilane, bis (6,7-dimethylperhydroquinolino) dimethoxysilane, bis (6,8 -Dimethylperhydroquinolino) dimethoxysilane, bis (6,9-dimethylperhydroquinolino) dimethoxysilane, bis (6,10-dimethylperhydroquinolino) dimethoxysilane, bis (7,8-dimethylperhydroquinolino)
Dimethoxysilane, bis (7,9-dimethylperhydroquinolino) dimethoxysilane, bis (7,10-dimethylperhydroquinolino) dimethoxysilane, bis (8,9-dimethylperhydroquinolino) dimethoxysilane, bis (8,10 -
Examples thereof include bis (dimethyl-substituted perhydroquinolino) dimethoxysilane compounds such as dimethylperhydroquinolino) dimethoxysilane and bis (9,10-dimethylperhydroquinolino) dimethoxysilane.

Further, bis (2,3,4-trimethylperhydroquinolino) dimethoxysilane, bis (3,4,5-trimethylperhydroquinolino) dimethoxysilane, bis (4,5,6-
Trimethylperhydroquinolino) dimethoxysilane, bis (5,6,7-trimethylperhydroquinolino) dimethoxysilane, bis (6,7,8-trimethylperhydroquinolino)
Bis (trimethyl-substituted perhydroquinolino) dimethoxysilane compounds such as dimethoxysilane, bis (7,8,9-trimethylperhydroquinolino) dimethoxysilane and bis (8,9,10-trimethylperhydroquinolino) dimethoxysilane; .

Further, (perhydroquinolino) (2-methylperhydroquinolino) dimethoxysilane, (perhydroquinolino) (3-methylperhydroquinolino) dimethoxysilane, (perhydroquinolino) (4-methylperhydroquinolino) Dimethoxysilane, (perhydroquinolino)
(5-methylperhydroquinolino) dimethoxysilane,
(Perhydroquinolino) (6-methylperhydroquinolino) dimethoxysilane, (perhydroquinolino) (7-methylperhydroquinolino) dimethoxysilane, (perhydroquinolino) (8-methylperhydroquinolino) dimethoxysilane, (per (Perhydroquinolino) (methylperhydroquinolino) dimethoxysilane compounds such as (hydroquinolino) (9-methylperhydroquinolino) dimethoxysilane and (perhydroquinolino) (10-methylperhydroquinolino) dimethoxysilane.

Of the above compounds, bis (perhydroquinolino) dimethoxysilane is preferred. As the compound represented by the general formula (1-b), specifically,
Bis (perhydroisoquinolino) dimethoxysilane and the like can be mentioned.

Further, bis (1-methylperhydroisoquinolino) dimethoxysilane, bis (3-methylperhydroisoquinolino) dimethoxysilane, bis (4-methylperhydroisoquinolino) dimethoxysilane, bis (5 -Methylperhydroisoquinolino) dimethoxysilane, bis (6-
Methyl perhydroisoquinolino) dimethoxysilane, bis (7-methylperhydroisoquinolino) dimethoxysilane, bis (8-methylperhydroisoquinolino) dimethoxysilane, bis (9-methylperhydroisoquinolino) dimethoxy Examples include bis (methyl-substituted perhydroisoquinolino) dimethoxysilane compounds such as silane and bis (10-methylperhydroisoquinolino) dimethoxysilane.

Further, bis (1,3-dimethylperhydroisoquinolino) dimethoxysilane, bis (1,4-dimethylperhydroisoquinolino) dimethoxysilane, bis (1,5-dimethylperhydroisoquinolino) Dimethoxysilane, bis (1,6-dimethylperhydroisoquinolino) dimethoxysilane, bis (1,7-dimethylperhydroisoquinolino)
Dimethoxysilane, bis (1,8-dimethylperhydroisoquinolino) dimethoxysilane, bis (1,9-dimethylperhydroisoquinolino) dimethoxysilane, bis (1,10-
Dimethyl perhydroisoquinolino) dimethoxysilane,
Bis (3,4-dimethylperhydroisoquinolino) dimethoxysilane, bis (3,5-dimethylperhydroisoquinolino) dimethoxysilane, bis (3,6-dimethylperhydroisoquinolino) dimethoxysilane, bis ( 3,7-dimethylperhydroisoquinolino) dimethoxysilane, bis (3,
8-dimethylperhydroisoquinolino) dimethoxysilane, bis (3,9-dimethylperhydroisoquinolino) dimethoxysilane, bis (3,10-dimethylperhydroisoquinolino) dimethoxysilane, bis (4,5- Dimethylperhydroisoquinolino) dimethoxysilane, bis (4,6-dimethylperhydroisoquinolino) dimethoxysilane, bis (4,7-dimethylperhydroisoquinolino) dimethoxysilane, bis (4,8-dimethylper) Hydroisoquinolino) dimethoxysilane, bis (4,9-dimethylperhydroisoquinolino) dimethoxysilane, bis (4,10-dimethylperhydroisoquinolino) dimethoxysilane, bis (5,6-dimethylperhydroiso) Quinolino) dimethoxysilane, bis (5,7-dimethylperhydroisoquinolino) dimethoxysilane, bis (5,8-dimethylperoxide) Isokinorino)
Dimethoxysilane, bis (5,9-dimethylperhydroisoquinolino) dimethoxysilane, bis (5,10-dimethylperhydroisoquinolino) dimethoxysilane, bis (6,7-
Dimethyl perhydroisoquinolino) dimethoxysilane,
Bis (6,8-dimethylperhydroisoquinolino) dimethoxysilane, bis (6,9-dimethylperhydroisoquinolino) dimethoxysilane, bis (6,10-dimethylperhydroisoquinolino) dimethoxysilane, bis ( 7,8-dimethylperhydroisoquinolino) dimethoxysilane, bis (7,9-dimethylperhydroisoquinolino) dimethoxysilane, bis (7,10-dimethylperhydroisoquinolino)
Dimethoxysilane, bis (8,9-dimethylperhydroisoquinolino) dimethoxysilane, bis (8,10-dimethylperhydroisoquinolino) dimethoxysilane, bis (9,10
-Bis (dimethyl-substituted perhydroisoquinolino) dimethoxysilane compounds such as dimethylperhydroisoquinolino) dimethoxysilane.

Further, bis (1,3,4-trimethylperhydroisoquinolino) dimethoxysilane, bis (3,4,5-trimethylperhydroisoquinolino) dimethoxysilane, bis (4,5,6-trimethyl) Perhydroisoquinolino) dimethoxysilane, bis (5,6,7-trimethylperhydroisoquinolino) dimethoxysilane, bis (6,7,8-trimethylperhydroisoquinolino) dimethoxysilane, bis (7,8 , 9-
And bis (trimethyl-substituted perhydroisoquinolino) dimethoxysilane compounds such as trimethylperhydroisoquinolino) dimethoxysilane and bis (8,9,10-trimethylperhydroisoquinolino) dimethoxysilane.

Further, (perhydroisoquinolino) (2-methylperisoquinolino) dimethoxysilane, (perhydroisoquinolino) (3-methylperisoquinolino) dimethoxysilane, (perhydroisoquinolino) (4-methylperisoquinolino) dimethoxysilane, (perhydroisoquinolino) (5-methylperisoquinolino) dimethoxysilane,
(Perhydroisoquinolino) (6-methylperisoquinolino) dimethoxysilane, (perhydroisoquinolino) (7-
(Methyl perisoquinolino) dimethoxysilane, (perhydroisoquinolino) (8-methylperisoquinolino) dimethoxysilane, (perhydroisoquinolino) (9-methylperisoquinolino) dimethoxysilane, (perhydro (Perhydroisoquinolino) (methylperisoquinolino) dimethoxysilane compounds such as isoquinolino) (10-methylperisoquinolino) dimethoxysilane.

Among the above compounds, bis (perhydroisoquinolino) dimethoxysilane is preferred. Specific examples of the compound represented by the general formula (1-c) include (perhydroquinolino) (perhydroisoquinolino) dimethoxysilane, (perhydroquinolino) (1-methylperhydroisoquinolino) Dimethoxysilane, (perhydroquinolino) (3-methylperhydroisoquinolino) dimethoxysilane, (perhydroquinolino) (4-methylperhydroisoquinolino) dimethoxysilane, (perhydroquinolino) (5-methylperhydro (Isoquinolino) dimethoxysilane, (perhydroquinolino) (6-methylperhydroisoquinolino) dimethoxysilane, (perhydroquinolino) (7-methylperhydroisoquinolino) dimethoxysilane, (perhydroquinolino) (8 -Methyl perhydroisoquinolino) dimethoxysilane, (perhydroquinolino) (9-meth (Cilperhydroisoquinolino) dimethoxysilane, (perhydroquinolino) (10-
Methyl perhydroisoquinolino) dimethoxysilane,
(2-methylperhydroquinolino) (perhydroisoquinolino) dimethoxysilane, (3-methylperhydroquinolino) (perhydroisoquinolino) dimethoxysilane,
(4-methylperhydroquinolino) (perhydroisoquinolino) dimethoxysilane, (5-methylperhydroquinolino) (perhydroisoquinolino) dimethoxysilane,
(6-methylperhydroquinolino) (perhydroisoquinolino) dimethoxysilane, (7-methylperhydroquinolino) (perhydroisoquinolino) dimethoxysilane,
(8-methylperhydroquinolino) (perhydroisoquinolino) dimethoxysilane, (9-methylperhydroquinolino) (perhydroisoquinolino) dimethoxysilane,
(10-methylperhydroquinolino) (perhydroisoquinolino) dimethoxysilane, (2-methylperhydroquinolino) (1-methylperhydroisoquinolino) dimethoxysilane, (3-methylperhydroquinolino) (3- (Methyl perhydroisoquinolino) dimethoxysilane, (4-methylperhydroquinolino) (4-methylperhydroisoquinolino) dimethoxysilane, (5-methylperhydroquinolino) (5-methylperhydroisoquinolino) dimethoxy Silane, (6-methylperhydroquinolino) (6-methylperhydroisoquinolino) dimethoxysilane, (7-methylperhydroquinolino) (7-methylperhydroisoquinolino) dimethoxysilane, (8-methylperhydroquinoline) Norino) (8-methylperhydroisoquinolino) dimethoxysilane, (9-methylperhydroquinolino) ) (9-methylperhydroisoquinolino) dimethoxysilane, and (10-methylperhydroisoquinolino) (10-methylperhydroisoquinolino) dimethoxysilane.

Among the above compounds, (perhydroquinolino) (perhydroisoquinolino) dimethoxysilane is preferred. Specific examples of the compound represented by the general formula (1-d) include bis (1,2,3,4-tetrahydroquinolino) dimethoxysilane.

Further, bis (2-methyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (3-methyl-1,
2,3,4-tetrahydroquinolino) dimethoxysilane, bis (4-methyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (6-methyl-1,2,3,4-tetrahydroquino Lino) dimethoxysilane, bis (7-methyl-1,2,3,4-
Tetrahydroquinolino) dimethoxysilane, bis (8-methyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (9-methyl-1,2,3,4-tetrahydroquinolino)
And bis (methyl-substituted-1,2,3,4-tetrahydroquinolino) dimethoxysilane compounds such as dimethoxysilane.

Further, bis (2,3-dimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane and bis (2,4-dimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane , Bis (2,6-dimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (2,7-dimethyl-1,2,3,4-
Tetrahydroquinolino) dimethoxysilane, bis (2,8-
Dimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (2,9-dimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (3,4-dimethyl-1, 2,
3,4-tetrahydroquinolino) dimethoxysilane, bis (3,6-dimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (3,7-dimethyl-1,2,3,4- Tetrahydroquinolino) dimethoxysilane, bis (3,8-dimethyl)
-1,2,3,4-tetrahydroquinolino) dimethoxysilane,
Bis (3,9-dimethyl-1,2,3,4-tetrahydroquinolino)
Dimethoxysilane, bis (4,6-dimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (4,7-dimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (4,8-dimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (4,9-dimethyl-1,2,3,4-
Tetrahydroquinolino) dimethoxysilane, bis (6,7-
Dimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (6,8-dimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (6,9-dimethyl-1, 2,
3,4-tetrahydroquinolino) dimethoxysilane, bis (7,8-dimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (7,9-dimethyl-1,2,3,4- Tetrahydroquinolino) dimethoxysilane, bis (8,9-dimethyl)
And bis (dimethyl-substituted-1,2,3,4-tetrahydroquinolino) dimethoxysilane compounds such as -1,2,3,4-tetrahydroquinolino) dimethoxysilane.

Further, bis (2,3,4-trimethyl-1,2,3,4-
Tetrahydroquinolino) dimethoxysilane, bis (2,3,
6-trimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (2,3,7-trimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (2,3, 8-trimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (2,3,9-trimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (3,4, 6-trimethyl
-1,2,3,4-tetrahydroquinolino) dimethoxysilane,
Bis (3,4,7-trimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (3,4,8-trimethyl-1,2,
3,4-tetrahydroquinolino) dimethoxysilane, bis (3,4,9-trimethyl-1,2,3,4-tetrahydroquinolino)
Dimethoxysilane, bis (4,6,7-trimethyl-1,2,3,4-
Tetrahydroquinolino) dimethoxysilane, bis (4,6,
8-trimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (4,6,9-trimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (6,7, 8-trimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (6,7,9-trimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (7,8, 9-trimethyl
And bis (trimethyl-substituted-1,2,3,4-tetrahydroquinolino) dimethoxysilane compounds such as -1,2,3,4-tetrahydroquinolino) dimethoxysilane.

Further, bis (2,3,4,6-tetramethyl-1,2,
3,4-tetrahydroquinolino) dimethoxysilane, bis (2,3,4,7-tetramethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (2,3,4,8-tetra Methyl-
1,2,3,4-tetrahydroquinolino) dimethoxysilane,
Bis (2,3,4,9-tetramethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (3,4,6,7-tetramethyl-1,2,3,4-tetrahydro Quinolino) dimethoxysilane, bis (3,4,6,8-tetramethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (3,4,6,9-tetramethyl-1,2 , 3,4-Tetrahydroquinolino) dimethoxysilane, bis (4,6,7,8-tetramethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (4,6,7,9- Bis (tetramethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane and bis (6,7,8,9-tetramethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane Methyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane compound.

Of the above compounds, bis (1,2,3,4-tetrahydroquinolino) dimethoxysilane is preferred.
As the compound represented by the general formula (1-e), specifically, bis (1,2,3,4-tetrahydroisoquinolino)
Dimethoxysilane and the like.

Further, bis (1-methyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, bis (3-methyl
-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, bis (4-methyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, bis (6-methyl-1,2,3 , 4-tetrahydroisoquinolino) dimethoxysilane, bis (7-methyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, bis (8-methyl-1,2,3,4-tetrahydroisoquino) Lino) dimethoxysilane, bis (9-methyl-1,2,3,4-
Bis (methyl-substituted-1,2,3,4-tetrahydroisoquinolino) such as tetrahydroisoquinolino) dimethoxysilane
A dimethoxysilane compound is exemplified.

Also, bis (1,3-dimethyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, bis (1,4-dimethyl
Dimethyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, bis (1,6-dimethyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, bis (1,7-dimethyl- 1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, bis (1,8-dimethyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, bis (1,9-dimethyl-1,
2,3,4-tetrahydroisoquinolino) dimethoxysilane, bis (3,4-dimethyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, bis (3,6-dimethyl-1,2,
3,4-tetrahydroisoquinolino) dimethoxysilane,
Bis (3,7-dimethyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, bis (3,8-dimethyl-1,2,3,4-
Tetrahydroisoquinolino) dimethoxysilane, bis (3,9-dimethyl-1,2,3,4-tetrahydroisoquinolino)
Dimethoxysilane, bis (4,6-dimethyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, bis (4,7-
Dimethyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, bis (4,8-dimethyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, bis (4,9-dimethyl- 1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, bis (6,7-dimethyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, bis (6,8-dimethyl-1,
2,3,4-tetrahydroisoquinolino) dimethoxysilane, bis (6,9-dimethyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, bis (7,8-dimethyl-1,2,
3,4-tetrahydroisoquinolino) dimethoxysilane,
Bis (7,9-dimethyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, bis (8,9-dimethyl-1,2,3,4-
Bis (dimethyl-substituted-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane compounds such as tetrahydroisoquinolino) dimethoxysilane;

Further, bis (1,3,4-trimethyl-1,2,3,4-
Tetrahydroisoquinolino) dimethoxysilane, bis (1,3,6-trimethyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, bis (1,3,7-trimethyl-1,2,
3,4-tetrahydroisoquinolino) dimethoxysilane,
Bis (1,3,8-trimethyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, bis (1,3,9-trimethyl-
1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, bis (3,4,6-trimethyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, bis (3,4,7- Trimethyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, bis (3,4,8-trimethyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, bis (3,4, 9-trimethyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, bis (4,6,7-trimethyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, bis (4, 6,8-trimethyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, bis (4,6,9-trimethyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, bis ( 6,7,8-trimethyl-1,2,3,4-tetrahydroisoquinolino dimethoxysilane, bis (6,7,9-trimethyl-1,2,3,4-tetrahydroisoquinolino Dimethoxysilane, bis (7,8,9-
And bis (trimethyl-substituted-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane compounds such as trimethyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane.

Further, bis (1,3,4,6-tetramethyl-1,2,
3,4-tetrahydroisoquinolino) dimethoxysilane,
Bis (1,3,4,7-tetramethyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, bis (1,3,4,8-tetramethyl-1,2,3,4- Tetrahydroisoquinolino) dimethoxysilane, bis (1,3,4,9-tetramethyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, bis (3,4,
6,7-tetramethyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, bis (3,4,6,8-tetramethyl-
1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, bis (3,4,6,9-tetramethyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, bis (4,6 , 7,8-Tetramethyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, bis (4,6,7,9-tetramethyl-1,2,3,4-
Bis (tetramethyl-substituted-1,2,3,4) such as tetrahydroisoquinolino) dimethoxysilane and bis (6,7,8,9-tetramethyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane 4-tetrahydroisoquinolino) dimethoxysilane compound.

Of the above compounds, bis (1,2,3,4-tetrahydroisoquinolino) dimethoxysilane is preferred. As the compound represented by the general formula (1-f), specifically, (1,2,3,4-tetrahydroquinolino)
(1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, (2-methyl-1,2,3,4-tetrahydroquinolino) (1-
Methyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, (3-methyl-1,2,3,4-tetrahydroquinolino) (3-methyl-1,2,3,4-tetrahydroiso Quinolino)
Dimethoxysilane, (3-methyl-1,2,3,4-tetrahydroquinolino) (4-methyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, (4-methyl-1,2, 3,4-tetrahydroquinolino) (4-methyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, (4-methyl-1,2,3,4-
Tetrahydroquinolino) (6-methyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, (6-methyl-1,
2,3,4-tetrahydroquinolino) (6-methyl-1,2,3,4-
(Tetrahydroisoquinolino) dimethoxysilane, (6-methyl-1,2,3,4-tetrahydroquinolino) (7-methyl-1,
2,3,4-tetrahydroisoquinolino) dimethoxysilane, (7-methyl-1,2,3,4-tetrahydroquinolino) (7-
Methyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, (7-methyl-1,2,3,4-tetrahydroquinolino) (8-methyl-1,2,3,4-tetrahydroiso Quinolino)
Dimethoxysilane, (8-methyl-1,2,3,4-tetrahydroquinolino) (8-methyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, (8-methyl-1,2, 3,4-tetrahydroquinolino) (9-methyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, (9-methyl-1,2,3,4-
Compounds such as tetrahydroquinolino) (9-methyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane.

Among the above compounds, (1,2,3,4-tetrahydroquinolino) (1,2,3,4-tetrahydroisoquinolino) dimethoxysilane is preferred. Specific examples of the organosilicon compound (C-1) represented by the general formula (1) include compounds represented by the following chemical structural formulas.

[0137]

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[0138]

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The organosilicon compound (C-2) represented by the general formula (2) includes a perhydroquinolino compound represented by the general formula (2-a) and a perhydroquinolino compound represented by the general formula (2-b). Hydroisoquinolino compounds and the like can be mentioned.

[0140]

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R ⁴ in these general formulas represents a substituent on a saturated ring of R ³ N, and represents a hydrogen atom or a carbon atom having 1 carbon atom.
To 24 unsaturated or saturated aliphatic hydrocarbon groups.
Preferred specific examples of R ⁴ include a hydrogen atom, a methyl group,
Ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, sec-butyl and the like. Further, the number of hydrocarbon substituents on the saturated ring of R ³ N may be one or more.

As the compound represented by the general formula (2-a), specifically, ethyl (perhydroquinolino)
Dimethoxysilane, n-propyl (perhydroquinolino)
Dimethoxysilane, isopropyl (perhydroquinolino) dimethoxysilane, n-butyl (perhydroquinolino) dimethoxysilane, isopropyl (perhydroquinolino) dimethoxysilane, t-butyl (perhydroquinolino) dimethoxysilane, sec-butyl (perhydroquinolino) ) Dimethoxysilane, n-pentyl (perhydroquinolino) dimethoxysilane, isopentyl (perhydroquinolino) dimethoxysilane, cyclopentyl (perhydroquinolino) dimethoxysilane, n-hexyl (perhydroquinolino) dimethoxysilane, cyclohexyl (perhydroquinolino) Dimethoxysilane, texyl (perhydroquinolino) dimethoxysilane, n-octyl (perhydroquinolino) dimethoxysilane, phenyl (perhydroquinolino) dimethoxysila , Piperidino (perhydroquinolino) dimethoxysilane, diethylamino (Pas - Hidorokinorino) Per hydroxamic glue aminosilane compounds such as dimethoxysilane and the like.

Further, ethyl (2-methylperhydroquinolino) dimethoxysilane, n-propyl (2-methylperhydroquinolino) dimethoxysilane, isopropyl (2-methylperhydroquinolino) dimethoxysilane, n-butyl (2-methyl Perhydroquinolino) dimethoxysilane, isopropyl (2-methylperhydroquinolino) dimethoxysilane, t-butyl (2-methylperhydroquinolino) dimethoxysilane, sec-butyl (2-methylperhydroquinolino) dimethoxysilane, n-pentyl (2-methylperhydroquinolino) dimethoxysilane, isopentyl (2-methylperhydroquinolino) dimethoxysilane, cyclopentyl (2-methylperhydroquinolino) dimethoxysilane, n-hexyl (2-methylperhydroquinolino) dimethoxysilane, cyclohexyl (2-me Helper hydroxy Norino) dimethoxysilane, thexyl (2-methyl-perhydroquinolino) dimethoxysilane, n- octyl (2-methyl-perhydroquinolino) dimethoxysilane, phenyl (2
2-, such as methyl perhydroquinolino) dimethoxysilane
Methyl perhydroquinolinosilane compound is exemplified.

Further, isopropyl (3-methylperhydroquinolino) dimethoxysilane, isopropyl (4-methylperhydroquinolino) dimethoxysilane, isopropyl (5-methylperhydroquinolino) dimethoxysilane, isopropyl (6-methylperhydroquinolino) Dimethoxysilane, isopropyl (7-methylperhydroquinolino)
Methyl-substituted perhydroquinolinosilane compounds such as dimethoxysilane, isopropyl (8-methylperhydroquinolino) dimethoxysilane, isopropyl (9-methylperhydroquinolino) dimethoxysilane, and isopropyl (10-methylperhydroquinolino) dimethoxysilane. .

Among the above compounds, ethyl (per-hydroquinolino) dimethoxysilane, n-propyl (perhydroquinolino) dimethoxysilane, isopropyl (perhydroquinolino) dimethoxysilane, n-butyl (perhydroquinolino) dimethoxysilane, isobutyl (Perhydroquinolino) dimethoxysilane, t-butyl (perhydroquinolino) dimethoxysilane, sec-butyl (perhydroquinolino) dimethoxysilane, n-hexyl (perhydroquinolino) dimethoxysilane, piperidino (per-hydroquinolino) dimethoxysilane, Compounds such as diethylamino (perhydroquinolino) dimethoxysilane are preferred.

Specific examples of the compound represented by the general formula (2-b) include ethyl (perhydroisoquinolino) dimethoxysilane, n-propyl (perhydroisoquinolino) dimethoxysilane, isopropyl (per Hydroisoquinolino) dimethoxysilane, n-butyl (perhydroisoquinolino) dimethoxysilane, isopropyl (perhydroisoquinolino) dimethoxysilane, t-butyl (perhydroisoquinolino) dimethoxysilane, sec-butyl (per Hydroisoquinolino) dimethoxysilane, n-
Pentyl (perhydroisoquinolino) dimethoxysilane, isopentyl (perhydroisoquinolino) dimethoxysilane, cyclopentyl (perhydroisoquinolino)
Dimethoxysilane, n-hexyl (perhydroisoquinolino) dimethoxysilane, cyclohexyl (perhydroisoquinolino) dimethoxysilane, texyl (perhydroisoquinolino) dimethoxysilane, n-octyl (perhydroisoquinolino) dimethoxysilane And perhydroisoquinolinosilane compounds such as phenyl (perhydroisoquinolino) dimethoxysilane, piperidino (perhydroisoquinolino) dimethoxysilane and diethylamino (per-hydroisoquinolino) dimethoxysilane.

Further, ethyl (2-methylperhydroisoquinolino) dimethoxysilane, n-propyl (2-methylperhydroisoquinolino) dimethoxysilane, isopropyl (2-methylperhydroisoquinolino) dimethoxysilane, n -Butyl (2-methylperhydroisoquinolino) dimethoxysilane, isopropyl (2-methylperhydroisoquinolino) dimethoxysilane, t-butyl (2-methylperhydroisoquinolino) dimethoxysilane, sec-butyl (2 -Methylperhydroisoquinolino) dimethoxysilane, n-pentyl (2-methylperhydroisoquinolino) dimethoxysilane, isopentyl (2-methylperhydroisoquinolino) dimethoxysilane, cyclopentyl (2-methylperhydroisoquino) Lino) dimethoxysilane, n-hexyl (2-methylperhydroisoquino No) dimethoxysilane, cyclohexyl (2-methylperhydroisoquinolino) dimethoxysilane, texyl (2-methylperhydroisoquinolino) dimethoxysilane, n-octyl (2-methylperhydroisoquinolino) dimethoxysilane, phenyl 2-methyl perhydroisoquinolinosilane compounds such as (2-methylperhydroisoquinolino) dimethoxysilane.

Further, isopropyl (3-methylperhydroisoquinolino) dimethoxysilane, isopropyl (4-methylperhydroisoquinolino) dimethoxysilane, isopropyl (5-methylperhydroisoquinolino) dimethoxysilane, isopropyl (6 -Methylperhydroisoquinolino) dimethoxysilane, isopropyl (7-methylperhydroisoquinolino) dimethoxysilane, isopropyl (8-methylperhydroisoquinolino) dimethoxysilane, isopropyl (9-methylperhydroisoquinolino)
Examples include methyl-substituted perhydroisoquinolinosilane compounds such as dimethoxysilane and isopropyl (10-methylperhydroisoquinolino) dimethoxysilane.

Among the above organosilicon compounds, ethyl (perhydroisoquinolino) dimethoxysilane, n-propyl (perhydroisoquinolino) dimethoxysilane, isopropyl (perhydroisoquinolino) dimethoxysilane, n-butyl (Perhydroisoquinolino) dimethoxysilane, isobutyl (perhydroisoquinolino) dimethoxysilane, t-butyl (perhydroisoquinolino) dimethoxysilane, sec-butyl (perhydroisoquinolino) dimethoxysilane, n-hexyl Compounds such as (perhydroisoquinolino) dimethoxysilane, piperidino (perhydroisoquinolino) dimethoxysilane, and diethylamino (perhydroisoquinolino) dimethoxysilane are preferred.

Specific examples of the organosilicon compound (C-2) represented by the general formula (2) include the compounds represented by the following chemical structural formulas.

[0151]

Embedded image

[0152]

Embedded image

The organosilicon compound (C-1) represented by the general formula (1) can be obtained, for example, by reacting tetramethoxysilane or dichlorodimethoxysilane with two equivalents of a magnesium or lithium salt of an HNR secondary amine. Can be synthesized.

The organosilicon compound (C-2) represented by the general formula (2) can be obtained by combining alkyltrimethoxysilane or alkylchlorodimethoxysilane with HNR
It can be synthesized by an equivalent reaction of a secondary amine with a magnesium or lithium salt.

In the present invention, the organosilicon compounds described above can be used alone or in combination of two or more as the electron donor (C). Olefin Polymerization Catalyst The olefin polymerization catalyst used in the present invention is a Ziegler-type non-demineralization catalyst as described above, and comprises (A) a solid titanium catalyst component and (B) an organoaluminum compound as described above. And (C) an electron donor.

FIG. 1 shows a process for preparing such an olefin polymerization catalyst. In the present invention, a prepolymerized catalyst [I] can be formed by preliminarily (co) polymerizing an olefin with the above catalyst component, and specifically, [I] the solid titanium catalyst component (A) described above. An olefin polymerization catalyst comprising (B) an organoaluminum compound and, if necessary, (C) an electron donor, a prepolymerization catalyst obtained by prepolymerizing an olefin, [II] an electron donor, Depending on,
[III] An olefin polymerization catalyst can also be formed from the organoaluminum compound.

The [II] electron donor is the same as the organosilicon compound exemplified as (C) the electron donor, and [II]
The organic aluminum compound [I] is the same as the compound exemplified as the organic aluminum compound (B). Incidentally, the electron donor and the organoaluminum compound, during the pre-polymerization,
At the time of the main polymerization, the same compound can be used, or different compounds can be used.

Examples of the olefin used in the prepolymerization include ethylene, propylene, 1-butene and 1-butene.
Pentene, 1-hexene, 3-methyl-1-butene, 3-methyl
1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4,4-dimethyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4 -Ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-
Α-olefins having 2 or more carbon atoms, such as dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. These α-olefins can be used alone or in combination of two or more.

The olefin used in the prepolymerization may be the same as or different from the α-olefin having 2 to 20 carbon atoms used in the main polymerization described later. In the present invention, the method of performing the prepolymerization is not particularly limited. For example, the prepolymerization can be performed in a liquid state of the olefins or the polyene compound, or can be performed in the presence of an inert solvent. It is also possible to carry out under conditions. Of these, it is preferable to perform prepolymerization in the presence of an inert solvent, that is, by adding an olefin and each catalyst component to the inert solvent and under relatively mild conditions. At this time, the reaction may be carried out under a condition in which the produced prepolymer is dissolved in the polymerization medium, or may be carried out under a condition in which the prepolymer is not dissolved, but it is preferably carried out under a condition in which the prepolymer is not dissolved.

The prepolymerization is usually carried out at about -20 to + 100 ° C.
Preferably about -20 to + 80 ° C, more preferably -1.
It is desirable to carry out at 0 to + 40 ° C. The prepolymerization can be carried out in any of a batch system, a semi-continuous system, and a continuous system.

In the prepolymerization, a catalyst having a higher concentration than the catalyst concentration in the system in the main polymerization can be used. The concentration of the catalyst component in the prepolymerization varies depending on the catalyst component used, etc., and the concentration of the solid titanium catalyst component (A) is usually about 0.001 to 5000 mmol, in terms of titanium atom, per liter of polymerization volume. , Preferably about 0.01 to 1000 mmol, particularly preferably 0.1
Desirably, it is ~ 500 mmol.

(B) The organoaluminum compound is selected from (A)
0.01 to 2000 per gram of solid titanium catalyst component
g, preferably 0.03 to 1000 g, more preferably 0.05 to 200 g, in an amount such that a preliminary (co) polymer is produced, and (A) per mole of titanium in the solid titanium catalyst component, Usually about 0.1-1000 mol, preferably about 0.5-500 mol, particularly preferably 1-10
Used in an amount of 0 mol.

In the prepolymerization, (C) the electron donor is usually used in an amount of 0.01 to 50 mol, preferably 0.05 to 50 mol, per 1 mol of titanium atom in the solid titanium catalyst component (A).
30 mol, more preferably 0.1 to 10 mol, can be used as needed.

In the prepolymerization, a molecular weight regulator such as hydrogen may be used. When the prepolymerized catalyst is obtained in a suspended state as described above, in the next step (main) polymerization, the prepolymerized catalyst can be used as it is in a suspended state or can be produced from the suspension. The pre-polymerized catalyst may be used separately.

As the above prepolymerized catalyst, for example, the prepolymerized catalyst obtained in a suspension state can be used as it is as a catalyst for olefin polymerization in some cases.
An olefin polymerization catalyst can be formed from [I] a prepolymerization catalyst, [III] an electron donor, and if necessary, [II] an organoaluminum compound.

The olefin polymerization catalyst used in the present invention may contain other components useful for olefin polymerization, in addition to the above components. α-Olefin polymerization method In the method for producing a propylene random copolymer according to the present invention, in the presence of a catalyst containing an olefin polymerization catalyst or a prepolymerization catalyst as described above, propylene, ethylene and carbon atoms of 4 to At least one α-olefin selected from 20 olefins is copolymerized (main polymerization).

Specific examples of the α-olefin having 4 to 20 carbon atoms are as described above, and the α-olefin having 4 or more carbon atoms may be further added to cyclopentene, cycloheptene, norbornene, and 5-ethyl-2-olefin. Norbornene,
It is also possible to copolymerize cycloolefins such as tetracyclododecene and 2-ethyl-1,4,5,8-tetramethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene. it can.

Among the α-olefins to be copolymerized with propylene, ethylene, 1-butene, 3-
Methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1
-Penten, vinylcyclohexane and the like are preferably used.

In the present invention, propylene and one other α-olefin may be copolymerized.
One or more other α-olefins may be copolymerized.
In the present invention, when propylene is copolymerized with another α-olefin such as ethylene, ethylene is added in an amount of 0.008 to 0.1 with respect to 1 mol of propylene.
It is desirable to use it in an amount of 7 mol, preferably 0.04 to 0.1 mol.

When propylene is copolymerized with one kind of α-olefin having 4 or more carbon atoms, the α-olefin having 4 or more carbon atoms is added to 0.001 mol of propylene.
It is desirable to use it in an amount of 8 to 0.17 mol, preferably 0.04 to 0.1 mol.

Propylene, ethylene and α having 4 or more carbon atoms
-When copolymerizing with an olefin, ethylene is used in an amount of 0.005 to 0.11 mol, preferably 0.03 to 0.07 mol, and 1 to 4 mol of propylene per mol of propylene. It is desirable to use the olefin in an amount of 0.003 to 0.06 mol, preferably 0.01 to 0.03 mol.

In the present invention, even if the copolymerization amount of α-olefins other than propylene is particularly increased, the composition distribution is narrow, the disturbance of the composition distribution is small, and the molecular weight distribution (Mw / Mn) excellent in stereoregularity is obtained. A wide propylene-based random copolymer can be obtained.

The above-mentioned vinyl compound or polyene compound can be copolymerized with the above-mentioned α-olefin within a range not to impair the object of the present invention.
In the present invention, the polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method.

When the polymerization takes a reaction form of slurry polymerization, the above-mentioned inert organic solvent can be used as the reaction solvent, and an olefin liquid at the reaction temperature can be used.

In the polymerization, (A) the solid titanium catalyst component or [I] the prepolymerization catalyst is usually used in an amount of about 0.001 to 1 in terms of titanium atom per liter of polymerization volume.
It is used in an amount of 00 mmol, preferably about 0.005 to 20 mmol.

The (B) (or [II]) organoaluminum compound is generally such that the metal atom in the (B) organoaluminum compound is about 1 to 20 moles per mole of titanium atom in the polymerization system.
It is used in an amount such that it amounts to 00 moles, preferably about 2 to 500 moles.

The (C) (or [III]) electron donor is
(B) (or [II]) It is used usually in an amount of about 0.001 to 10 mol, preferably 0.01 to 5 mol, per 1 mol of aluminum atom of the organoaluminum compound.

As described above, when the [I] prepolymerization catalyst is used in this polymerization, the [II] organoaluminum compound may not be used in some cases. If hydrogen is used during the polymerization, the molecular weight of the obtained copolymer can be adjusted, and a copolymer having a high melt flow rate can be obtained.

In the polymerization method of the α-olefin in the present invention, the polymerization is usually carried out at a temperature of about 20 to 300 ° C., preferably about 50 to 150 ° C., although it varies depending on the kind of the α-olefin, the form of polymerization and the like. Normal pressure ~ 100kg / cm
² , preferably under a pressure of about ² to 50 kg / cm ² .

In the present invention, the polymerization can be carried out 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 stages by changing the reaction conditions.

According to the method for producing a propylene random copolymer according to the present invention as described above, the amount of sticky components required for removing the olefin polymerization catalyst is small, the blocking resistance is excellent, and the low-temperature heat sealability is improved. A propylene-based random copolymer capable of exhibiting excellent film characteristics can be obtained.

[0182]

Industrial Applicability The propylene random copolymer according to the present invention has a low melting point, excellent moldability for films and the like, good transparency, excellent low-temperature heat sealability, blocking resistance and slip resistance. A film having excellent properties can be formed. This film has excellent blocking resistance not only during molding but also during storage and use.

According to the method for producing a propylene random copolymer according to the present invention, since a specific Ziegler-type non-demineralizing catalyst is used, the propylene random copolymer according to the present invention having the above effects can be obtained. It can be manufactured at low cost.

[0184]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

The film formed from the propylene-based random copolymer obtained in each of Examples and Reference Examples was tested for the heat-sealing start temperature, transparency, slip property and blocking resistance by the following test methods. Done. <Test Method> (1) Heat seal start temperature The heat seal start temperature was measured according to JIS Z1521. (2) Transparency (Haze) The haze, which is an index of the transparency of the film, is ASTM D
It was measured according to 1003. (3) Slip property According to ASTM D 1894, a slip speed of 200 m /
Then, a slip test was performed under the conditions of a load of 210 g and the static friction coefficient and the dynamic friction coefficient were measured. (4) Blocking resistance A blocking test was performed under the conditions of a load of 20 kg and a blocking temperature of 50 ° C in accordance with ASTM D1893, and the blocking force was measured.

[0186]

[Example 1] [Preparation of solid titanium catalyst component (A-1)] 7.14 g (75 mmol) of anhydrous magnesium chloride, 37.5 m of decane
and 35.1 ml of 2-ethylhexyl alcohol (2
25 mmol) and heated at 130 ° C. for 2 hours to form a homogeneous solution. Thereafter, 1.70 g (11.5 mmol) of phthalic anhydride was added to the homogeneous solution, and the mixture was further stirred and mixed at 130 ° C. for 1 hour to dissolve phthalic anhydride in the homogeneous solution and cooled to room temperature. .

In 200 ml (1.8 mol) of titanium tetrachloride, 0.0714 g (0.07 g) of solid anhydrous magnesium chloride was added.
After suspending (75 mmol), the mixture was kept at -20 ° C, and the homogeneous solution obtained above was added dropwise thereto over 1 hour. After dropping, the temperature of the resulting solution was raised to 1 over 4 hours.
The temperature was raised to 10 ° C., and when the temperature reached 110 ° C., 5.03 ml (18.8 mmol) of diisobutyl phthalate was added. Stir at a temperature of 110 ° C. for a further 2 hours.

After completion of the reaction for 2 hours, a solid portion was collected by hot filtration, and the solid portion was resuspended in 375 ml of 1,2,4-trichlorobenzene, and then heated again at 130 ° C. for 1 hour. . After completion of the reaction, a solid portion was collected by hot filtration, and
Washed with decane and hexane. This washing,
The process was performed until no titanium compound was detected in the washing solution.

As described above, the solid titanium catalyst component (A
A hexane slurry of -1) was obtained. A part of the solid titanium catalyst component (A-1) (hexane slurry) was collected and dried, and the composition of the catalyst component was analyzed.

The solid titanium catalyst component (A-1) comprises 1.1% by weight of Ti, 21.0% by weight of Mg, 0.2% by weight of 2-ethylhexoxy group (-OEH group) and 0.2% by weight of diisobutyl phthalate. It contained 12.3% by weight. [Preparation of Preliminary Polymerization Catalyst (I-1)] 200 m purged with nitrogen
100 ml of purified hexane was placed in a 1-liter glass reactor, and 2 mmol of triethylaluminum, 0.4 mmol of dicyclopentyldimethoxysilane and the solid titanium catalyst component (A-1) obtained above were added in an amount of 0% in terms of titanium atom. After charging 0.2 mmol, propylene was fed for 1 hour at a rate of 1.0 liter / hour.

After the supply of propylene was completed, the solid portion obtained by filtration was washed twice with purified hexane, and the resulting prepolymerized catalyst (I-1) was resuspended in decane and transferred to a catalyst bottle in its entirety. Thus, a prepolymerized catalyst (I-1) was obtained. [Main polymerization] 400 g of propylene, 5.5 liters of ethylene and 4.5 liters of hydrogen were charged into an autoclave having an inner volume of 2 liters, and the temperature was raised to 60 ° C. Hydroisoquinolino) dimethoxysilane (0.4 mmol) and the prepolymerized catalyst (I-1) obtained above were converted to a titanium atom by 0.04.
After charging 02 mmol, the mixture was kept at 70 ° C. for 30 minutes to copolymerize propylene and ethylene. With respect to the obtained propylene / ethylene random copolymer, the ethylene content, the melt flow rate, the melting point, the amount of the xylene-soluble component at 20 ° C., and the molecular weight distribution (Mw / Mn) were measured by the methods described above.

The results are shown in Table 1. Next, a 30 μm-thick film was formed by a T-die molding method using the propylene / ethylene random copolymer obtained as described above.

The above films were subjected to the above-mentioned tests for the heat-sealing initiation temperature, transparency, slip properties and blocking resistance. Table 2 shows the results.

[0194]

Example 2 In the main polymerization of Example 1, except that the ethylene charge was changed to 6 liters,
A propylene / ethylene random copolymer was obtained.

With respect to the obtained propylene / ethylene random copolymer, the ethylene content, melt flow rate, melting point, amount of xylene-soluble component at 20 ° C., and molecular weight distribution (Mw / Mn) were measured by the methods described above.

Table 1 shows the results. Next, a 30 μm-thick film was formed in the same manner as in Example 1 using the propylene / ethylene random copolymer obtained as described above.

The above-mentioned test was conducted on the heat-sealing start temperature, transparency, slip property and blocking resistance of the film obtained as described above. Table 2 shows the results.

[0198]

Reference Example 1 In the main polymerization of Example 1, except that dicyclopentyldimethoxysilane was used instead of bis (perhydroisoquinolino) dimethoxysilane.
In the same manner as in the above, a propylene / ethylene random copolymer was obtained.

With respect to the obtained propylene / ethylene random copolymer, the ethylene content, melt flow rate, melting point, amount of xylene-soluble components at 20 ° C., and molecular weight distribution (Mw / Mn) were measured by the methods described above.

The results are shown in Table 1. Next, a 30 μm-thick film was formed in the same manner as in Example 1 using the propylene / ethylene random copolymer obtained as described above.

The above test was conducted on the film obtained as described above for the heat sealing start temperature, transparency, slip property and blocking resistance. Table 2 shows the results.

[0202]

[Reference Example 2] [Preparation of solid titanium catalyst component (A-2)] 7.14 g (75 mmol) of anhydrous magnesium chloride, 37.5 m of decane
and 35.1 ml of 2-ethylhexyl alcohol (2
25 mmol) and heated at 130 ° C. for 2 hours to form a homogeneous solution. Then, phthalic anhydride 1.
7 g (11.5 mmol) was added, and the mixture was further stirred and mixed at 130 ° C. for 1 hour to dissolve phthalic anhydride in the above homogeneous solution.

After the homogeneous solution thus obtained was cooled to room temperature, titanium tetrachloride (T
iCl ₄ ) was dripped in 200 ml (1.8 mol) over 1 hour. After the dropwise addition, the temperature of the resulting solution was raised to 110 ° C over 4 hours, and when the temperature reached 110 ° C, 5.03 ml (18.8 mmol) of diisobutyl phthalate was added. Stir at a temperature of 110 ° C. for a further 2 hours.

After the 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} heated again at 110 ° C. for 2 hours. After completion of the reaction, a solid portion was collected by hot filtration and washed with toluene and hexane at 110 ° C. This washing was performed until no titanium compound was detected in the washing solution.

The solid titanium catalyst component (A-2) obtained as described above was obtained as a hexane slurry. A part of the solid titanium catalyst component (A-2) was collected and dried, and the composition was analyzed.

The solid titanium catalyst component (A-2) contained 2.4% by weight of titanium, 20% by weight of magnesium, and 13% by weight of diisobutyl phthalate. [Main polymerization] 400 g of propylene, 5.5 liters of ethylene, and 4.5 liters of hydrogen were charged into an autoclave having an internal volume of 2 liters, and the temperature was raised to 60 ° C., and 0.4 mmol of triethylaluminum, dicyclopentyldimethoxy After charging 0.4 mmol of silane and 0.002 mmol of the solid titanium catalyst component (A-2) obtained above in terms of titanium atom, the mixture was kept at 70 ° C. for 30 minutes to copolymerize propylene and ethylene. I let it.

The obtained propylene / ethylene random copolymer was measured for ethylene content, melt flow rate, melting point, amount of xylene-soluble component at 20 ° C., and molecular weight distribution (Mw / Mn) by the methods described above.

The results are shown in Table 1. Next, a 30 μm-thick film was formed in the same manner as in Example 1 using the propylene / ethylene random copolymer obtained as described above.

[0209] The above-mentioned test was conducted on the film obtained as described above for the heat sealing start temperature, transparency, slip property and blocking resistance. Table 2 shows the results.

[0210]

Reference Example 3 The procedure of Example 1 was repeated except that dicyclopentyldimethoxysilane was used in place of bis (perhydroisoquinolino) dimethoxysilane and the ethylene charge was changed to 4 liters. In the same manner as in 1, a propylene / ethylene random copolymer was obtained.

With respect to the obtained propylene / ethylene random copolymer, the ethylene content, melt flow rate, melting point, amount of xylene-soluble component at 20 ° C., and molecular weight distribution (Mw / Mn) were measured by the methods described above.

The results are shown in Table 1. Next, a 30 μm-thick film was formed in the same manner as in Example 1 using the propylene / ethylene random copolymer obtained as described above.

The above test was conducted on the film obtained as described above for the heat-sealing start temperature, transparency, slip property and blocking resistance. Table 2 shows the results. Done.

[0214]

[Table 1]

[0215]

[Table 2]

[Brief description of the drawings]

FIG. 1 shows an example of a process for preparing an olefin polymerization catalyst used in the present invention and a process for producing a propylene-based random copolymer according to the present invention.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hideki Nakagawa 3-chome, Shinko Shinmachi, Sakai-shi, Osaka

Claims (3)

[Claims] 1. A catalyst obtained by copolymerizing propylene with at least one α-olefin selected from ethylene and an α-olefin having 4 to 20 carbon atoms in the presence of a Ziegler catalyst. A propylene-based random copolymer containing a halogen-containing catalyst residue of (1) having a propylene content of 90 to 99.5% by weight, and (ii) a differential scanning calorimeter. Melting point measured by (DSC) is 110 to 14
0 ° C., (iii) the amount of the xylene-soluble component at 20 ° C. is 1 to 7% by weight, and (iv) the molecular weight distribution (M) measured by gel permeation chromatography (GPC).
w / Mn) is in the range of 6 to 10, and (v) the melt flow rate (JIS K-6758, 230 ° C., load 2.16 kg) is 0.1.
A propylene-based random copolymer, which is within a range of from 10 to 10 g / 10 minutes. (A) (a) a liquid magnesium compound, (b)
Liquid titanium compound, (c) electron donor and (d) solid 2
A solid titanium catalyst component obtained by contacting a valent metal halide, (B) an organoaluminum compound, and (C)
In the presence of an olefin polymerization catalyst comprising an electron donor represented by the following general formula (1) or (2), propylene, at least one α selected from ethylene and α-olefins having 4 to 20 carbon atoms, -A process for producing a propylene-based random copolymer, characterized by copolymerizing with an olefin; [In the formula (1) or (2), R ¹ has 1 to 1 carbon atoms.
A hydrocarbon group having ^{2 to} 24 carbon atoms, R ² represents a hydrocarbon group having 2 to 24 carbon atoms,
Represents a hydrocarbon amino group or a hydrocarbon alkoxy group having 1 to 24 carbon atoms, and R ³ N has 7 carbon atoms forming a skeleton together with a nitrogen atom.
The above polycyclic amino groups are shown]. 3. (I) (A) (a) a liquid magnesium compound, (b) a liquid titanium compound, (c) an electron donor and (d)
A solid titanium catalyst component obtained by contacting a solid divalent metal halide, (B) an organoaluminum compound, and (C) an electron donor represented by the general formula (1) or (2). In the presence of an olefin polymerization catalyst comprising a prepolymerization catalyst obtained by prepolymerizing an olefin, [II] an organoaluminum compound, and [III] an electron donor represented by the general formula (1) or (2). A method for producing a propylene-based random copolymer, comprising copolymerizing propylene with at least one kind of α-olefin selected from ethylene and an α-olefin having 4 to 20 carbon atoms.