JPH0632826A - Catalyst for alpha-olefin polymerization - Google Patents

Abstract

PURPOSE:To provide a catalyst capable of producing alpha-olefin polymer powder of a highly stereoregular, high-stiffness and high-bulk density in high yield. CONSTITUTION:This catalyst for alpha-olefin polymerization is composed of (A) a Ti-contg. catalytic component obtained by prepolymerization in the following three steps: (1) olefin polymerization, (2) vinylcycloalkane polymerization, and (3) olefin polymerization in the presence of an electron-donating compound, (B) an organoaluminum compound, and (C) an electron-donating compound.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an α-olefin polymerization catalyst, and more particularly to an α-olefin polymerization catalyst capable of producing an α-olefin polymer such as highly rigid polypropylene in a high yield.

[0002]

2. Description of the Related Art There have been several attempts to add a nucleating agent to a polymer in order to increase the crystallization rate of the polymer and thus produce a highly rigid propylene polymer.
One of the methods of adding a nucleating agent to a propylene polymer is to polymerize a small amount of vinylcycloalkane prior to the polymerization of propylene, and convert the vinylcycloalkane polymer functioning as a nucleating agent into a propylene polymer as a final target. A method of incorporating is known (Japanese Patent Laid-Open No. 60-139710).
However, this method has a problem that the bulk density of the obtained propylene polymer powder is significantly reduced. As a method of solving this problem, a step of prepolymerizing propylene prior to the main polymerization of propylene (step 1)
And a method of carrying out a step (step 2) of prepolymerizing vinylcycloalkane (Japanese Patent Laid-Open No. 1-2170).
No. 15). The effect of improving the bulk density of the polymer powder by this method is that step 1 is first performed, and then step 2 is performed.
However, in this case, there is an adverse effect that the catalytic activity during the main polymerization of propylene decreases. Furthermore, when the present inventors conducted a gas phase polymerization experiment of olefins by this method, the situation of generation of bulk polymer and scale-out to the wall of the polymerization reactor occurred, and stable polymerization of olefins for a long time occurred. There is a problem of difficulty.

Further, the polymerization reactivity of vinylcycloalkane is significantly lower than that of propylene and the like, and for the purpose of increasing the polymerization rate, a method of carrying out the polymerization at a high temperature is carried out. As a result, the main polymerization of propylene is carried out. As a result, the catalytic activity deteriorates. Furthermore, for the purpose of improving the stereoregularity of the propylene polymer, has an attempt been made to carry out prepolymerization of vinylcycloalkane in the presence of an electron-donating compound,
This causes a problem that the polymerization reactivity of vinylcycloalkane is lowered.

Further, in the presence of a titanium compound, an organoaluminum compound and an organosilicon compound, prepolymerization of an olefin is carried out in multiple stages, a different organosilicon compound is used in each prepolymerization stage, and in at least one stage of each prepolymerization stage. A method for prepolymerizing an olefin suitable for obtaining a polypropylene having excellent transparency, which comprises polymerizing a branched olefin, a vinylcycloalkane, and a styrene compound, has also been proposed (JP-A-4-96907).
However, even with this method, a decrease in the polymerization ability of the catalyst during the main polymerization of propylene cannot be avoided.

[0005]

DISCLOSURE OF THE INVENTION The present invention is a catalyst for α-olefin polymerization which exhibits high stereoregularity and high rigidity and can produce an α-olefin polymer powder such as propylene having a high bulk density in a high yield. The purpose is to provide.

[0006]

Means for Solving the Problems As a result of intensive studies, the present inventors have carried out preliminary polymerization of olefins in two stages,
Between these prepolymerizations, a titanium-containing catalyst component obtained by prepolymerizing vinylcycloalkane and prepolymerizing the second stage olefin in the presence of an electron donating compound is used as an organoaluminum compound and an electron donating compound. The present invention has been completed by finding that the catalyst combined with the compound can achieve the object of the present invention.

That is, the gist of the present invention is to obtain (A) an olefin polymer-containing and vinylcycloalkane polymer obtained by carrying out the following prepolymerization steps in that order in the presence of a titanium-containing catalyst and an organoaluminum compound. A combination-containing catalyst component, a step of polymerizing an olefin, a step of polymerizing a vinylcycloalkane, a step of polymerizing an olefin in the presence of an electron-donating compound, (B) an organoaluminum compound and (C) an electron-donating compound It is a catalyst for α-olefin polymerization.

Catalyst component A catalyst component (hereinafter referred to as component A), which is one component of the catalyst of the present invention, is a titanium-containing catalyst (hereinafter referred to as component a).
And an organoaluminum compound (hereinafter referred to as component b)
It is obtained by prepolymerizing in the presence of a specific method.

(1) Component a As component a, titanium trichloride, titanium tetrachloride, trike
Lorethoxytitanium, dichlordiethoxytitanium, dichro
Lordibutoxy titanium, dichlordiphenoxy titanium,
Titanium halide compounds such as chlortributoxytitanium
Is mentioned. As titanium trichloride, titanium tetrachloride
TiCl reduced with metallic aluminum ₃・ 1/3 AlCl
₃Eutectic and titanium tetrachloride with organoaluminum compound
After reduction, heat treatment, electric children such as ether and ester
Additive compound, further halogen element, and / or halogenation
Halogen containing hydrocarbons, titanium tetrachloride, silicon tetrachloride, etc.
Use activated titanium trichloride treated with organic compounds
You can A more detailed method for preparing activated titanium trichloride is
For example, JP-A-47-34478 and 50-74594.
No. 50-74595, No. 50-12390,
50-123091, 52-107294, and
53-14192, 53-65286, 53-
It is disclosed in Japanese Patent No. 65287.

Use of a contact product of a magnesium compound represented by the general formula MgR ¹ _n R ² _2-n or a component containing them (hereinafter, these are referred to as magnesium-containing compounds) and the above titanium halide compound. You can In the above general formula, R ¹ and R ² are halogen atoms, O
H group, hydrocarbon group and alkoxy group represented by OR ³ are shown. When 0 <n <2, R ¹ and R ² may be the same or different.

Examples of the halogen atom include chlorine, bromine and iodine. The hydrocarbon group has 1 to 20 carbon atoms.
Individual alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and the like. The alkyl groups include methyl, ethyl, propyl, butyl, hexyl, 2-ethylhexyl, decyl, and the like, and the cycloalkyl groups include cyclopentyl. , Cyclohexyl, methylcyclohexyl, etc., aryl groups include phenyl, tolyl, xylyl, naphthyl, etc., and aralkyl groups include benzyl, phenethyl, 3-phenylpropyl, etc. R ³ of the alkoxy group represented by OR ³ represents a hydrocarbon group, which may be the same as the above hydrocarbon group.

Specific examples of magnesium compounds include M
gCl ₂ , MgBr ₂ , ClMgOH, MgEt ₂ , M
gBu ₂ , MgHe ₂ , MgPh ₂ , EtMgBu, E
tMgCl, BuMgCl, BuMgBr, HeMgC
1, PhMgCl, Mg (OEt) ₂ , Mg (OBu)
₂ , Mg (OHe) ₂ , Mg (OPh) ₂ , EtOMg
Cl, BuOMgCl, etc. are mentioned. In the above compounds, Et: methyl, Bu: butyl, He: hexyl and Ph: phenyl are shown, respectively. The magnesium-containing compound can be prepared from metallic magnesium by a conventional method.

Component a is the above-mentioned titanium halide compound,
In addition to the magnesium-containing compound and the electron-donating compound and / or the halogen-containing compound, and the above-mentioned three or four components, those obtained by contacting with a metal oxide can also be used.

Examples of the electron-donating compound include carboxylic acids, carboxylic acid anhydrides, carboxylic acid esters, carboxylic acid halides, alcohols, ethers, ketones, amines, amides, nitriles, aldehydes,
Examples thereof include alcoholates, phosphorus, arsenic and antimony compounds bonded to an organic group through carbon or oxygen, phosphoamides, thioethers, thioesters, carbonic acid esters and the like. Of these, carboxylic acids, carboxylic acid anhydrides, carboxylic acid esters, carboxylic acid halides,
Alcohols and ethers are preferably used.

Specific examples of the carboxylic acid include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, pivalic acid, acrylic acid, methacrylic acid, crotonic acid and other aliphatic monocarboxylic acids, malonic acid. , Succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid, fumaric acid and other aliphatic dicarboxylic acids, tartaric acid and other aliphatic oxycarboxylic acids, cyclohexanemonocarboxylic acid, cyclohexenemonocarboxylic acid, cis-1,2- Cyclohexanedicarboxylic acid, cis-4-methylcyclohexene-1,
Alicyclic carboxylic acids such as 2-dicarboxylic acid, benzoic acid, toluic acid, anisic acid, aromatic monocarboxylic acids such as p-tertiary butyl benzoic acid, naphthoic acid and cinnamic acid, phthalic acid, isophthalic acid, Terephthalic acid, naphthalic acid, trimellitic acid, hemimellitic acid, trimesic acid, pyromellitic acid,
Examples thereof include aromatic polycarboxylic acids such as mellitic acid. As the carboxylic acid anhydride, acid anhydrides of the above carboxylic acids can be used.

As the carboxylic acid ester, mono- or polyvalent esters of the above-mentioned carboxylic acids can be used, and specific examples thereof include butyl formate, ethyl acetate, butyl acetate, isobutyl isobutyrate, propyl pivalate, pivalic acid. Isobutyl, ethyl acrylate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, diethyl malonate, diisobutyl malonate, diethyl succinate, dibutyl succinate, diisobutyl succinate, diethyl glutarate, dibutyl glutarate, diisobutyl glutarate, Diisobutyl adipate, dibutyl sebacate, diisobutyl sebacate, diethyl maleate, dibutyl maleate, diisobutyl maleate,
Monomethyl fumarate, diethyl fumarate, diisobutyl fumarate, diethyl tartrate, dibutyl tartrate, diisobutyl tartrate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, methyl p-toluate, p
-Ethyl tertiary butyl benzoate, ethyl p-anisate,
Ethyl α-naphthoate, isobutyl α-naphthoate, ethyl cinnamate, monomethyl phthalate, monobutyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate, dioctyl phthalate, di2-ethylhexyl phthalate, phthalic acid Diallyl, diphenyl phthalate, diethyl isophthalate, diisobutyl isophthalate, diethyl terephthalate, dibutyl terephthalate, diethyl naphthalate, dibutyl naphthalate, triethyl trimellitate, tributyl trimellitate, tetramethyl pyromelliticate, tetraethyl pyromelliticate, tetrabutyl pyromelliticate. Etc.

As the carboxylic acid halide, acid halides of the above carboxylic acids can be used.
Specific examples thereof include acetic acid chloride, acetic acid bromide, acetic acid iodide, propionic acid chloride, butyric acid chloride,
Butyric acid bromide, butyric acid iodide, pivalic acid chloride, pivalic acid bromide, acrylic acid chloride, acrylic acid bromide, acrylic acid iodide, methacrylic acid chloride, methacrylic acid bromide, methacrylic acid iodide, crotonic acid chloride, malonic acid chloride, malonic acid bromide, Succinic acid chloride, succinic acid bromide,
Glutaric acid chloride, glutaric acid bromide, adipic acid chloride, adipic acid bromide, sebacic acid chloride,
Sebacic acid bromide, maleic acid chloride, maleic acid bromide, fumaric acid chloride, fumaric acid bromide, tartaric acid chloride, tartaric acid bromide, cyclohexanecarboxylic acid chloride, cyclohexanecarboxylic acid bromide, 1-
Cyclohexenecarboxylic acid chloride, cis-4-methylcyclohexenecarboxylic acid chloride, cis-4-methylcyclohexenecarboxylic acid bromide, benzoyl chloride,
Benzoyl bromide, p-toluic acid chloride, p-toluic acid bromide, p-anisic acid chloride, p-anisic acid bromide, α-naphthoic acid chloride, cinnamic acid chloride,
Examples thereof include cinnamic acid bromide, phthalic acid dichloride, phthalic acid dibromide, isophthalic acid dichloride, isophthalic acid dibromide, terephthalic acid dichloride, and naphthalic acid dichloride. Also, a monoalkyl halide of a dicarboxylic acid such as adipic acid monomethyl chloride, maleic acid monoethyl chloride, maleic acid monomethyl chloride, phthalic acid butyl chloride may be used.

Alcohols are represented by the general formula R ⁴ OH. In the formula, R ⁴ is alkyl having 1 to 12 carbons,
Alkenyl, cycloalkyl, aryl and aralkyl. Specific examples thereof include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, octanol, 2-ethylhexanol, cyclohexanol,
Benzyl alcohol, allyl alcohol, phenol,
Examples include cresol, xylenol, ethylphenol, isopropylphenol, p-tertiarybutylphenol, n-octylphenol and the like.

The ethers are represented by the general formula R ⁵ OR ⁶ . In the formula, R ⁵ and R ⁶ are alkyl, alkenyl, cycloalkyl, aryl and aralkyl having 1 to 12 carbon atoms, and R ⁵ and R ⁶ may be the same or different. Specific examples thereof include diethyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether,
Examples include diisoamyl ether, di-2-ethylhexyl ether, diallyl ether, ethyl allyl ether, butyl allyl ether, diphenyl ether, anisole, ethyl phenyl ether.

Examples of the halogen-containing compound include metal halides, non-metal halides, halogenated hydrocarbons, silicon halide compounds, halogen-containing alcohols and the like.

As the metal halide, AlCl ₃ , Si
Cl ₄ , SnCl _4, etc. are B as non-metal halides.
Examples of halogenated hydrocarbons such as Cl ₃ , PCl ₅ , and SOCl are dichloroethane, tetrachloroethane, hexachloroethane, trichloroethylene, tetrachloroethylene, dichloropropane, octachloropropane, trichlorocyclohexane, dichlorobenzene, and hexachloro. Chlorbenzene, etc., as the silicon halide compound,
Dichlorosilane, trichlorosilane, methyldichlorosilane, ethyldichlorosilane, dimethylchlorosilane,
Diethylchlorosilane, ethylchlorosilane, butylchlorosilane, phenyldichlorosilane, and the like are halogen-containing alcohols such as 2-chloroethanol, 2,
2,2-trichloroethanol, 1,1,1-trichloro-2-propanol, p-cresol, 1-bromo-
2-butanol and the like can be mentioned. Examples of metal oxides include silica and alumina.

As the component a, it is particularly preferable to use a so-called magnesium-supported titanium catalyst component obtained by contacting the titanium halide compound, the magnesium compound and the electron-donating compound and / or the halogen-containing compound. . As a specific preparation method thereof, for example, the method disclosed in the following patent publication can be adopted. JP-A-55-36203, 55
-127406, Sho 57-63310, Sho 58-8
No. 3006, No. 58-198503, No. 59-206
407, Sho 60-115603, Sho 61-7304
No. 62-146904 and 63-264607

(2) Component b Component b is represented by the general formula R ⁷ _n AlX _3-n (wherein R ⁷ is an alkyl group or an aryl group, X is a halogen atom, an alkoxy group or a hydrogen atom, and n is 1 ≦ n is any number within the range of 3), and examples thereof include trialkyl aluminum, dialkyl aluminum monohalide, monoalkyl aluminum dihalide, alkyl aluminum sesquihalide, dialkyl aluminum monoalkoxide and dialkyl aluminum monohydride. Particularly preferred are alkylaluminum compounds having 1 to 18 carbon atoms, preferably 2 to 6 carbon atoms, or mixtures or complex compounds thereof. Specifically, trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisobutyl aluminum,
Tributyl aluminum, triisopropyl aluminum, trialkyl aluminum such as trihexyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum bromide,
Dialkyl aluminum iodide, dialkyl aluminum monohalide such as diisobutyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, methyl aluminum dibromide, ethyl aluminum dibromide, ethyl aluminum diiodide, monoalkyl aluminum dihalide such as isobutyl aluminum dichloride, Alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride, dimethyl aluminum methoxide, diethyl aluminum ethoxide, diethyl aluminum phenoxide, dipropyl aluminum ethoxide, diisobutyl aluminum ethoxide, dialkyl aluminum monoalkoxides such as diisobutyl aluminum phenoxide, dimethy Aluminum hydride, diethyl aluminum hydride, dipropyl aluminum hydride, dialkyl aluminum hydride such as diisobutyl aluminum hydride. Among these, when titanium trichloride or activated titanium trichloride is used as the component a, a dialkylaluminum monohalide, especially diethylaluminum chloride, and a component b are contacted with titanium tetrachloride by the magnesium compound. When the obtained magnesium-supported titanium catalyst component is used, trialkylaluminum, particularly triethylaluminum and triisobutylaluminum are desirable.

(3) Preliminary Polymerization Preliminary polymerization carried out to obtain the component A comprises the following three steps. A step of polymerizing an olefin (step 1), a step of polymerizing a vinylcycloalkane (step 2), a step of polymerizing an olefin in the presence of an electron-donating compound (step 3). It is important to perform steps 1 to 3 in that order.

As the olefins used in Steps 1 and 3, in addition to ethylene, propylene, 1-butene, 1
Examples include α-olefins such as -hexene and 4-methyl-1-pentene, and different olefins can be used in step 1 and step 3, but propylene is particularly preferably used together. The vinyl cycloalkane used in step 2 has 5 to 10 carbon atoms, for example, vinyl cyclobutane, vinyl cyclopentane, vinyl cyclohexane,
Examples thereof include vinyl-3-methylcyclopentane, vinyl-2-methylcyclohexane, vinyl-3-methylcyclohexane, and vinylnorbornane, with vinylcyclohexane being particularly preferable. The electron-donating compound used in step 3 is an electron composed of an electron-donating compound that may be used when preparing the component a and an organic silicon compound having a Si—O—C bond or a Si—N—C bond. It is selected from among donor compounds.

The organosilicon compound is preferably a compound having a Si--O--C bond, and such a compound has the general formula R ⁸ _n Si (OR ⁹ ) _4-n [wherein R ⁸ is a hydrocarbon group. Or a halogen atom, R ⁹ is a hydrocarbon group, 0 ≦ n
≦ 3 is shown. ] The compound represented by these is mentioned. The hydrocarbon group represented by R ⁸ in the above general formula is an alkyl group,
Examples thereof include a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkadienyl group, a cycloalkenyl group and a cycloalkazinyl group. Examples of the halogen atom of R ⁸ include chlorine, bromine, iodine and the like. or,
Examples of the hydrocarbon group for R ⁹ include an alkyl group, a cycloalkyl group, an aryl group and an alkenyl group. Furthermore,
The hydrocarbon group of n R ^{8 and} the hydrocarbon group of R ⁹ of (4-n) OR ⁹ may be the same or different.

Specific examples thereof include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraisobutoxysilane, tetraphenoxysilane, tetra (p-methylphenoxy) silane, tetrabenzyloxysilane, methyltrimethoxysilane and methyl. Triethoxysilane, methyltributoxysilane, methyltriphenoxysilane, ethyltriethoxysilane, propyltriethoxysilane, ethyltriisobutoxysilane, ethyltriphenoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltributoxysilane, Butyltriphenoxysilane, isobutyltriisobutoxysilane, octyltriethoxysilane,
Vinyltriethoxysilane, allyltrimethoxysilane, phenyltrimethoxysilane, dimethyldiisopropoxysilane, dimethyldibutoxysilane, dimethyldihexyloxysilane, dimethyldiphenoxysilane,
Diethyldiethoxysilane, diethyldiisobutoxysilane, diethyldiphenoxysilane, dibutyldiisopropoxysilane, dibutyldibutoxysilane, dibutyldiphenoxysilane, diisobutyldiethoxysilane,
Diisobutyldiisobutoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldibutoxysilane, dibenzyldiethoxysilane, divinyldiphenoxysilane, diallyldipropoxysilane, diphenyldiallyloxysilane, methylphenyldimethoxysilane, cyclohexylmethyldimethoxysilane, Examples thereof include chlorophenyldiethoxysilane. Among the above electron-donating compounds, organic silicon compounds and carboxylic acid esters, particularly organic silicon compounds, are desirable.

The prepolymerization consisting of the above-mentioned three steps is preferably carried out in the presence of an inert medium in each step. As the inert medium, saturated aliphatic hydrocarbons such as hexane, heptane and octane, saturated alicyclic hydrocarbons such as cyclopentane and cyclohexane, and aromatic hydrocarbons such as benzene, toluene and xylene can be used. The inert medium is used in an amount such that the concentration of the component a is 1 to 500 g / liter. The prepolymerization is usually 100 ° C or lower, preferably 30 ° C.
C. or lower, more preferably -30.degree. C. to + 15.degree. C. Of course, it is free to change the temperature in each step and further in each step. The polymerization system may be a batch system, a batch system or a continuous system.

Component b has a concentration of 1 to 1,000 in each step.
It is used so as to be 20 mmol / liter, preferably 20 to 200 mmol / liter, and when the component a is titanium trichloride or active titanium trichloride, it is 0.5 to 200 gram mol, preferably 1 to 1 gram atom of titanium in the component a. Is 1
When the component a is a magnesium-supported titanium catalyst component, it is used in an amount of 0.5 to 100 gmol, preferably 1 to 20 gmol. Of course, it is possible to change the concentration of each step.

The electron-donating compound present in step 3 is 0.001 per mol of the component b present in step 3.
It is used in a proportion of ˜100 mol, preferably 0.01-10 mol.

The olefin supplied to Steps 1 and 3 may be in a gas phase or a liquid phase, and the vinylcycloalkane supplied to Step 2 may be newly supplied to Step 2 if necessary. It is also possible to pre-contact with a certain component b and then supply. In step 1 and step 3, the olefin polymer produced therein is incorporated into the component a, and the amount thereof is 0.01 to 10 in step 1 per 1 g of the component a.
0 g, preferably 0.1 to 50 g, in step 3 0.1 to
100 g, preferably 0.3-100 g, step 1
And, in the total of Step 3, 0.2 to 20 per gram of ingredient
It is 0 g, preferably 0.5 to 150 g. When the amount of preliminary polymerization in step 1 is less than 0.01 g per 1 g of the component a, the polymerization rate of vinylcycloalkane in step 2 decreases, and in order to secure the required amount of preliminary polymerization in step 2, This raises the prepolymerization temperature or prolongs the prepolymerization time, which significantly reduces the catalytic activity of component A. If the total amount of polymerization in step 1 and step 3 is less than 0.2 g per 1 g of the component a, α-
The bulk density of the olefin polymer decreases.

The amount of vinylcycloalkane prepolymerized in step 2 may be 1 to 5,000 ppm by weight in the α-olefin polymer obtained by using the catalyst of the present invention. The amount depends on the degree of polymerization activity of the component a and thus the component A, but when the component a is titanium trichloride or active titanium trichloride, it is usually 0.001 to 50 g per 1 g of the component a and magnesium is the component a. In the case of the supported type titanium catalyst component, it is 0.
It is from 01 to 100 grams.

The reaction mixture after completion of each of step 1 and step 2 may be directly supplied to the next step, or may be supplied to the next step after washing with the above-mentioned inert medium and / or removal of unreacted monomers and the like. May be. In the present invention, the unreacted vinylcycloalkene monomer in step 2 is not removed, and the method of supplying the reaction mixture of step 2 as it is to step 3 is more advantageous in the effect of the present invention. Represented and preferred. The prepolymerization can be carried out in the presence of a molecular weight modifier such as hydrogen, if necessary.

The component A thus prepared is
Although it can be diluted or washed with the above-mentioned inert medium, it is particularly preferable to wash it from the viewpoint of preventing storage deterioration of the component A. After washing, it may be dried if necessary. In this case, it is particularly preferable to dry the line segment A at a temperature of room temperature or lower and under reduced pressure so as not to reduce the catalytic activity. Further, when the component A is stored, it is desirable to store it at a low temperature as long as possible, and it is -50 ° C to + 30 ° C, particularly -2.
A temperature range of 0 ° C to + 5 ° C is recommended.

Organoaluminum Compound The organoaluminum compound which is one component of the catalyst of the present invention (hereinafter referred to as component B) is selected from the organoaluminum compounds (component b) used when preparing the above component A. To be done. It is desirable to select them according to the kind of the component a, as in the case of preparing the component A,
The desirable compounds may be the same as those used for preparing the component A. Similarly to the case of preparing the component A, the ratio of the component B to the component A is preferably changed according to the type of the component a.
It may be the same as the case of preparing.

Electron-donating compound An electron-donating compound which is one component of the catalyst of the present invention (hereinafter referred to as
It is called component C. ) Is a compound that may be used in preparing the component a and Step 3 in preparing the component A.
It is selected from the organosilicon compounds that can be used in step A. Among these, compounds that are preferably used when preparing the component A, that is, organosilicon compounds and carboxylic acid esters, and particularly organosilicon compounds are desirable. Component C is component c
The component B is used in an amount of 0.1 to 40 gram atom, preferably 1 to 25 gram atom, as aluminum atom per 1 gram mole.

The catalyst of the present invention comprising the above-mentioned component A, component B and component C exhibits excellent performance as a catalyst for homopolymerizing α-olefins or copolymerizing with other olefins.

(Co) polymerization of α -olefin The (co) polymerization of α-olefin is carried out in the presence of the above catalyst in the presence of α
-Olefins, especially α-olefins having 3 to 10 carbon atoms, such as propylene, 1-butene, 4-methyl-1-
Homopolymerize pentene, 1-hexene, etc.
It is carried out by random or block copolymerization of an olefin and another α-olefin and / or ethylene or a diolefin having 3 to 10 carbon atoms. The polymerization reaction of the α-olefin may be either a gas phase or a liquid phase, and when the polymerization is performed in the liquid phase, normal butane, isobutane, normal pentane, isopentane, hexane, heptane,
It can be carried out in an inert hydrocarbon such as octane, cyclohexane, benzene, toluene, xylene and in a liquid monomer. The polymerization temperature is usually -80 ° C to + 150 ° C,
It is preferably in the range of 40 to 120 ° C. The polymerization pressure is
For example, the pressure may be 1 to 60 atm. Further, the molecular weight of the obtained polymer is controlled by the presence of hydrogen or other known molecular weight regulator. In the copolymerization, α
The amount of the other olefin to be copolymerized with the olefin is α
-Usually up to 30% by weight, especially 0.3 to
It is selected in the range of 15% by weight. The polymerization reaction is carried out by a continuous or batch reaction, and the conditions therefor may be those usually used. Further, the copolymerization reaction may be carried out in one step or in two or more steps.

[0039]

EXAMPLES The present invention will be specifically described with reference to examples. The percentages (%) in the examples are by weight unless otherwise specified. The heptane-insoluble content (hereinafter abbreviated as HI), which represents the proportion of the crystalline polymer in the polymer, is the remaining amount when extracted with boiling n-heptane in a modified Soxhlet extractor for 6 hours. Polymer melt flow rate (MFR) is ASTM D1238, bulk density is ASTM
D1895-69 Method A was used for the measurement. The flexural modulus of the polymer can be measured by ASTM D
790. The crystallization temperature was 23 for the sample using a differential scanning calorimeter DSC Delta7 type manufactured by Perkin Elmer.
After holding at 0 ° C. for 10 minutes, the temperature was lowered at a rate of 50 ° C./minute for measurement. DuPont Impact has a resin temperature of 210 ° C
Then, mold the resin into a disk with a diameter of 20 mm and a thickness of 2 mm,
After 72 hours, it was measured according to JIS K6718 (−20 ° C.).

Example 1 Preparation of component a The component a was prepared according to the method described in Example 1 of JP-A-55-83006. That is, 0.95 g of anhydrous magnesium chloride, 10 ml of decane and 4.7 ml of 2-ethylhexanol were stirred at 125 ° C. for 2 hours,
Phthalic anhydride 0.55 was added, and the mixture was stirred at the same temperature for 1 hour to form a uniform solution. After cooling to room temperature, the whole amount was dropped into 40 ml of titanium tetrachloride kept at 120 ° C. over 1 hour. After the dropping is completed, the mixture is heated for 2 hours at 110 ° C.
Then, 0.54 ml of diisobutyl phthalate was added, and the mixture was stirred at the same temperature for 2 hours. The solid part separated by hot filtration was suspended in 200 ml of titanium tetrachloride and
The mixture was stirred at 10 ° C for 2 hours. After completion of the reaction, the solid portion separated by hot filtration was thoroughly washed with decane and hexane until the free titanium compound was not removed in the washing liquid. Component a prepared by the above method contains 2.0% titanium.
Included.

Preliminary Polymerization (1) Preliminary Polymerization of Propylene (Step 1) 100 ml of purified hexane, 6 mmol of triisobutylaluminum (hereinafter, referred to as TIBAL) and component a in terms of titanium atom were placed in a 200 ml glass flask purged with nitrogen gas. Then, propylene gas was continuously fed so that 2 g of polypropylene was produced per 1 g of component a, and propylene was prepolymerized at 0 ° C. for 1 hour. Then, nitrogen gas was blown in to purge unreacted propylene.

(2) Preliminary Polymerization of Vinylcyclohexane (Step 2) Subsequently, after adding 4 mmol of TIBAL, 10 g of vinylcyclohexane (hereinafter referred to as VCH) was charged, and prepolymerization of VCH was carried out at 10 ° C. for 5 hours. It was When a part of the product was extracted and analyzed, the prepolymerization amount of VCH was 1 g per 1 g of the component a.

(3) Prepolymerization of Propylene (Step 3) After the completion of the prepolymerization of VCH, the temperature of the polymerization system was lowered to 0 ° C.
Without removing unreacted VCH monomer, 1 mmol of diphenyldimethoxysilane (hereinafter referred to as DPMS) was charged, and propylene gas was continuously supplied so that the amount of polypropylene produced was 1 g per 1 g of the component a. Prepolymerization was carried out for 30 minutes at 0 ° C. After completion of polymerization
After sufficiently purging with nitrogen gas and separating a solid product, the solid product was washed 5 times with purified hexane. Component A thus obtained
The total amount of the prepolymers was 4.5 g per 1 g of the component a.

Polymerization of Propylene In an autoclave having an internal volume of 1.5 liter which has been purged with nitrogen gas, 55 mg of the component A obtained above, 0.4 mmol of triethylaluminum (hereinafter referred to as TEAL), 0.08 mmol of DPMA and liquefied. After charging 1 liter of propylene and 600 ml of hydrogen gas, propylene was polymerized at 70 ° C. for 1 hour. After the polymerization was completed, the unreacted propylene was purged to obtain 200 parts of white polymer powder.
g was obtained. Therefore, the catalytic activity of component A is 20,000 g.
It was PP / g · component a. The obtained polymer powder had an HI of 98.0%, a bulk density of 0.46 g / cm ³ , and an MF.
R is 8.0g / 10 minutes, 1 contained in the powder
Fine powder having a particle size of 00 μm or less was 0%. Further, an antioxidant was added to the above powder and, after sufficiently mixing, pellets were prepared with a granulator and the characteristics of the polymer were measured. The results are shown in Table 1.

[0045] In a similar manner to Step 1 of Comparative Example 1 prepolymerization Example 1, per component A1G 4.5
A catalyst component containing g of propylene polymer was obtained. Polymerization of Propylene Polymerization of propylene was carried out in the same manner as in Example 1 except that the catalyst component obtained above was used, and the results are shown in Table 1.
It was shown to.

[0046] A flask as used in Comparative Example 2 prepolymerization Example 1, purified hexane 100 ml,
TIBAL 6 mmol and component a are 2 in terms of titanium atom
After charging millimolar, charge 10g of VCH and make 1 at 50 ℃.
VCH prepolymerization was carried out for a time to prepare a catalyst component.
The preliminary weight amount was 1 g per 1 g of the component a. Polymerization of Propylene Polymerization of propylene was carried out in the same manner as in Example 1 except that the catalyst component obtained above was used, and the results are shown in Table 1.
It was shown to.

[0047] Instead of TIBAL used during the prepolymerization in Example 2 prepolymerization Example 1, T
Preliminary polymerization was carried out in the same manner as in Example 1 except that EAL was used to prepare Component A. The preliminary weight of each step is shown in Table 1. Polymerization of Propylene Polymerization of propylene was carried out in the same manner as in Example 1 except that the component A obtained above was used, and the results are shown in Table 1.

[0048] Instead of DPMA used in step 3 in the prepolymerization of Example 3 prepolymerization Example 1, except for using propyltriethoxysilane performs a preliminary polymerization in the same manner as in Example 1, the component A Prepared. The preliminary weight is shown in Table 1. Polymerization of Propylene Component A obtained in Example 1 was replaced with component A obtained above, DPMA was replaced with propyltriethoxysilane, and the amount of hydrogen used was 250 ml.
Polymerization of propylene was carried out in the same manner as in Example 1, and the results are shown in Table 1.

Example 4 Preliminary Polymerization Preliminary polymerization was carried out in the same manner as in Example 1 except that phenyltrimethoxysilane was used in place of the DPMS used in the prepolymerization step 3 of Example 1, and component A was obtained. Prepared. The preliminary weight is shown in Table 1. Polymerization of Propylene Example 1 except that Component A obtained above in Example 1 was replaced with Component A obtained above, phenyltrimethoxysilane was used instead of DPMA, and the amount of hydrogen used was 200 ml. Polymerization of propylene was carried out in the same manner as above, and the results are shown in Table 1.

[0050] Instead of the vinyl cyclohexane used in Example 5 prepolymerization Example 1, Step 2, except for using vinyl cyclopentane, performs preliminary polymerization in the same manner as in Example 1 to prepare a component A. The preliminary weight is shown in Table 1. Polymerization of Propylene Polymerization of propylene was carried out in the same manner as in Example 1 except that the component A obtained above was used, and the results are shown in Table 1.

Example 6 Preliminary Polymerization After the completion of step 2 of Example 1, the polymerized product was washed 5 times with purified hexane to remove unreacted VCH. Then TIB
After charging 10 mmol of AL and 1 mmol of DPMS, Step 3 of Example 1 was performed to prepare Component A. Polymerization of Propylene Polymerization of propylene was carried out in the same manner as in Example 1 except that the component A obtained above was used, and the results are shown in Table 1.

Comparative Example 3 Preliminary Polymerization The same procedure as in Step 1 of Example 1 was carried out, and subsequently,
TIBAL (4 mmol) was added, then VCH (10 g) was added, and VCH was prepolymerized at 50 ° C. for 1 hour to obtain a catalyst component. Polymerization of Propylene Polymerization of propylene was carried out in the same manner as in Example 1 except that the catalyst component obtained above was used, and the results are shown in Table 1.
It was shown to.

[0053] Similarly Step 1 of Comparative Example 4 prepolymerization Example 1, hexane in a flask, TIBA
After charging L and component a, add 10 g of VCH,
VCH prepolymerization was carried out at 50 ° C. for 1 hour. After completion of the polymerization, the polymerization product was washed 5 times with purified hexane to remove unreacted VCH. Then, 6 mmol of TIBAL was charged, and propylene gas was added to the component a1 of polypropylene.
A catalyst component was prepared by continuously supplying propylene so as to produce 2 g per gram and polymerizing propylene at 0 ° C. for 1 hour. Polymerization of Propylene Polymerization of propylene was carried out in the same manner as in Example 1 except that the catalyst component obtained above was used, and the results are shown in Table 1.
It was shown to.

Comparative Example 5 Preliminary Polymerization 100 ml of purified hexane was added to the flask used in Example 1.
6 mmol of TEAL and 2 mmol of the component a obtained in Example 1 in terms of titanium atom were charged, and then 10 g of VCH was charged. Then, propylene gas was continuously fed so that 2 g of polypropylene was produced per 1 g of the component a, and 0 was supplied.
Copolymerization of VCH and propylene was performed at 1 ° C. for 1 hour to prepare a catalyst component. Polymerization of Propylene Polymerization of propylene was carried out in the same manner as in Example 1 except that the catalyst component obtained above was used, and the results are shown in Table 1.
It was shown to.

[0055]

[Table 1]

[0056]

[Table 2]

Example 7 Preliminary Polymerization Component A was preliminarily polymerized in the same manner as in Example 1 to obtain Component A. Block Copolymerization of Propylene and Ethylene Using the component A obtained above, propylene was polymerized in the same manner as in Example 1. Subsequently, a mixed gas of ethylene and propylene (50/50, weight ratio) was continuously introduced into the reactor to carry out gas phase copolymerization of ethylene and propylene at 70 ° C.
I went there for 1 hour. After the polymerization was completed, unreacted monomers were purged to obtain a white polymer powder. Table 2 shows the catalytic activity during the copolymerization of ethylene and propylene and the physical properties of the obtained polymer.
It was the street.

Comparative Example 6 Prepolymerization In the same manner as in Comparative Example 1, prepolymerization of the component a was carried out to obtain a catalyst component. Block Copolymerization of Propylene and Ethylene Block copolymerization of propylene and ethylene was carried out in the same manner as in Example 7 except that the catalyst component obtained above was used, and the results are shown in Table 2.

[0059] In the same manner as in Comparative Example 7 prepolymerization Comparative Example 3, and preliminarily polymerization of components a, to obtain a catalyst component. Block Copolymerization of Propylene and Ethylene Block copolymerization of propylene and ethylene was carried out in the same manner as in Example 7 except that the catalyst component obtained above was used, and the results are shown in Table 2.

[0060]

[Table 3]

Example 8 Preparation of component a (activated titanium trichloride) A 2 liter flask equipped with a stirrer was placed in a constant temperature water bath kept at 0 ° C., and 700 ml of purified heptane and 250 ml of tetrachloride were placed in this flask. Titanium was added and mixed.
Then, while maintaining the temperature of this titanium tetrachloride heptane solution at 0 ° C., 315 ml of diethylaluminum chloride,
117 ml of ethylaluminum dichloride and 400 ml
A mixture consisting of purified heptane of 1. was mixed drop-wise over 3 hours. After the dropping is completed, heat the contents while stirring to 1
After a lapse of time, the temperature was raised to 65 ° C., and the reduced solid was obtained by stirring at this temperature for 1 hour. The reduced solid obtained was separated, washed with purified heptane, and then dried under reduced pressure at 65 ° C. for 30 minutes. Next, a suspension in which 25 g of this reduced solid was dispersed in 100 ml of purified heptane was prepared. Then, in this suspension, an amount of hexachloroethane corresponding to 1 gram mol of hexachloroethane per 1 gram atom of titanium in the reduced solid was prepared. 10 ethane
It was added in the form of a solution containing 25 g of hexachloroethane in 0 ml, and a further 0.02 per gram atom of titanium in the reduced solid.
An amount of dinormal butyl ether corresponding to 6 grammol was added and mixed with stirring. The mixture was then heated with stirring to 80 ° C. and stirred for 5 hours, then the solid obtained was washed 5 times with 100 ml of purified heptane and washed at 65 ° C. for 3 hours.
Component 0 was prepared by drying for 0 minutes.

Preliminary Polymerization (1) Step 1 In a 200 ml glass flask purged with nitrogen gas, 100 ml of purified hexane, 20 mmol of diethylaluminum chloride (hereinafter referred to as DEAC) and component a obtained above in terms of titanium atom. After charging 15 mmol, propylene gas was continuously supplied so that 2 g of polypropylene was produced per 1 g of the component a, and propylene was prepolymerized at 0 ° C. for 1 hour. Then, inject nitrogen gas,
Unreacted propylene was purged. (2) Step 2 Subsequently, after adding 10 mmol of DEAC, VCH was added.
After charging 10 g, VCH was preliminarily polymerized at 10 ° C. for 3 hours. When a part of the product was extracted and analyzed, the total amount of prepolymerization in Step 1 and Step 2 was 3 g per 1 g of the component. (3) Step 3 After the step 2, the temperature of the polymerization system was lowered to 0 ° C. and unreacted V
Without removing the CH monomer, 4.5 mmol of methyl methacrylate was charged, and propylene gas was continuously supplied so that the amount of polypropylene produced was 1 g per 1 g of the component a, and prepolymerization was performed at 0 ° C. for 30 minutes. I went. After the completion of polymerization, it was sufficiently replaced with nitrogen gas, and after separating the solid product,
It was washed 5 times with purified hexane. The total amount of prepolymerized component A thus obtained was 4.5 g per 1 g of component a. Random copolymerization of propylene and ethylene Into an autoclave having an internal volume of 1.5 liter which has been subjected to nitrogen gas substitution, 275 mg of the component A obtained above and DEAC
4.7 mmol, 0.24 mmol of methyl methacrylate, 1 liter of liquefied propylene and 600 ml of hydrogen gas were added. Next, ethylene gas was continuously supplied so that the polymerization pressure was maintained at 40 kg / cm ² · G, and the temperature was 65 ° C.
At 1 hour, random copolymerization of propylene and ethylene was performed. After the completion of the polymerization, unreacted monomers and hydrogen gas were purged, and then the produced polymer was put into 1 liter of isopropanol to remove the catalyst. The catalytic activity and the physical properties of the obtained polymer are shown in Table 3.

[0063] In a similar manner to Step 1 of Comparative Example 8 prepolymerization Example 8, per component A1G 4.5
A catalyst component containing g of propylene polymer was obtained. Random Copolymerization of Propylene and Ethylene Random copolymerization of propylene and ethylene was performed in the same manner as in Example 8 except that the catalyst component obtained above was used, and the results are shown in Table 3.

[0064] In a glass flask of Comparative Example 9 prepolymerization nitrogen gas was 200 ml, purified hexane 100ml, DEAC20 mmol and Example 8
After charging 15 mmol of the component a obtained in step 1 in terms of titanium atom, 10 g of VCH was charged, and VC was added for 40 minutes at 50 ° C.
Prepolymerization of H was performed to prepare a catalyst component. The amount of prepolymerization was 1 g per 1 g of the component a. Random Copolymerization of Propylene and Ethylene Random copolymerization of propylene and ethylene was performed in the same manner as in Example 8 except that the catalyst component obtained above was used, and the results are shown in Table 3.

[0065]

[Table 4]

[0066]

When an α-olefin such as propylene is polymerized or copolymerized by using the α-olefin polymerization catalyst of the present invention, an α-olefin having high stereoregularity and high rigidity and high bulk density is obtained. A (co) polymer powder can be obtained in high yield.

[Brief description of drawings]

FIG. 1 is a flow chart showing the steps for preparing a catalyst of the present invention.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] July 28, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0033

[Correction method] Change

[Correction content]

The reaction mixture after completion of each of step 1 and step 2 may be directly supplied to the next step, or may be supplied to the next step after washing with the above-mentioned inert medium and / or removal of unreacted monomers and the like. May be. In the present invention, vinylcyclohexane alkane unreacted monomer in step 2, without removing, as the reaction mixture of step 2, is better to adopt a method of supplying the step 3, Table more remarkably the effect of the present invention I am preferable. The prepolymerization can be carried out in the presence of a molecular weight modifier such as hydrogen, if necessary.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0034

[Correction method] Change

[Correction content]

The component A thus prepared is
Although it can be diluted or washed with the above-mentioned inert medium, it is particularly preferable to wash it from the viewpoint of preventing storage deterioration of the component A. After washing, it may be dried if necessary. In this case, it is particularly preferable to dry the component A at a temperature of room temperature or lower and under reduced pressure so as not to reduce the catalytic activity. Further, when the component A is stored, it is desirable to store it at a high temperature and a low temperature as possible.
A temperature range of 0 ° C to + 5 ° C is recommended.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0040

[Correction method] Change

[Correction content]

Example 1 Preparation of component a The component a was prepared according to the method described in Example 1 of JP-A-55-83006. That is, 0.95 g of anhydrous magnesium chloride, 10 ml of decane and 4.7 ml of 2-ethylhexanol were stirred at 125 ° C. for 2 hours,
Phthalic anhydride 0.55 was added, and the mixture was stirred at the same temperature for 1 hour to form a uniform solution. After cooling to room temperature, the whole amount was dropped into 40 ml of titanium tetrachloride kept at 120 ° C. over 1 hour. After the dropping is completed, the mixture is heated for 2 hours at 110 ° C.
The temperature was raised to 0.55 ml , diisobutyl phthalate (0.54 ml) was added, and the mixture was stirred at the same temperature for 2 hours. The solid part separated by hot filtration was suspended in 200 ml of titanium tetrachloride,
The mixture was stirred at 0 ° C for 2 hours. After completion of the reaction, the solid portion separated by hot filtration was thoroughly washed with decane and hexane until the free titanium compound was not removed in the washing liquid. Component a prepared by the above method contains 2.0% titanium.
Included.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0044

[Correction method] Change

[Correction content]

Polymerization of Propylene In an autoclave having an internal volume of 1.5 liter which has been purged with nitrogen gas, 55 mg of the component A obtained above, 0.4 mmol of triethylaluminum (hereinafter referred to as TEAL), 0.08 mmol of DPMS , After charging 1 liter of liquefied propylene and 600 ml of hydrogen gas, propylene was polymerized at 70 ° C. for 1 hour. After the polymerization was completed, the unreacted propylene was purged to obtain 200 parts of white polymer powder.
g was obtained. Therefore, the catalytic activity of component A is 20,000 g.
It was PP / g · component a. The obtained polymer powder had an HI of 98.0%, a bulk density of 0.46 g / cm ³ , and an MF.
R is 8.0g / 10 minutes, 1 contained in the powder
Fine powder having a particle size of 00 μm or less was 0%. Further, an antioxidant was added to the above powder, and after sufficiently mixing, pellets were prepared by a granulator and the physical properties of the polymer were measured. The results are shown in Table 1.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0046

[Correction method] Change

[Correction content]

[0046] A flask as used in Comparative Example 2 prepolymerization Example 1, purified hexane 100 ml,
TIBAL 6 mmol and component a are 2 in terms of titanium atom
After charging millimolar, charge 10g of VCH and make 1 at 50 ℃.
VCH prepolymerization was carried out for a time to prepare a catalyst component.
The amount of prepolymerization was 1 g per 1 g of the component a. Polymerization of Propylene Polymerization of propylene was carried out in the same manner as in Example 1 except that the catalyst component obtained above was used, and the results are shown in Table 1.
It was shown to.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0047

[Correction method] Change

[Correction content]

[0047] Instead of TIBAL used during the prepolymerization in Example 2 prepolymerization Example 1, T
Preliminary polymerization was carried out in the same manner as in Example 1 except that EAL was used to prepare Component A. In addition, preliminary polymerization of each step
The amount was as shown in Table 1. Polymerization of Propylene Polymerization of propylene was carried out in the same manner as in Example 1 except that the component A obtained above was used, and the results are shown in Table 1.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0048

[Correction method] Change

[Correction content]

[0048] Instead of DPMS used in step 3 in the prepolymerization of Example 3 prepolymerization Example 1, except for using propyltriethoxysilane performs a preliminary polymerization in the same manner as in Example 1, the component A Prepared. The amount of preliminary polymerization is shown in Table 1. Polymerization of Propylene Component A obtained above in place of the component A obtained in Example 1, propyltriethoxysilane in place of DPMS , and 250 ml of hydrogen were used.
Polymerization of propylene was carried out in the same manner as in Example 1, and the results are shown in Table 1.

[Procedure Amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0049

[Correction method] Change

[Correction content]

Example 4 Preliminary Polymerization Preliminary polymerization was carried out in the same manner as in Example 1 except that phenyltrimethoxysilane was used in place of the DPMS used in the prepolymerization step 3 of Example 1, and component A was obtained. Prepared. The amount of preliminary polymerization is shown in Table 1. Polymerization of Propylene Example 1 except that the component A obtained in Example 1 was replaced with the component A obtained above, phenyltrimethoxysilane was used in place of DPMS , and the amount of hydrogen used was 200 ml. Polymerization of propylene was carried out in the same manner as above, and the results are shown in Table 1.

[Procedure Amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0050

[Correction method] Change

[Correction content]

[0050] Instead of the vinyl cyclohexane used in Example 5 prepolymerization Example 1, Step 2, except for using vinyl cyclopentane, performs preliminary polymerization in the same manner as in Example 1 to prepare a component A. The amount of preliminary polymerization is shown in Table 1. Polymerization of Propylene Polymerization of propylene was carried out in the same manner as in Example 1 except that the component A obtained above was used, and the results are shown in Table 1.

[Procedure Amendment 10]

[Document name to be amended] Statement

[Correction target item name] 0055

[Correction method] Change

[Correction content]

[0055]

[Table 1]

[Procedure Amendment 11]

[Document name to be amended] Statement

[Correction target item name] 0062

[Correction method] Change

[Correction content]

Preliminary Polymerization (1) Step 1 In a 200 ml glass flask purged with nitrogen gas, 100 ml of purified hexane, 20 mmol of diethylaluminum chloride (hereinafter referred to as DEAC) and component a obtained above in terms of titanium atom. After charging 15 mmol, propylene gas was continuously supplied so that 2 g of polypropylene was produced per 1 g of the component a, and propylene was prepolymerized at 0 ° C. for 1 hour. Then, inject nitrogen gas,
Unreacted propylene was purged. (2) Step 2 Subsequently, after adding 10 mmol of DEAC, VCH was added.
After charging 10 g, VCH was preliminarily polymerized at 10 ° C. for 3 hours. When a part of the product was extracted and analyzed, the total amount of prepolymerization in Step 1 and Step 2 was 3 g per 1 g of the component. (3) Step 3 After the step 2, the temperature of the polymerization system was lowered to 0 ° C. and unreacted V
Without removing the CH monomer, 4.5 mmol of methyl methacrylate was charged, and propylene gas was continuously supplied so that the amount of polypropylene produced was 1 g per 1 g of the component a, and prepolymerization was performed at 0 ° C. for 30 minutes. went. After the completion of the polymerization, the atmosphere was sufficiently replaced with nitrogen gas, the solid product was separated, and then washed with purified hexane five times. The total amount of prepolymerized component A thus obtained was 4.5 g per 1 g of component a. Random copolymerization of propylene and ethylene Into an autoclave having an internal volume of 1.5 liter which has been subjected to nitrogen gas substitution, 275 mg of the component A obtained above and DEAC
4.7 mmol, 0.24 mmol of methyl methacrylate, 1 liter of liquefied propylene and 600 ml of hydrogen gas were added. Next, ethylene gas was continuously supplied so that the polymerization pressure was maintained at 40 kg / cm ² · G, and the temperature was 65 ° C.
At 1 hour, random copolymerization of propylene and ethylene was performed. After the completion of the polymerization, unreacted monomers and hydrogen gas were purged, and then the produced polymer was put into 1 liter of isopropanol to remove the catalyst. The catalytic activity and the physical properties of the obtained polymer are shown in Table 3.

Claims (1)

[Claims] 1. An olefin polymer-containing and vinyl cycloalkane polymer-containing catalyst component obtained by performing the following prepolymerization steps in the order of (A) a titanium-containing catalyst and an organoaluminum compound, and an olefin. A catalyst for polymerizing vinylcycloalkane, a step of polymerizing an olefin in the presence of an electron donating compound, (B) an organoaluminum compound and (C) an electron donating compound .