JPH0354123B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to the production of olefin polymers (hereinafter, the use may include olefin copolymers) by polymerization of olefins (hereinafter, the use may include olefin copolymerization). Regarding the method. In particular, the present invention relates to a method for producing an olefin polymer that can yield a highly stereoregular polymer in high yield when applied to the polymerization of an α-olefin having 3 or more carbon atoms. Furthermore, in the polymerization of α-olefins having 3 or more carbon atoms, even if the melt index of the polymer is changed using a molecular weight regulator such as hydrogen during polymerization, the stereoregularity of the polymer is not significantly reduced. Regarding the possible methods. There have already been many proposals regarding methods for producing solid catalyst components containing magnesium, titanium, halogen, and electron donors as essential components. It is also known that highly stereoregular polymers can be obtained with high catalytic activity. However, many of them require further improvement in terms of activity and stereoregularity of the polymer. For example, in order to obtain high-quality olefin polymers without post-polymerization post-treatment operations, the formation ratio of stereoregular polymers must be extremely high, and the polymer yield per transition metal must be sufficiently high. must not. Depending on the type of target polymer, some of the conventionally proposed technologies can be said to be at an acceptable level from the above viewpoint, but the residual halogen content in the polymer, which is related to rusting in molding machines, is From the point of view of
There are only a few that can be said to have sufficient performance. Moreover, most of them have the disadvantage that when producing a polymer with a large melt index, the yield and stereoregularity are considerably reduced. An object of the present invention is to provide a method for polymerizing olefins which has excellent sustainability of catalytic activity, and even better polymerization activity per unit catalyst and stereoregular polymerization ability. Another object of the present invention is to provide a polymerization method in which the stereoregularity index does not tend to decrease even in the production of high melt index polymers.
Other objects and effects of the present invention will become clearer from the following description. That is, according to the present invention, (A) a highly active titanium catalyst component containing magnesium, titanium, halogen, and methyl ester of aromatic orthodicarboxylic acid as essential components, (B) an organoaluminum compound catalyst component, and (C) Si-O- An olefinic polymer characterized by polymerizing or copolymerizing an olefin in the presence of a catalyst formed from an organosilicon compound catalyst component having a C bond (provided that the propylene content is 40 to 90 mol%, the crystallinity is (excluding random copolymers of 40% by weight or less of propylene and α-olefin having 4 or more carbon atoms). The titanium catalyst component (A) used in the present invention is a highly active catalyst component containing magnesium, titanium, halogen, and a specific electron donor described below as essential components.
This titanium catalyst component (A) contains magnesium halide with lower crystallinity than commercially available magnesium halides, and usually has a specific surface area of about 50 m ² /g or more, preferably about 60 to about 800 m ² /g. , more preferably about 100 to about 400 m ² /g, and its composition is not substantially changed by washing with hexane at room temperature. However, if an organic or inorganic compound that acts to lower the apparent specific surface area is deposited or mixed, high performance may be exhibited even if the specific surface area is smaller than the above range. For example, when aluminum trichloride is combined with magnesium in a 0.5 molar amount, the specific surface area is, for example, 20 m ² /g.
It may be. In the titanium catalyst component (A),
Halogen/titanium (atomic ratio) is about 5 to about 200,
In particular, the electron donor/titanium (molar ratio) is about 0.1 to about 10, especially about 0.2.
Preferably, the magnesium/titanium (atomic ratio) is about 2 to about 100, particularly about 4 to about 50. Component (A) may also contain other electron donors, metals, elements, functional groups, etc. Such a titanium catalyst component (A) can be obtained, for example, by mutual contact of a magnesium compound (or magnesium metal), an electron donor and a titanium compound, but optionally with other reactants, such as silicon, Compounds such as phosphorus and aluminum can be used. As a method for producing such a titanium catalyst component (A), for example, JP-A-50-108385 and JP-A-50-126590 are used.
No. 51-20297, No. 51-28189, No. 51-
No. 64586, No. 51-92885, No. 51-136625, No. 25
-87489, 52-100596, 52-147688,
No. 52-104593, No. 53-2580, No. 53-40093,
No. 53-43094, No. 55-135102, No. 55-135103
No. 56-811, No. 56-11908, No. 56-18606
It can be manufactured according to the method disclosed in No. A few examples of these titanium catalyst components (A) and production methods will be briefly described below. (1) A magnesium compound or a complex compound of a magnesium compound and an electron donor,
Grinding or not grinding, with or without grinding aids, pretreated with electron donors and/or reaction aids such as organoaluminum compounds and halogen-containing silicon compounds, or without pretreatment. The solid obtained is reacted with a titanium compound that forms a liquid phase under reaction conditions. However, the above electron donor is used at least once. (2) A liquid magnesium compound that does not have reducing ability and a liquid titanium compound are reacted in the presence of an electron donor to precipitate a solid titanium complex. (3) React the material obtained in (2) with a titanium compound. (4) React the material obtained in (1) or (2) with an electron donor and a titanium compound. (5) A magnesium compound or a complex compound of a magnesium compound and an electron donor,
Grinding in the presence or absence of grinding aids etc. and in the presence of titanium compounds, pre-treated with electron donors and/or reaction aids such as organoaluminum compounds and halogen-containing silicon compounds; The solid obtained without this is treated with a halogen or a halogen compound or an aromatic hydrocarbon. However, the above electron donor is used at least once. (6) Treating the compound with a halogen or a halogen compound. Among these catalyst components, those using liquid titanium halide in catalyst preparation or those using halogenated hydrocarbons during or after the action of the titanium compound are particularly preferred. In the present invention, the electron donor contained in the titanium catalyst component (A) is a methyl ester of aromatic orthodicarboxylic acid. Specifically, methyl phthalate,
Dimethyl phthalate, dimethyl 2,3-naphthalene dicarboxylate, dimethyl 1,2-naphthalene dicarboxylate, etc. These may also be used in the form of addition compounds or complex compounds with other compounds such as aluminum compounds, phosphorus compounds, and amine compounds. It can also be used in When supporting these aromatic orthodicarboxylic acids, it is not necessarily necessary to use them as starting materials, but by using compounds that can be converted into these during the preparation process of the titanium catalyst component and converting them into these compounds during the preparation process. Good too. In the present invention, the magnesium compound used for preparing the solid titanium catalyst component [A] is, for example, a magnesium compound having a reducing ability, that is, a magnesium compound having a magnesium-carbon bond or a magnesium-hydrogen bond, such as dimethylmagnesium, diethylmagnesium. , dipropylmagnesium, dibutylmagnesium, dihexylmagnesium, diamylmagnesium, dioctylmagnesium, methylmagnesium chloride, ethylmagnesium chloride, isopropylmagnesium chloride, butylmagnesium chloride, octylmagnesium chloride, butylmagnesium hydride, amylmagnesium hydride, ethylbutylmagnesium, butylethoxymagnesium, etc., and these magnesium compounds are
For example, it may be used in the form of a complex compound with organoaluminium or the like. Further, these magnesium compounds may be in a solid state or a liquid state. On the other hand, magnesium compounds without reducing ability include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride; methoxymagnesium chloride;
Alkoxymagnesium halides such as ethoxymagnesium chloride, isopropoxymagnesium chloride, butoxymagnesium chloride, octoxymagnesium chloride; allyloxymagnesium halides such as phenoxymagnesium chloride, methylphenoxymagnesium chloride; ethoxymagnesium, isopropoxymagnesium, butoxymagnesium, n- octoxymagnesium,
Alkoxymagnesium such as 2-ethylhexoxymagnesium; phenoxymagnesium,
Examples include allyloxymagnesium such as dimethylphenoxymagnesium; magnesium carboxylates such as magnesium laurate and magnesium stearate. Further, these magnesium compounds without reducing ability may be derived from the above-mentioned magnesium compounds having reducing ability, or may be derived during preparation of the catalyst component. Moreover, the magnesium compound may be a complex compound with other metals, a composite compound, or a mixture with other metal compounds. Furthermore, it may be a mixture of two or more of these compounds. Among these, preferred magnesium compounds are those without reducing ability, and particularly preferred are halogen-containing magnesium compounds, particularly magnesium chloride, alkoxymagnesium chloride, and allyloxymagnesium chloride. In the present invention, there are various titanium compounds () used for preparing the solid titanium catalyst component [A], but usually Ti(OR) _g X _4-g (R is a hydrocarbon group, X is a halogen, 0≦g A tetravalent titanium compound represented by ≦4) is suitable. More specifically,
Titanium tetrahalides such as _TiCl4 , _TiBr4 , _TiI4, Ti( _OCH3 ) _Cl3 , Ti( _{OC2H5 ) Cl3} , Ti
Trihalogenated alkoxytitanium such as ( _{OisoC4H9 ) Br3 ;} Ti( _OCH3 ) _2Cl2 , _Ti ( _OC2H5 ) _{2Cl2 ,} Ti
_{Dihalogenated alkoxy} titanium such as ( _{On − C4H9} ) _2Cl2 , Ti( _OC2H5 ) _2Br2 ; Ti( _OCH3 ) _3Cl , Ti
(OC ₂ H ₅ ) ₃ Cl, Ti (On−C ₄ H ₉ ) ₃ Cl, Ti
Monohalogenated trialkoxytitanium such as (OC ₂ H ₅ ) ₃ Br; Ti(OCH ₃ ) ₄ , Ti(OC ₂ H ₅ ) ₄ , Ti(On−
Examples include tetraalkoxytitanium such as C ₄ H ₉ ) ₄ . Preferred among these are halogen-containing titanium compounds, particularly titanium tetrahalide, and particularly preferred is titanium tetrachloride. These titanium compounds may be used alone or in the form of a mixture. Alternatively, it may be used after being diluted with a hydrocarbon or halogenated hydrocarbon. In preparing the titanium catalyst component (A), a titanium compound, a magnesium compound, an electron donor to be supported, and other electron donors that may be used as necessary, such as alcohol, phenol,
The amount of monocarboxylic acid ester, silicon compound, aluminum compound, etc. to be used varies depending on the preparation method and cannot be unconditionally specified, but for example, the amount of the electron donor to be supported per 1 mole of magnesium compound.
0.05 to 5 mol, titanium compound 0.05 to 1000
The proportion can be on the order of moles. In the present invention, olefin polymerization or copolymerization is carried out using a combination catalyst of the solid catalyst component [A] obtained as described above, an organoaluminum compound catalyst component [B], and a silicon compound [C]. As the component [B], () an organoaluminum compound having at least one Al-carbon bond in the molecule, for example, the general formula R ¹ mAl(OR ² )nHpXq (where R ¹ and R ² are carbon atoms, Usually 1 or
15 hydrocarbon groups, preferably 1 to 4 hydrocarbon groups, which may be the same or different from each other. X is halogen, m is 0<m≦3, 0≦n<3, p is 0≦p<
3. Even if q is a number of 0≦q<3, and m+
n + p + q = 3), a group metal compound represented by the general formula M ¹ AlR ¹ ₄ (where M ¹ is Li, Na, K, and R ¹ is the same as above); Examples include complex alkylated products with aluminum. Examples of the organoaluminum compounds belonging to the above () include the following. General formula R ¹ mAl(OR ² ) _3-n (where R ¹ and R ² are the same as above. m is preferably a number of 1.5≦m≦3), general formula R ¹ mAlX _3-n ( Here ^{, R 1 is} the _same as above. ≦
m<3. ), general formula R ¹ mAl(OR ² )nXq (where R ¹ and R ² are the same as above, X is halogen, 0<m≦3, 0≦n<3, 0≦q<3,
+n+q=3). In aluminum compounds belonging to (),
More specifically, triethylaluminum, tributylaluminum, etc., trialkylaluminum, trialkenylaluminum such as triisoprenylaluminum, dialkylaluminum alkoxide such as diethylaluminum ethoxide, dibutylaluminum butoxide, ethylaluminum sesquiethoxide, butylaluminum sesqui Besides alkyl aluminum sesquialkoxides such as butoxide, R ¹ _2.5 Al (OR ² )
Partially alkoxylated alkyl aluminum halides, such as diethylaluminum chloride, dibutyl aluminum chloride, diethyl aluminum bromide, ethyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquichloride, with an average composition expressed as _0.5 , etc. Alkylaluminum sesquihalides such as bromides, partially halogenated alkyl aluminum dihalides such as alkyl aluminum dihalides such as ethyl aluminum dichloride, propyl aluminum dichloride, butyl aluminum dibromide, etc., diethylaluminum hydride, dibutyl aluminum hydride, etc. Partially hydrogenated alkyl aluminum such as dialkyl aluminum hydride, alkyl aluminum dihydride such as ethyl aluminum dihydride, propyl aluminum dihydride, partially hydrogenated alkyl aluminum such as eryll aluminum ethoxy chloride, butyl aluminum butoxy chloride, ethyl aluminum ethoxy bromide etc. It is an alkoxylated and halogenated alkyl aluminum. Compounds belonging to the above () include LiAl
Examples include (C ₂ H ₅ ) ₄ and LiAl(C ₇ H ₁₅ ) ₄ . Further, as a compound similar to (), an organic aluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom may be used. Examples of such compounds include (C ₂ H ₅ ) ₂ AlOAl(C ₂ H ₅ ) ₂ , (C ₄ H ₉ ) ₂ AlOAl
( _C4H9 ) _{2 ,} Examples include: Among these, it is particularly preferable to use trialkylaluminum and the above-mentioned alkyl aluminum in which two or more aluminums are combined. The organosilicon compound catalyst component [C] having a Si--O--C bond used in the present invention is, for example, an alkoxysilane, an aryloxysilane, or the like. An example of such is the formula RnSi(OR ¹ ) _4-o , where 0≦n≦3, R is a hydrocarbon group, such as an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, a haloalkyl group, an aminoalkyl group. groups, etc., or halogen, R ¹
is a hydrocarbon group, such as an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an alkoxyalkyl group, provided that n R, (4-n)
The ^OR groups may be the same or different. ) can be mentioned. Other examples include siloxanes having ^one OR group and silyl esters of carboxylic acids. Other examples include compounds in which two or more silicon atoms are bonded to each other via oxygen or nitrogen atoms. The above organosilicon compounds can be produced by reacting a compound without Si-O-C bond with a compound having O-C bond in advance or by reacting them at the polymerization site.
It may be used by converting it into a compound having a bond.
Examples of this include combinations of halogen-containing silane compounds or silicon hydrides that do not have Si-O-C bonds, and alkoxy group-containing aluminum compounds, alkoxy group-containing magnesium compounds, other metal alcoholates, alcohols, formic acid esters, ethylene oxides, etc. Examples include combination use. The organosilicon compound may also contain other metals (eg, aluminum, tin, etc.). More specifically, trimethylmethoxysilane,
Trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane, diphenyldiethoxysilane, ethyltrimethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane , γ-chloropropyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlortriethoxysilane, ethyltriethoxysilane Isopropoxysilane, vinyltributoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriallyloxysilane, vinyltris(β-methoxyethoxy)silane, vinyltriacetoxysilane, dimethyltetraethoxysilane Examples include siloxane and phenyldiethoxydiethylaminosilane. Among these, particularly preferred are methyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, vinyltributoxysilane, ethyl silicate, These are those represented by the formula RnSi(OR ¹ ) _4-o, such as diphenyldimethoxysilane, diphenyldiethoxysilane, and methylphenylmethoxysilane. Component [C] can also be used in the form of an adduct with other compounds. Olefins used for polymerization include ethylene,
These include propylene, 1-butene, 4-methyl-1-pentene, 1-octene, etc., and these can be copolymerized as well as homopolymerized. In copolymerization, polyunsaturated compounds such as conjugated dienes and non-conjugated dienes can be selected as copolymerization components. Polymerization can be carried out in either liquid phase or gas phase. When carrying out liquid phase polymerization, an inert solvent such as hexane, heptane or kerosene may be used as the reaction medium, but the olefin itself may also be used as the reaction medium. The amount of catalyst to be used is, per reaction volume, component [A] is about 0.0001 to about 1.0 mmol in terms of titanium atoms, component [B] is about 1 mole of titanium atom in component [A], and component [B] is Component [C] is added to component [C] per mole of metal atom in component [B] such that the amount of metal atoms in component is about 1 to about 2000 mol, preferably about 5 to about 500 mol. The amount of Si atoms is preferably about 0.001 to about 10 moles, preferably about 0.01 to about 2 moles, particularly preferably about 0.05 to about 1 mole. These catalyst components [A], [B], and [C] may be brought into contact with each other during polymerization, or may be brought into contact with each other before polymerization. In contacting before polymerization, only two arbitrary components may be freely selected and brought into contact, or a portion of each component may be brought into contact with two or three components. Furthermore, each component may be brought into contact with each other before polymerization under an inert gas atmosphere or under an olefin atmosphere. The polymerization temperature of the olefin is preferably about 20 to about 200°C, more preferably about 50 to about 180°C, and the pressure is about normal pressure to about 100 kg/cm ² , preferably about 2 to about 50 kg/cm ² . Preferably it is carried out under pressure conditions. Polymerization can be carried out in any of the batch, semi-continuous and continuous methods. Furthermore, it is also possible to carry out the polymerization in two or more stages with different reaction conditions. In the present invention, especially α-
When applied to the stereoregular polymerization of olefins,
Polymers with a high stereoregularity index can be produced with high catalytic efficiency. In addition, in olefin polymerization using the same solid catalyst component as previously proposed, in many cases, when trying to obtain a polymer with a large melt index by using hydrogen, the stereoregularity tends to decrease to a considerable extent. However, by adopting the present invention, it is possible to reduce this tendency. Furthermore, in relation to high activity, the polymer yield per unit solid catalyst component is superior to conventional proposals at the level of obtaining polymers with the same stereoregularity index, so catalyst residues in the polymer can be reduced. In particular, it is possible to reduce the halogen content, and it is possible to omit the catalyst removal operation.
The tendency of molds to rust during molding can be significantly suppressed. In addition, it is not only possible to change the melt index of the polymer with a smaller amount of molecular weight regulators such as hydrogen than in conventional catalyst systems, but surprisingly, it is possible to increase the amount of molecular weight regulators such as hydrogen added. According to
It has the advantage that the activity of the catalyst system tends to improve. This is something that did not exist in conventional catalyst systems, and when trying to obtain a high melt index polymer with conventional catalyst systems, increasing the amount of molecular weight regulator such as hydrogen reduces the partial pressure of the olefin monomer. As a result, the activity of the polymerization system inevitably decreases, but the catalyst system according to the present invention does not cause these problems at all, and on the contrary, the activity tends to be improved. In addition, with conventional catalyst systems, activity decreases with the passage of polymerization time, but with this catalyst system, this is almost not observed, so for example, when used in multi-stage continuous polymerization, the amount of polymer produced can be significantly increased. Connect. Furthermore, since this catalyst system is very stable even at high temperatures, for example, even when propylene is polymerized at 90°C, no significant decrease in stereoregularity is observed. Next, the present invention will be explained in more detail with reference to examples. Example 1 [Preparation of catalyst component [A]] 20 g of anhydrous magnesium chloride, dimethyl phthalate
4.9ml, titanium tetrachloride 3.3ml and silicone oil (TSS-451, 20cs manufactured by Shin-Etsu Chemical Co., Ltd.) 3.0 as a grinding aid.
Internal volume 800 containing 2.8 kg of stainless steel (SUS-32) balls with a diameter of 15 mm in a nitrogen atmosphere.
ml, charged into a stainless steel (SUS-32) ball mill container with an inner diameter of 100 mm, and subjected to an impact acceleration of 7 G for 24
contact for an hour. 15g of the obtained co-pulverized material is 1,2
- Suspended in 150 ml of dichloroethane and heated to 80°C for 2 hours.
After contacting with stirring for a period of time, the solid portion is collected by filtration, thoroughly washed with purified hexane until no free 1,2-dichloroethane is detected during washing, and then dried to obtain catalyst component [A]. The components were 4.4% by weight of titanium, 61.0% by weight of chlorine, and 17.0% by weight of magnesium in terms of atoms, and the specific surface area was 233 m ² /g. [Polymerization] Purified hexane in an autoclave with an internal volume of 2
Charge 750 ml of triethylaluminum 2.51 mmol, diphenyldimethoxysilane 0.250 mmol and the above catalyst component [A] under a propylene atmosphere at room temperature.
was charged in an amount of 0.015 mmol in terms of titanium atoms. hydrogen
After introducing 200 ml, the temperature was raised to 70°C and polymerization was carried out for 4 hours. The pressure during polymerization was maintained at 7 kg/cm ² G.
After the polymerization was completed, the slurry containing the produced polymer was filtered and separated into a white powdery polymer and a liquid phase. The yield of white powdery polymer after drying was 106.9g,
The extraction residue rate with boiling n-heptane was 97.5%.
The MI was 10 and the apparent density was 0.37 g/ml.
On the other hand, 2.2g of solvent-soluble polymer was obtained by concentrating the liquid phase.
I got it. Therefore the activity is 7300g-pp/mmol-
Ti and total II was 95.5%. Example 2 [Preparation of catalyst component [A]] 20 g of anhydrous magnesium chloride, dimethyl phthalate
4.9ml and silicone oil (TSS-451, 20cs, manufactured by Shin-Etsu Chemical Co., Ltd.) as a grinding aid in a nitrogen atmosphere with a diameter of 15mm.
A ball mill container made of stainless steel (SUS-32) with an internal volume of 800 ml and an inner diameter of 100 mm containing 2.8 kg of stainless steel (SUS-32) balls of 1.2 mm in diameter was charged, and the balls were brought into contact with each other for 24 hours at an impact acceleration of 7 G. 15 g of the obtained co-pulverized material was suspended in 150 ml of titanium tetrachloride,
After contacting with stirring at 110°C for 2 hours, the solid part was collected by filtration, thoroughly washed with purified hexane until no free titanium tetrachloride was detected in the washing liquid, and then dried. get. The components were 1.4% by weight of titanium, 56.0% by weight of chlorine, and 18.0% by weight of magnesium in terms of atoms, and the specific surface area was 176 m ² /g. [Polymerization] Purified hexane in an autoclave with an internal volume of 2
Charge 750 ml of triethylaluminum 2.51 mmol, diphenyldimethoxysilane 0.250 mmol and the above catalyst component [A] under a propylene atmosphere at room temperature.
was charged in an amount of 0.015 mmol in terms of titanium atoms. hydrogen
After introducing 200 ml, the temperature was raised to 70°C and polymerization was carried out for 4 hours. The pressure during polymerization was maintained at 7 kg/cm ² G.
After the polymerization was completed, the slurry containing the produced polymer was filtered and separated into a white powdery polymer and a liquid phase. The yield of white powdery polymer after drying was 121.0g,
The extraction residue rate with boiling n-heptane was 95.3%.
The MI was 11 and the apparent density was 0.32 g/ml.
On the other hand, by concentrating the liquid phase, 4.7g of solvent-soluble polymer was obtained.
I got it. Therefore the activity is 8400g-pp/mmol-
Ti and total II was 91.7%. Example 3 [Preparation of catalyst component [A]] High-speed stirring device with internal volume 2 (manufactured by Tokushu Kika Kogyo)
After sufficiently replacing with N ₂ , 700ml of refined kerosene, commercially available.
10 g of MgCl ₂ , 24.2 g of ethanol, and 3 g of Emazol 320 (manufactured by Kao Atlas Co., Ltd., sorbitan distearate) were added, and the temperature of the system was raised while stirring.
The mixture was stirred at 120° C. and 800 rpm for 30 minutes. Under high speed stirring,
Using a Teflon tube with an inner diameter of 5 mm, the liquid was transferred to a 2-glass flask (equipped with a stirrer) that had been previously cooled to -10°C and filled with refined kerosene 1. The produced solid was collected by filtration and thoroughly washed with hexane to obtain a carrier. After suspending 7.5 g of the carrier in 150 ml of titanium tetrachloride at room temperature, the temperature was raised to 120° C. with stirring. 80 while heating up
1.1 ml of dimethyl phthalate was added at °C. 120℃2
After stirring and mixing for an hour, the solid part was collected by filtration, suspended again in 150 ml of titanium tetrachloride, and again
Stirring and mixing was performed at 120°C for 2 hours. Furthermore, a reaction solid was collected by filtration and washed with a sufficient amount of purified hexane to obtain a solid catalyst component [A]. The component is titanium 3.2 in terms of atoms.
% by weight, 60.0% by weight of chlorine, 17.0% by weight of magnesium, and the specific surface area was 218 m ² /g. [Polymerization] Purified hexane in an autoclave with an internal volume of 2
Charge 750 ml of triethylaluminum 2.51 mmol, diphenyldimethoxysilane 0.250 mmol and the above catalyst component [A] under a propylene atmosphere at room temperature.
was charged in an amount of 0.015 mmol in terms of titanium atoms. hydrogen
After introducing 200 ml, the temperature was raised to 70°C and polymerization was carried out for 4 hours. The pressure during polymerization was maintained at 7 kg/cm ² G.
After the polymerization was completed, the slurry containing the produced polymer was filtered and separated into a white powdery polymer and a liquid phase. The yield of white powdery polymer after drying was 136.1g,
The extraction residue rate with boiling n-heptane was 96.4%.
The MI was 22 and the apparent density was 0.43 g/ml.
On the other hand, 3.6g of solvent-soluble polymer was obtained by concentrating the liquid phase.
I got it. Therefore the activity is 9300g-pp/mmol-
Ti and total II was 93.9%. Examples 4, 5, 6, 7, 8, 9, 10 Using the solid catalyst component [A] described in Example 1,
Diphenyldimethoxysilane added during polymerization
0.25 mmol, phenyltrimethoxysilane 0.25
mmol, vinyltrimethoxysilane 0.30 mmol,
Methyltrimethoxysilane 0.45mmol, tetraethoxysilane 0.30mmol, ethyltriethoxysilane 0.25mmol, vinyltriethoxysilane 0.25
mmol, methylphenyldimethoxysilane 0.25m
The same procedure as in Example 1 was carried out except that the value was changed to mol. The polymerization results are shown in Table 1.

[Table] Examples 11, 12, 13 Amount of hydrogen added during polymerization: 400ml, 800ml, 1600ml
Polymerization was carried out in the same manner as in Example 4, except that . The polymerization results are shown in Table 2.

【table】 [Brief explanation of drawings]

Figure 1 is a flowchart showing the steps for preparing the catalyst used in the method of the present invention.

Claims (1)

[Scope of Claims] 1 (A) a highly active titanium catalyst component containing magnesium, titanium, halogen, and methyl ester of aromatic orthodicarboxylic acid as essential components, (B) an organoaluminum compound catalyst component, and (C) Si- An olefin-based polymer characterized by polymerizing or copolymerizing an olefin in the presence of a catalyst formed from an organosilicon compound catalyst component having an O-C bond (provided that the propylene content is 40 to 90 mol%, (excluding random copolymers of propylene with a crystallinity of 40% by weight or less and α-olefin having 4 or more carbon atoms).