JPS62246906A - Olefin polymerization catalyst - Google Patents

Abstract

PURPOSE:To obtain the titled catalyst which excells in retentivity of polymerization activity and can permit high-temperature polymerization, by mixing a specific catalyst component with an organoaluminum compound. CONSTITUTION:A solid component (a) essentially consisting of Mg, Ti and a halogen is obtained by contacting a magnesium compound (i) (e.g., MgCl2) with a titanium compound (ii) (e.g., TiCl2) and, optionally, a halogenating agent and an electron donor (iii). A catalyst component (A) is obtained by contacting component (a) with a silicon compound (b) having a bond of formula I (e.g., phenyltriethoxysilane) in an amount equivalent to an atomic ratio of Si in component (b) to Ti in component (a) (Si/Ti) of 0.01-1,000 and a silicon compound (c) having a bond of formula II (e.g., a compound of formula III) in an amount equivalent to an atomic ratio of Si in component (c) to Ti in component (a) (Si/Ti) of 0.01-1,000 at -50-200 deg.C. Component A is mixed with 0.1-1,000pts.wt., per pt.wt. component A, organoaluminum compound (B) (e.g., triethylaluminum).

Description

[Detailed description of the invention] Technical field The present invention relates to an olefin polymerization catalyst.

The catalyst of the present invention can polymerize olefins with excellent sustainability of polymerization activity, and can perform polymerization operations at elevated polymerization temperatures.

PRIOR ART In recent years, many proposals have been made to prepare highly stereoregular polymers of α-olefins having 3 or more carbon atoms using solid components containing titanium, magnesium, and halogen as essential components.

According to the conventional proposed method, in addition to the above-mentioned solid components and organoaluminum compounds, an electron-donating compound is used during one polymerization to increase the stereoregularity of the product polymer. I needed to.

The use of electron-donating compounds as such third components complicates the catalyst system, making it difficult to control product performance. Due to the reaction between the aluminum compound and the electron-donating compound as the third component, the sustainability of the polymerization rate is low, the polymerization temperature cannot be increased, and the molecular weight of the polymer cannot be controlled. Here are some problems. Therefore, it is desired to develop a catalyst system that can produce a highly stereoregular monomer at a high catalyst yield without using an electron-donating compound as a third component.

As a solution to this problem, Japanese Patent Application Laid-Open No. 138715/1983 has been proposed. This proposal consists of tetravalent titanium, magnesium,
A titanium complex (1) containing halodane and an electron donor as essential components and an organosilicon compound (2) having an S l -0-C bond are reacted in the coexistence of an organoaluminum compound, or This is a method in which a titanium composite is treated with an aluminum compound and then polymerized using a catalyst system formed from a solid component reacted with the organosilicon compound and an organoaluminium.

Although this proposal has produced polymers with a certain degree of stereoregularity, it is insufficient to cover all the fields in which product polymers are currently used. In addition, the use of organoaluminium during the production of solid components causes deterioration of the catalyst over time5,j? + 7 years old Refine solid component during polymerization;
There are many issues that need to be resolved, such as restrictions on the ratio of the amount of W machine aluminum compound used, stereoregularity of the polymer produced, molecular weight, etc., which change with polymerization time.

Summary of the Invention The present invention provides an olefin polymerization catalyst characterized by a combination of the following component (3) and component (B).

Component (A): Component (a), component (b), and component (
Catalyst component obtained by contacting e), Component (a): Solid component containing titanium, magnesium and halodane as essential components, Component (b): Si
Silicon compound having -0-C bond, component (e):
51-Silicon compound having M bond, component (B) diorganoaluminum compound.

Seriously, the present invention consists of the following component (A) and component (B)?
An object of the present invention is to provide an olefin polymerization catalyst characterized by a combination of the following.

Component (A: the following component (a), component (b) and component (c)
) Catalyst component obtained by contacting Component (a): Solid component containing titanium, magnesium and halodane as essential components, Component (b): S
Silicon compound having an i-o-C bond, component (c):
Silicon compound having a Si-H bond, component (d): nialium halodane compound, component (B): organoaluminum compound.

Effects of the Invention According to the present invention, the problems of the above-mentioned prior art can be solved. Furthermore, compared to known catalysts such as catalysts that use electron-donating compounds as the third component, they have unique features such as good sustainability of polymerization activity and the ability to raise the polymerization temperature. These characteristics are extremely important in industrial production, and enable extremely advantageous industrial production.

Detailed Description of the Invention (Catalyst) The catalyst of the present invention is characterized by a combination of component (A) and component (B).

Components Known components can be used as component (a), which is a solid component containing titanium, magnesium and halo r7 as essential components, which can be used in the production of component (A) used in the present invention.

For example, JP-A-53-45688, JP-A-54-3894
No. 54-31092, No. 54-39483, No. 54-94591, No. 54-118484, No. 54
-131589, 55-75411, 55-9
No. 0510, No. 55-90511, No. 55-1274
No. 05, No. 55-147507, No. 55-15500
No. 3, No. 56-18609, No. 56-70005,
No. 56-72001, No. 56-86905, No. 56
-90807, 56-155206, 57-3
No. 803, No. 57-34103, No. 57-92007
No. 57-121003, No. 58-5309, No. 58-5310, No. 58-5311, No. 58-87
No. 06, No. 58-27732.

No. 58-32604, No. 58-32605, No. 58
-67703, 58-117206, 58-1
No. 27708, No. 58-183708, No. 58-18
No. 3709, No. 59-149905, No. 59-149
No. 906, etc. can be used.

In addition to the above-mentioned essential components, other components such as silicon, aluminum, and boron may be used in the component (a), and these may remain in the component (a).

Magnesium sources used to produce the above component (a) include magnesium halide, dialkoxymagnesium, alkoxymagnesium halide, magnesium oxyhalide, dialkylmagnesium, magnesium oxide, magnesium hydroxide, magnesium carboxylate, etc. Examples include magnesium compounds.

Further, the titanium source has a general formula preferably having about 1 to 10 carbon atoms, where X represents a halogen and n represents a number of 0≦n≦4. ) are titanium compounds represented by:

Specific examples include TlC24, TiBr4, Ti(OC
2H5)Cj3゜Ti(OC2H5)2C22,TI
(OC2H5), C1, Ti (0-ic, H7)c
t3, Ts (0-nc4H2)cts, Ti
(0-nC4H7) 2C12, TI (OC2H5
)Br,,rt(OC2H5)(oc4Hp)2cz
, TI(0-nC4Hp)3Ct.

TI (0-C6H5)C20,'r'1(0-iC4
H,)2C22,Ti (QC5H,,)C2,,TI
(QC6H,,)C43,Ti(OC2H5)4,Ti
(0-nC5H7) 4, Tl (0-nc4H9)
4, Tl (0-IC4H7)4, Ti (0-nC4H
15) 4, Ti(0-nC8H4,)4, TI[0CH
2CH(C2H5)C4H1]4 etc.

Alternatively, a nine-molecule compound may be obtained by reacting Ttxj (where X' represents a halogen) with an electron donor.

Specific examples include TiCl2・CH3COC2H5, T
iCl2・CH3CO2C2H5, TiC14・C6H
5No2, TiC24-CH3CO2t.

TiCl2・CH3COct%TICt4・C6H5C
O2C2H5, TiCl2-CICCI::2H.

Examples include TiCl2.C4H401.

As the halogen source, halogens contained in compounds such as the above-mentioned halogen sources and titanium sources are usually used, but other known halogenating agents can also be used.

An electron donor can be used when forming component (a). As this electron donor.

Contains #1g electron donors such as alcohols, phenols, ketones, aldehydes, carboxylates, esters of organic or inorganic acids, ethers, acid amides, acid anhydrides, electron donors, ammonia, amines, nitriles Examples include nitrogen-containing electron donors such as , isocyanate, and the like.

More specifically, methanol, ethanol, pro! 2-nor, pentanol, hegisanol, octatool, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol,
Alcohols having 1 to 18 carbon atoms such as isopropylpencyl alcohol; 6 to 18 carbon atoms which may have an alkyl group such as phenol, furesol, xylenol, ethylphenol, propylphenol, cumylphenol, nonilph, /-ol, naphthol, etc. 25 phenols; acetone, methyl ethyl ketone, methyl isobutyl ketone.

Ketones having 3 to 15 carbon atoms such as acetophenone and inosyphenone: Ketones having 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, naphthaldehyde, etc.
aldehydes; methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, ethyl stearate, methyl chloroacetate, ethyl dichloroacetate, methacryl Methyl acid, ethyl crotonate, ethyl cyclohexanecarzanate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate,
Ethyl toluate, amyl toluate, ethyl ethylbenzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, diethyl phthalate, diptyl phthalate,
Carbon-based A2-20 acid esters such as dihectyl phthalate, γ-butyrolactone, α-・f-relolactone, coumarin, phthalide, and ethylene carbonate; silicic acids such as ethyl silicate, butyl silicate, and phenyltriethoxysilane Inorganic acid esters such as esters @ acids and fluids having 2 to 15 carbon atoms such as niacetyl chloride, benzoyl chloride, toluic acid chloride, anisyl chloride, phthaloyl chloride, and iso-phthaloyl chloride: methyl ether, ethyl ether, Inzolovir. 2 to 2 carbon atoms such as ether, butyl ether, aluminum ether, tetrahydrofuran, anisole, diphenyl ether, etc.
Ethers of 0: Acetamides such as acetic acid amide, benzoic acid amide, toluic acid amide, etc.: Amines such as methylamine, ethylamine, diethylamine, tributylamine, piperinone, tribenzylamine, aniline, pyridine, picoline, tetramethylethylenediamine, etc. ; acetonitrile, benzonitrile, tolnitrile natononitriles: and the like. Two or more types of these electron donors can be used.

Component (a) is produced by, for example, the following production method using the above-mentioned titanium source, magnesium source, and halodane source, and further, if necessary, other components such as an electron donor.

B. A method of bringing magnesium halide, an electron donor, and a titanium-containing compound into contact.

First, alumina is a method in which magnesia is treated with a compound containing halodane, and then brought into contact with a compound containing magnesium halodide, an electron donor, and titanium halodane.

C. A method of contacting a solid component obtained by contacting a magnesium halide with a titanium tetraalkoxide and a specific polymeric silicon compound with a titanium halide compound and/or a silicon halodane compound.

2. A method in which a magnesium compound is dissolved in a titanium tetraalkoxide and an electron donor, and precipitated with a halogenating agent or a titanium halogen compound to bring the titanium compound into contact with a solid component.

E. A method in which an organomagnesium compound such as a Grignard reagent is reacted with a halodating agent, a reducing agent, etc., and then brought into contact with a ζ child donor and a titanium compound.

5. A method of contacting an alkoxymagnesium compound with a halogenating agent and/or a titanium compound in the presence or absence of an electron donor.

Component (b) used for producing component (A) is 5
It is a silicon compound having l-0-C bonds.

Specific examples include (cH,)st(OCH5)3, (C
H3)5 i (OC2H5) 3, (C2H5)2S
l(OCH3)2, (n-C6H11) S l (O
CRs) 5, (C2H5)Sl(OC2H5)3,
(n-C11)H21) S 1 (OC2H5) 3
, (CH2=CH) S i (OCH3)3, Ct(
CH2)3S1(OCH3)3,S i (OCH,)
4, (C2H5)2Sl(OC2H5)2, (c 17
H55) S l (OCH3) 3.5l (OC2H
5) 4, (C6Hs)S i (OCH3) 5, (
C6H5)2Sl(OCH3)2, (C6H5)(CH
3) Si(OCH3)2, (C6H5)Sl(OC2H
5) 3, (C6H5)2Sl(OC2H5)2, NC(
CH2)2Sl(OC2H5)3, (C6H5)(CH
3) Si(OC2H5)2-(n-C3H,)S
i (OC2H5)3, (cH,)st(oc3H,)
3.

(C6H5) (CH2) St (OC2H5),, CH3 CH3 (CH3) 3cm5 t (OCH,) 3, (CH
3), a silicon compound having an S 1-0-C bond such as C-8t(OC2H5)5 but not having a 5l-H bond can be exemplified.

Component (C) used in the present invention is a silicon compound bearing an 81-H bond. Specific examples include H81CL5,
I(2SiCA2.I(,SiC9,I((Cf(3)
StCj2゜H(C2H5)SiCf2, (C2H5)
3SiH, H(CH3)2SIC2゜(C2H5)2S
iH2, H(CH5)S i (OCI5)2, H8i
(OCH3)3, H2S1(OC2H5)2, H(C
)H3) 2S 1N(CH3) 2, (C2CH2C
H20)2Sl(CHs)Hl(CH3)(C2H5)
2SIH1(CM,)H8I(OC2H5)2,(CH
, )H8l (NC)f, )2, (C6H5)SiHC
l2, (C6H5)SiH3, H81(OCI(2CI
(2Ct)3, CH3(CH2), SiH(CH5)2
, H8S(OC2H5)5, (CH5) 2H8i N
(C2H5) 2 , H81(N(CH3) 2 )
5, (C6H5)(CH3)so+2, (C6H5)(
CH3)2stH.

CH3(CH2)7SIH3, (CI, CH2CH2)
5S iH.

(C6H5)2SIH2, (C6H5)2SiH(C'
H, ), (n-C5)Il, 0)5SiH, (C6H5
)3SiH.

H(CH,) 2S IQs i (CH,) 2H,
)((CM, )2SiN)(St(CH3)2)I
.

(CH3)381081(CH,)2H,H(CH,)
2Si(C6H4)St(CHI.H1H iH3 (CH3), Si0(S10)Si(CI(3)3,
(C) (3SIO)3SIH.

! Roxane, ethylhydrogensiloxane, etc. are currently available.

Component (2) of the catalyst of the present invention includes the above component (&), component (
Components (a) to (d) are obtained by contacting component (b) and component (c), but the following component (d) is further added to these components.
) can also be used to make bags.

Component (d) used in the above invention is an aluminum halodane compound. Specifically, AtC1, AzBr
No. 3 inorganic aluminum halide, At(OC2H5
)Cf2, At(OCH3)2Ct, At(OC2H5
)2ctAt(OlCH,)C62, At(0-nc4
H,)Cf2,At(OC6H5)CH2,A'(OC
6H19) Cf2, At(0-nc4H2)2C6,
Examples include aluminum halides containing hydrocarbon residues having about 1 to 10 carbon atoms, such as At(OC2H5)Br2.

The contact conditions of component (a), component (b), component (c), or each of these components and component (d) may be arbitrary as long as the effects of the present invention are recognized, but in general, The following conditions are preferred. The contact temperature is about -50 to 200°C, preferably 0 to 150°C. Contact methods include mechanical methods such as rotary gall mills, vibration mills, jet mills, and media agitation mills; in the presence of an inert diluent;
Examples include a method of contacting by stirring.

Examples of the inert diluent used at this time include aliphatic or aromatic hydrocarbons, halohydrocarbons, and polysiloxanes.

Although the quantitative ratio of component (a), component (b), and component (c) may be arbitrary as long as the effects of the present invention are observed, it is generally preferably within the following range. Ingredient (&) and Ingredient (
The quantitative ratio of b) is the atomic ratio of silicon in component (b) to the titanium component constituting component (a) (silicon/tita/), which is 0.
．． It may be within the range of 0.01 to 1000, preferably 0.1 to 1000.
Within the range of 100.

The quantitative ratio of component (a) and component (e) may be within the range of 0.01-1000 in terms of the atomic ratio of silicon in component (c) to the titanium component constituting component (a) (silicon/titanium);
Preferably it is within the range of 0.1 to 100.

When using component (d) in addition to the above components (a) to (e) in the composition of component prisoners, component (a) to component (d)
The quantitative ratio of component (,) to component (c) is the same as when using these three components described above, and the component (,) to be used in addition is the same as when using these three components.
d) f! r, the atomic ratio of aluminum in component (a) to the titanium component constituting component (a) (aluminum/
Titanium) may be within the range of 0.01 to 1000, preferably within the range of 0.1 to 100.

Component (B) Component (B) is an organoaluminum compound. Specific examples include RH-nAtXn or anie mAz (oR
') m (here, R2 and R3 are hydrocarbon residues or aqueous having about 1 to 20 carbon atoms, which may be the same or different, R4 is a hydrocarbon residue, and X is), logno, nb and m are each 0
There are some that are expressed as 3.0 (m (the number of 3). Specifically, (a) trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, trioctylaluminum, trialkylaluminum such as decylaluminum, (b) alkylaluminum rhamnohydride such as diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride, ethylaluminum dichloride, (c) diethylaluminylhamnohydride, Examples include diisobutylaluminum hydride, aluminum alkoxides such as diethylaluminum ethoxide, and noethylaluminum phenoxide.

These organoaluminum compounds (() to
≦a<3, R4 and R5 are hydrocarbon residues having about carbon a1 to about a20, which may be the same or different. ) can also be used in combination with an alkyl aluminum alkoxide. For example, a combination of triethylaluminum and noethylaluminum ethoxide, a combination of diethylaluminum monochloride and diethylaluminum ethoxide, a combination of ethylaluminum dichloride and ethylaluminum jetoxide, a combination of triethylaluminum, diethylaluminum ethoxide, and diethylaluminum chloride, Can be used in combination with

(Polymerization) The catalyst system of the present invention is applicable not only to ordinary slurry polymerization, but also to liquid-phase solvent-free polymerization, solution polymerization, or gas-phase polymerization that uses substantially no solvent. Ru.

It is also applicable to continuous polymerization, batch polymerization, or preliminary polymerization.

As the polymerization solvent in the case of slurry polymerization, saturated aliphatic or aromatic hydrocarbons such as hexane, hegetane, pentane, cyclohexane, benzene, and toluene are used alone or in mixtures.

The polymerization temperature is from room temperature to about 200°C, preferably from 50°C to
The temperature is 150° C., and hydrogen can be used as an auxiliary molecular weight regulator at that time. In addition, there are no particular restrictions on the amounts of component (A) and component (B) used, or in general,
It is preferably within the following range. Component (B) for component (A)
The weight ratio is from 01 to 1000, preferably from 10 to 500.

(Olefin) The olefin used for polymerization with the catalyst system of the present invention has the general formula R-CH=CH2 (where R is a hydrogen atom or a hydrocarbon residue having 1 to 10 carbon atoms, and has a branching group. ). Specifically, there are olefins such as ethylene, propylene, butene-1,4-pentene-1, and hexene-1,4-methylpentene-1. Preferred are ethylene and propylene.

In the case of these polymerizations, it is possible to carry out copolymerizations with up to 50" M weight percent, preferably 20 weight percent, of the above olefins relative to ethylene, and up to 30 weight percent of the above olefins relative to propylene. The above olefin,
In particular, copolymerization with ethylene can be carried out. Copolymerization with other copolymerizable polymers (for example, vinegar, vinyl, and olefins) can also be carried out.

Experimental Examples Example A-1 [Manufacture of component (A)] A thoroughly dried 0.4 liter ball mill that had been purged with nitrogen was filled with 40 stainless steel coals of 12wφ, and 20mm of MgCl2 was charged. , diheptyl phthalate 15.5
milliliter was introduced and ground for 48 hours in a rotary ball mill. After the pulverization was completed, the mixed pulverized composition was removed from the mill in a drydex. Subsequently, 8.8 grams of the pulverized composition was introduced into a flask that had been sufficiently purged with nitrogen, and further n-
25 ml of hebutane and 425 ml of TICt were introduced and reacted at 100° C. for 3 hours. After the reaction was completed, it was thoroughly washed with n-hebutane. When a part of the obtained solid component was taken out and analyzed for composition, the Ti-containing fluorescein was found to be
It was 3.01% by weight (component (a)).

50 milliliters of sufficiently purified n-hebutane was introduced into a flask that had been sufficiently purged with nitrogen, and then the components obtained above (
,) was introduced for 5 grams, and then contacted with component (c) at 70° C. for 2 hours. After the contact is complete, the product is washed with n-hebutane, and then 44% of phenyltriethoxysilane is added as component (b).
．． 5 ml was introduced, and the mixture was kept in contact at 30° C. for 2 hours.

After the contact was completed, the product was washed with n-hebutane to obtain component (A).

[Polymerization of propylene]

In a 1.5 liter stainless steel autoclave equipped with stirring and temperature control equipment, 500 milliliters of thoroughly dehydrated and deoxygenated n-hebutane and 125 milligrams of triethyl aluminum (component (B)) were added.
, and the catalyst component (component (A)) synthesized above at 15
Introduced milligrams. Then, add H2 to 60 miIJ +
Introducing J liter, raising the temperature and pressure, and increasing the polymerization pressure car to 5 kVc.
Polymerization was carried out under the following conditions: yt'G, polymerization temperature = 75°C, and polymerization time = 2 hours.

After the polymerization was completed, the obtained polymer slurry was separated by filtration, and the polymer was dried. The result was 83.6 grams of polymer. One filtrate yielded 0.92 grams of polymer. From the boiling hebutane extraction test, all products 1. ■ (hereinafter referred to as T-1.I) was 95.3 cents or 1 cent. Also, the MFR-8 of this polymer
, 7 - 710 minutes, polymer bulk specific gravity -0,387, Ac.

Example A-2 [Production of component (A)] Dehydrated and deoxidized n in a flask that was sufficiently purged with nitrogen.
- 100 ml of hebutane is introduced, then MgC
0.1 mol of l2, 0.2 mol of Ti(0-nC4H,)4
mol was introduced, and the reaction was carried out at 95°C for 2 hours. After the reaction is complete,
The temperature was lowered to 40° C., and then a total of 12 mm IJ of methylhydropolysiloxane (20 centistokes) was introduced and allowed to react for 3 hours. The generated solid component is
Washed with Hegetan.

The mixture was then purified in the same manner as above in a flask that was sufficiently purged with nitrogen. 50 ml of n-hebutane was introduced, and 0.03 mol of the solid component synthesized above was introduced in terms of Mg atoms. Next, add 5 IC14 to 25 ml of n-hebutane.
0.05 mol was mixed and introduced into a flask at 30°C for 30 minutes, and reacted at 70'C for 1 hour. After the reaction is complete, n
- Washed with hebutane.

Next, 0.003 mol of diheptyl phthalate was mixed with 25 ml of n-hebutane, and the mixture was introduced into a flask at 70° C. for 30 minutes, and reacted at 95° C. for 1 hour. After the reaction was completed, it was washed with n-heptane. Next, 245 milliliters of TiC was introduced and reacted at 100C for 6 hours. After the reaction was completed, it was thoroughly washed with n-hebutane. The titanium content was 2.45 weight percent. The solid component (A) was used as the final component (, ) for producing the solid component (A).

In the same manner as in Example A-1, 50 ml of n-hegetane was introduced into an iJ flask, and then the components obtained above (
) and then 1.8 milliliters of methylhydrodiene polysiloxane as component (e) were introduced.
Contact was carried out for 2 hours at 0°C. After the contact was completed, the mixture was washed with n-hebutane, and then 4.7 milliliter of diphenyldimethoxysilane as component (b) was introduced, and the mixture was brought into contact at 25° C. for 2 hours. After the contact was completed, the product was washed with n-hebutane to obtain component (A).

[Polymerization of propylene]

Polymerization of propylene was carried out in the same manner as in Example A-1, except that the amount of triethylaluminum used was 250 mg under the polymerization conditions of Example A-1. the result,
123 grams of polymer was obtained and the MF of this polymer was
R-6,5? /10 minutes.

T-4, I = 96.0 heavy weight 1 cent, I rimmer bulk specific gravity = 0.46 ΔC.

Example A-3 [Production of component (A)] In the synthesis of component (,) of Example A-2, Sicz4
The ingredients were prepared in the same manner as in Example A-2, except that the reaction time was changed to 90°C for 4 hours, 0.003 mol of phthaloyl chloride was used as the base of diheptyl phthalate, and the reaction was carried out at 95C for 1 hour. ) was synthesized.

In the same manner as in Example A-1, the component (&) obtained above was introduced into a flask, and then 2.0 ml of methylhydrodiene polysiloxane was introduced as component (c), and the temperature was heated at 50°C.
for 2 hours. After the contact was completed, it was washed with n-hegetane, and then the component (b) was (cH,), c-ss (oc
23.2 milliliters of H3) was introduced and contacted with H5 at 30°C for 4 hours. After the contact was completed, it was washed with n-heptane to obtain component (A).

[Polymerization of propylene]

Polymerization of propylene was carried out in the same manner as in Example A-1 except that component (A) obtained above was used. As a result, 148 grams of polymer was obtained, and the MFR-5,
8P/10 minutes, T-1, I-97, 5-cent, polymer bulk specific gravity = 0.46174-c.

Example A-4 [Production of component (A)] Dehydrated and deoxygenated n was placed in a flask that was sufficiently purged with nitrogen.
- 100 ml of hebutane is introduced, then MgC
0.1 mol of l2, 0.2 mol of Ti(0-nC4H,)4
mol was introduced, and the reaction was carried out at 95°C for 2 hours. After the reaction is complete,
The temperature was lowered to 35°C, 15 ml of 1.3.5.7-tetramethylfucrotetrasiloxane was introduced, and the mixture was reacted for 5 hours. The produced solid component was washed with n-hegetane. Next, 50 ml of n-hebutane was introduced into the flask which had been sufficiently purged with nitrogen, and the solid component synthesized above was converted into M
0.03 mol was introduced in terms of g atoms. Then Sicz4
0.06 mol was introduced at 20°C for 30 minutes, and the mixture was reacted at 50°C for 3 hours.

After the reaction was completed, it was washed with n-hebutane to obtain a solid component (&) for producing component (2). The titanium content in this solid component was 4.52 centimeters.

In the same manner as in Example A-1, the components (,) obtained above were added to Fura 4.
6 milliliters (component (b)) and methylhydrodiene? 2.7 ml of resiloxane, tolu (component (C)
) was introduced and contacted at 20°C for 2 hours. After the contact was completed, the product was washed with n-hebutane to obtain component (A).

[Polymerization of propylene]

Example A-1 except that the component (A) obtained above was used and the amount of triethylaluminum used was 50 mg.
Polymerization of propylene was carried out in the same manner.

As a result, 92 grams of polymer was obtained, and the Mra-t of this primer was 0.8? /10 minutes, T-1, I 93.
8 weight percent, polymer bulk specific gravity -0.46/ΔC Examples A-5 to 7 In the preparation of component (&) of Example A-2, component (c)
Example A except that the compounds shown in Table A- were used as
A catalyst was produced in the same manner as in Example A-2, and propylene polymerization was also carried out in the same manner as in Example A-2. The results are shown in Table A-.

Examples A-8 to 10 In the production of component (A) in Example A-3, component (b)
A catalyst was produced in the same manner as in Example A-3, except that the compounds shown in Table A-2 were used, and propylene polymerization was also carried out in the same manner as in Example A-3. The results are shown in Table A-2.

Examples A-11 to 13 In the polymerization of propylene in Example A-3, component (B)
Polymerization of propylene was carried out in the same manner as in Example A-3, except that the compounds shown in Table A-3 were used as the organic aluminum compound. The results are shown in Table A-3.

Example B-1 [Production of component (A)] 50 milliliters of sufficiently purified n-hebutane was introduced into a flask that had been sufficiently purged with nitrogen, and then 50 milliliters of sufficiently purified n-hebutane was introduced into the flask. The contact was made for 2 hours. After the contact is complete, the components (
4.6 ml of diphenyldimethoxyfuran as b) and 130.2 g of AtC as component (d) were introduced and brought into contact at 35° C. for 3 hours. After contact ends, n-
It was washed with hebutane and used as component (A).

[Polymerization of propylene] Polymerization of propylene was carried out in the same manner as in Example A-1, except that 15 milligrams of component (A) obtained above was used.

As a result, 85.8 grams of polymer was obtained.

One filtrate yielded 0.77 grams of polymer. Boiling hebutane extraction test, all products ■, ■ (hereinafter referred to as T-
I, abbreviated as I) was 96.1 weight/sercent. Moreover, the MFR of this remer was 8,11?710 min. The bulk specific gravity of the polymer was 0.371 iAC.

Example B-2 [Production of component (A)] Fifty milliliters of sufficiently purified n-hebutane was introduced into a flask that had been sufficiently purged with nitrogen to produce the catalyst component (A) obtained in Example A-2. 5 grams of the same component (a) as above, then 30.2 grams of ktct (component (d)), and 2.0 milliliter of methylhydrodiene polysiloxane were introduced and brought into contact at 70° C. for 2 hours. After contact ends
- Washed with hebutane. Then, 4.8 milliliters of phenyltriethquin silane was introduced and the mixture was kept in contact at 30° C. for 2 hours. After contacting, wash with n-hegetane and remove the component (A
).

[Polymerization of propylene]

Using the component (A) obtained above, propylene was polymerized in the same manner as in Example B-1, except that the amount of triethyl aluminum wam (component (B)) used was 250 mg.

As a result, 131 grams of polymer was obtained.
, I = 97.0 weight ff1-percent, polymer bulk specific gravity = 0.44 h plug.

Example B-3 [Production of component (A)] In the synthesis of component (a) of Example B-2, Sict4
The components ( , ) was synthesized.

The component (-) obtained above was introduced into a flask in the same manner as in Example B-1, and then 2.0 ml of methyl hydrodiene polysiloxane was added as component (c), and AtC130,2 was added as component (d). Introducing grams, 70
C for 2 hours. After the contact was completed, the product was washed with n-hebutane and then contacted as component (b) at 30° C. for 3 hours. After the contact was completed, the product was washed with n-hebutane to obtain component (A).

[Polymerization of propylene]

Polymerization of propylene was carried out in the same manner as in Example B-1 except that the component (A) obtained above was used.As a result, 155 grams of polymer was obtained, and the MFR of this polymer was 5.5 NOA in 10 minutes. , T4. I=97
, 8 M Sonoguscent, polymer bulk specific gravity = 0.46i
It was PAc.

Example B-4 [Production of component (A)] 5 grams of component (a) similar to that obtained in the production of component (A) in Examples A to 4 was introduced into a flask that had been sufficiently purged with nitrogen, To this was added 0.35 g of ALBrs as component (d), and the mixture was reacted at 50° C. for 1 hour. Next, (component (b)) and 2.2 ml of methylhydrononine polysiloxane were introduced and brought into contact at 20°C for 2 hours. After the contact was completed, it was washed with n-heptane to obtain component (A).

[Polymerization of propylene]

Example B-1 except that the component (A) obtained above was used and the amount of triethylaluminum was changed to 50 mg.
Polymerization of propylene was carried out in the same manner.

The result was 95 grams of polymer whose MFR = 9.6 y/1o min, T-1, I-94
, 5% by weight, polymer bulk specific gravity -0,46i! −
/cc.

Examples B-5 to 7 Example B- except that the compound shown in Table B- was used as component (e) in the production of the component (component body) of Example B-2.
A catalyst component was produced in the same manner as in Example B-2, and propylene polymerization was carried out in the same manner as in Example B-2.

The results are shown in Table B-.

Examples B-8 to 10 In the production of component (A) in Example B-3, component (b)
The production was carried out in the same manner as in Example B-3, except that the compounds shown in Table B-2 were used, and the polymerization of propylene was also carried out in the same manner as in Example B-3. The results are shown in Table B-2.

Examples B-11 to 13 In the polymerization of propylene in Example B-3, component (B)
Polymerization of propylene was carried out in the same manner as in Example B-3, except that the compounds shown in Table B-3 were used as the organic aluminum compound. The results are shown in Table B-3.

Examples B-14 to 16 In the preparation of component (A) in Example B-3, component (d)
The production was carried out in the same manner as in Example B-3, except that the amount of htct 3 used was changed as shown in Table B-4, and the polymerization of propylene was also carried out in the same manner as in Example B-3. The results are shown in Table 8-
4.

Procedural amendment (voluntary) April 3, 1985 2 Title of the invention Olefin polymerization catalyst λ Relationship to the case of the person making the amendment Patent applicant address 2-5-2 Marunouchi, Chiyoda-ku, Tokyo Name (a
os) Mitsubishi Yuka Co., Ltd. Agent address: 2-5-2 Marunouchi, Chiyoda-ku, Tokyo Mitsubishi Yuka Co., Ltd. Detailed description of the invention in the specification.

& Contents of the amendment (1) Between lines 13 and 14 on page 11 of the specification: ``The amounts of each of the above ingredients to be used are within the known range, and are arbitrary as long as the effects of the present invention are recognized.'' However, it is generally within the following range.

The amount of the titanium compound to be used may be in a molar ratio of 1.times.10 to 1000, preferably 0.01 to 10, relative to the amount of the magnesium compound used. When using a compound having a halogen source, the molar ratio relative to the amount of magnesium used may be within the range of lXl0-2 to 1000, regardless of whether the titanium compound and/or magnesium compound contains a halogen. , preferably within the range of 0.1 to 100.

The amount of the electron-donating compound to be used may be in a molar ratio of 10 to 10, preferably 0.01 to 5, relative to the amount of the magnesium compound used. Procedural amendment (voluntary) May 13, 1985 Commissioner of the Patent Office Mr. Akiyoshi Kuroda Toshi L Case indication Patent application No. 70494 of 1988 2 Title of the invention
Catalyst for Olefin Polymerization 1 Relationship with the Amendment Case Patent Applicant Address 2-5-2 Marunouchi, Chiyoda-ku, Tokyo Name (6
05) Mitsubishi Yuka Co., Ltd. Main agent address: 2-5-2 Marunouchi, Chiyoda-ku, Tokyo Mitsubishi Yuka Co., Ltd. Name (8191) Patent attorney Hisashi Hase:・i
Detailed description of the invention in the specification to be amended.

& Contents of the amendment (Details #1 ztM, between lines 8 and 99, add the following sentence.

``As this polymeric silicon compound, those represented by the following formula are suitable.

Cao ÷Si −0+.

Claims (1)

[Claims] (1) An olefin polymerization catalyst characterized by combining the following components (A) and (B). Component (A): Component (a), component (b), and component (
c) A catalyst component obtained by contacting Component (a): A solid component containing titanium, magnesium and halogen as essential components, Component (b): A silicon compound having a Si-O-C bond,
Component (c): a silicon compound having a Si-H bond; component (B): an organoaluminum compound.