JPS59129203A - Production of polyolefin - Google Patents

Abstract

PURPOSE:To produce a highly stereoregular polyolefin in high activity, by (co) polymerizing an alpha-olefin in the presence of a catalyst comprising a specified solid catalyst component, an organometallic compound, and a silane compound. CONSTITUTION:A catalyst is prepared by combining an organometallic compound (e.g., triethylaluminum) with a silane compound of formula I (wherein R<1-3> are each a 1-24C hydrocarbon residue, alkoxy, H, or a halogen, R<4> is a 1-24C hydrocarbon residue, and n is in the range of 1<=n<=30), and a solid catalyst component prepared by infiltrating a Ti compound (e.g., TiCl4) into a solid substance obtained by contacting a magnesium halide (e.g., MgCl2) with a silane compound of formula I and a compound of formula II (wherein R is H, a halogen, or a 1-24C hydrocarbon residue, R' is R<4>, 1<=r<=3, 0<=p, q<=6, and 1<=r+ p+q<=6). An alpha-olefin is (co)polymerized at 20-300 deg.C and a pressure of atmosphere -70kg/cm<2>G in the presence of the above catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for highly active polymerization or copolymerization of α-olefins with good stereoregularity using a novel catalyst.

As a highly stereoregular polymerization catalyst for a-olefin, a catalyst comprising a titanium halide and an organoaluminum compound has been known. However, although a highly stereoregular polymer can be obtained in polymerization using this catalyst system, it is necessary to remove catalyst residues in the resulting polymer, which has a low catalytic activity.

In recent years, many proposals have been made to improve the activity of catalysts. According to these proposals, it has been shown that a highly active catalyst can be obtained when a catalyst component in which titanium tetrachloride is supported on an inorganic solid carrier such as MgC12 is used.

However, in the production of polyolefins, it is preferable that the catalyst activity be as high as possible, and catalysts with even higher activity have been desired. It is also important that the amount of active moieties produced in the polymer is as small as possible.

As a result of intensive research on these points, the present inventors found that
In particular, a new catalyst was discovered. That is,
The present invention relates to a method for producing polyolefins with extremely high activity and high stereoregularity using a regular catalyst. By using the catalyst of the present invention, the monomer partial pressure during polymerization is low and Due to the short polymerization time, the amount of catalyst residue in the resulting polymer is extremely small, so the catalyst removal step can be omitted in the polyolefin production process.
In addition, many effects can be obtained, such as the amount of active moieties produced in the produced polymer is extremely small. The present invention will be explained in detail below.

The present invention is characterized in that CD (1) magnesium halide, (2) general formula R"+Si-0-)-nR' (where R1,
R2 and R3 represent a hydrocarbon residue having 1 to 224 carbon atoms, an alkoxy group, hydrogen or a halogen atom, and R4 represents a hydrocarbon residue having 1 to 24 carbon atoms.

n represents a compound represented by 1≦n≦60) and or a hydrocarbon residue having 1 to 24 carbon atoms; is an integer, 1≦r≦6.0≦p (6, O≦q(6
, 1≦r+p+q<6. 4) A solid catalyst component on which a titanium compound is supported, [■
] In the organometallic compound, R, I FC'' represents a hydrocarbon residue having 1 to 24 carbon atoms, an alkoxy group, hydrogen or a halogen atom, and R4 represents a hydrocarbon residue having 1 to 24 carbon atoms. n is 1≦n≦30) by polymerizing or copolymerizing an α-olefin using a catalyst consisting of a combination of compounds represented by the formula (1≦n≦30) to produce a highly active and highly stereoregular polyolefin “f:4’A”. Regarding the method.

In the present invention, (1) magnesium halide, (
2) -MEl' The compound represented by the formula R3+5i-O+R' -C and the method for obtaining the solid substance of the present invention are not particularly limited.
~400 degrees Celsius] The reaction can be carried out by contacting under heating at preferably 50°C to 600°C for usually 5 minutes to 20 hours, by co-pulverization, or by a suitable combination of these methods. You may let them.

However, there is no particular restriction on the reaction order of components (1) to (b).

The inert solvent is not particularly limited, and hydrocarbon compounds and/or derivatives thereof that do not normally inactivate the Ziegler type catalyst can be used. Specific examples of these include propane, butane, pentane, hexane, heptano, octane, benzene, toluene, xylene, cyclohexane, and other aliphatic saturated hydrocarbons, aromatic hydrocarbons, aliphatic hydrocarbons, and ethanol,
diethyl ether, tetrahydrofuran, ethyl acetate,
Examples include alcohols such as ethyl benzoate, ethers, and esters.

The co-pulverization process is usually carried out using equipment such as a ball mill, vibration mill, rod mill, or impact mill, and is usually carried out at a temperature of 0°C to 2°C.
00℃, temperature of 20℃~100℃, 05~
It is recommended to do this for 30 hours.

In the present invention, a method of obtaining a solid substance by co-pulverizing components (1) to (3) is particularly preferably employed.

In the present invention, the molar ratio of component (1) magnesium halide to component I (2) compound represented by the general formula R3+51-0suR4 is component (1):component ( 2) is i :'
The ratio is 0.001 to 10, preferably 1:0.0+ to 1. Component (3) fi'y complete set % formula % () In the ratio of component (1):component (3) is +: o, ooi ~ 10
, preferably 1:O, [11-1.

The solid catalyst component [I] is obtained by supporting the titanium compound on the solid carrier thus obtained.

A known method can be used to support the titanium compound on the carrier. For example, the solid support can be brought into contact with an excess of titanium compound under heating in the presence/absence of a solvent, preferably in the presence of a solvent such as 1,2-dichloroethane. This is conveniently carried out by heating both to 50°C to 300°C, preferably 80°C to 150°C. The reaction time is not particularly limited, but is usually 5 minutes or more, and long-term contact may be allowed, although it is not necessary. For example 5
Treatment times can range from minutes to 10 hours, preferably from 1 to 4 hours.

Of course, this treatment should be carried out in an atmosphere of inert gas free of oxygen and moisture. The means for removing unreacted titanium compounds immediately after the completion of the reaction is not limited, and it is possible to wash the Ziegler catalyst several times with an inert solvent and evaporate the washing liquid under reduced pressure to obtain a solid powder. Another method is to co-pulverize the solid support and the required amount of the titanium compound.

Co-grinding is carried out at Torimiya ℃~200℃
The catalyst components of the invention can be prepared by co-milling at a temperature of 0° C. for 0.5 to 30 hours. Of course, the co-grinding operation should be carried out in an inert gas atmosphere - and moisture should be avoided as much as possible.

The magnesium halide used in the present invention is actually 'J! f [I region f(D .

1 -j submersion type R3 (-Si -0-) used in the present invention
R' (where n 2 R1, R2, R3 have 1 to 24 carbon atoms, preferably 1 to 1
8 represents a hydrocarbon residue, an alkoxy group, hydrogen or a halogen atom, and R4 has 1 to 24 carbon atoms, preferably 1 to 18 carbon atoms.
The hydrocarbon residue of n is 1≦n≦60. ) Examples of compounds represented by are monomethyltrimethoxysilane, monoethyltrimethoxysilane, monophenyltrimethoxysilane, monomethyltriethoxysilane, monomethyltri-n-butoxysilane, and monomethyltri-5ec.
-butoxysilane, monomethyltriisopropoxysilane, monomethyltripentoxysilane, monomethyltrioctoxysilane, monomethyltristearoxysilane, monomethyltriphenoxysilane, dimethyldimethoxysilane, dimethyljethoxysilane, dimethyldiisopropoxysilane, dimethyldimethoxysilane Phenoxysilane, triethylmonoethoxysilane, trimethylmonoethoxysilane, trimethylmonoisopropoxysilane, triethylmonoethoxysilane, monomethyldimethoxymonochlorosilane, monomethyljethoxymonochlorosilane, monomethylmonoethoxydichlorosilane, monomethylbromosilane, monoethyldiphenoxymono chlorosilane,
Dimethylmonoethoxymonochlorosilane, monoethyltriethoxysilane, monoethyltriynepropoxysilane, monoethyltriphenoxysilane, diethyldimethoxysilane, diethyljethoxy 7rane, diethyldiphenoxysilane, triethylmonomethoxysilane, triethylmonoethoxysilane , triethylmonophenoxysilane, monoethylditoxymonochlorosilane, monoethyljethoxymonochlorosilane, monoethyldiphenoxymonochlorosilane, monoisoprobyltrinotoxysilane, momoroptyltrimethoxysilane, mono n
-butyltriethoxysilane, mono5ee-butyltriethoxysilane, monophenyltriethoxysilane, diphenyljethoxysilane, diphenylmonoethoxymonochlorosilane, monomethoxytrichlorosilane, monoethoxytrichlorosilane, monoisopropoxytrichlorosilane, mono n- Butoxytrichlorosilane, monopentoxytrichlorosilane, monooctoxytrichlorosilane, monostearoxytrichlorosilane, monophenokiditrichlorosilane, monop-methylphenokiditrichlorosilane, dimethoxydichlorosilane, jetoxydichlorosilane, diinepropoxydichlorosilane, diimpropoxydichlorosilane, n-Butoxydichlorosilane, dioctoxydichlorosilane, trimethoxymonochlorosilane, triethoxymonochlorosilane, triinpropoxymonochlorosilane, tri-n-butoxymonochlorosilane, trisec
-Butoxymonochlorosilane, tetraethoxysilane, tetraisogropoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinylethoxydichlorosilane, vinyljethoxymonochlorosilane, vinylmethoxydichlorosilane, vinylethoxydichlorosilane, allyltrimethoxysilane , allyltriethoxysilane, allyldimethoxymonochlorosilane, allyljethoxymonochlorosilane, allylmethoxydichlorosilane, allylethoxydichlorosilane, vinyltrifetch disilane, vinylethoxydiphenoxysilane, allyltriphenoxysilane, allylethoxydiphenoxysilane and The repeating unit obtained by condensing the compound 1 above is +Si -0+
Examples include chain or cyclic polysiloxanes shown in Table 2. It can also be used as a mixture of these.

Among these compounds, component (2) is preferably one in which at least one substituent has an olefinic hydrogen chloride group, such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriphenoxysilane, allyltrimethoxysilane. , allyltriethoxysilane, and allyltriphenoxysilane are particularly preferred.

In addition, as component (5), at least one substituent preferably has an aromatic hydrocarbon group, and monophenyltrimethoxysilane, monophenyltriethoxysilane is a preferred atom, a halogen atom, or has 1 to 1 carbon atoms. 24, preferably 1 to 18 hydrocarbon residues, and R' has 1 to 18 carbon atoms.
24, preferably 1 to 18 hydrocarbon residues. r,
p and q are integers, 1≦r≦6.0≦p (6,
Compounds represented by 0≦q (6, 1≦r + q (6)) include phenol, 1-naphthol, 2-naphthol, 2-phenanthrol, 7-enanthrol, anthranol, methylphenol, , ethylphenol, isoglopylphenol, dimethylphenol, diethylphenol, digylphenol, 1-dimethylphenol, triethylphenol
2-chlorophenol, 3-bromophenol, 4-chlorophenol, 2,6-cyclophenol, di-t
-Butyl-p-cresol, 2-cyclohexylphenonoto-2-allylphenol, 3-oxinstyreneisoprobenylphenol, catechol, hydroquinone, 2
．． Examples include 6-cyhydroxytoluene, vinylcatechol, hyrogallol, methoxyphenol, and 2-impropoxyphenol. Among these compounds, phenol and 1-naphthol are particularly preferred.

As the titanium compound used in the present invention, tetravalent titanium compounds and trivalent titanium compounds are suitable. Specifically, the tetravalent titanium compound has the general formula Ti (OR)n
X4-n (where R represents an alkyl group, aryl group or aralkyl group having 1 to 2 carbon atoms; X represents a halogen atom; n is C≦n≦4; Titanium tetrachloride, titanium tetrameride, titanium tetraiodide, monomethoxytrichlorotitanium, dimethoxydichlorotitanium, trimethoxymonochlorotitanium, tetramethoxytitanium, monoethoxytrichlorotitanium, jetoxydichlorotitanium, triethoxymonochlorotitanium, tetraethoxytitanium , monoimprovoxytrichlorotitanium, diisopropoxydichlorotitanium, triisopropoxymonochlorotitanium, tetraisopropoxytitanium,
Examples include monobutoxytrichlorotitanium, dibutoxydichlorotitanium, monopentoxytrichlorotitanium, monophenoxytrichlorotitanium, diphenoxydichlorotitanium, triphenoxymonochlorotitanium, and tetraphenoxytitanium. As hexavalent titanium compounds, titanium tetrahalides such as titanium tetrachloride and titanium tetrabromide can be used as hydrogen, aluminum, titanium, or
- Titanium trihalide obtained by reduction with an organometallic compound of a group III metal. Still general formula Tj
(OR)mX4-m (where R represents an alkyl group, aryl group, or aralkyl group having 1 to 20 carbon atoms, and 6X represents a halogen atom. m is 0<m<4.

Examples include trivalent titanium compounds obtained by reducing a tetravalent alkoxy titanium halide represented by ) with an organometallic compound of a metal in group 1-m of the periodic table.

In the present invention, the amount of the titanium compound used is not particularly limited, but it is usually adjusted so that the amount of the titanium compound contained in the solid product is 0.5 to 20M, preferably 1 to 10% by weight. is preferable.

As the organometallic compound used in the present invention, organometallic compounds of Groups 1 to 1 of the periodic table, which are known as components of Ziegler's compound, can be used, but organoaluminum compounds and organozinc compounds are particularly preferred. Specific examples include general formulas R,, AI, R2AIX, RAIX2, R2A
lOR, RAI (OR)
R may be the same or different by -1), or the general formula R
2Zn (R is an alkyl group having 1 to 20 carbon atoms and may be the same or different), and is represented by an organic zinc compound such as triethylaluminum, triisobutylaluminum, triisobutylaluminum, t! J 5ee-Butyl aluminum, t! J t
Examples include ert-butylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride, diimpropylaluminum chloride, ethylaluminum sesquichloride, diethylzinc, and mixtures thereof.

In the present invention, the ratio of the organometallic compound to the compound represented by the general formula (5) is usually % to 1 mole of the organometallic compound. 0001 to 5 mol, preferably 0.01 to 2 mol.

Component (5) The amount of the compound represented by the general formula % is preferably such that the Si:Ti ratio is in the range of 01 to 100:+ with respect to the titanium compound in the catalyst component [l], and in the range of 06 to 2C:1. The range is more preferred.

In the present invention, an organometallic compound and component (5) a compound represented by the general formula % can also be used as reactants. In this case, the reaction ratio is usually 0,001 to 1 mole, preferably 4,001 to 2 moles of the compound represented by the formula % of component (5) per mole of the organometallic compound.

(Si:
Ti ratio is 01 to 100:1, preferably 0.6 to 20:
This is No. 1 snake enclosure.

There is no particular restriction on the method for obtaining the reaction product of the organometallic compound and the compound represented by the general formula (%) of component (5). ℃, preferably 50° C. to 250° C. for 5 minutes to 20 minutes.

In the present invention, the amount of the organometallic compound to be used is not particularly limited, but it is usually 0.1 to 10% relative to the titanium compound.
00 moles can be used.

The olefin polymerization reaction using the catalyst of the present invention is carried out in the same manner as the olefin polymerization reaction using a conventional Ziegler type catalyst. That is, all reactions are carried out in the gas phase or in the presence of an inert solvent, in the absence of oxygen, water, etc.
Alternatively, the monomer itself can be used as a solvent. The polymerization conditions for olefin are: temperature is 20°C to 600°C, preferably 40°C to 180'Cf, pressure is normal pressure Vs to 70K9/cry'G, preferably 2Kq/a♂
・G to 60 is Z-・G. Although the molecular weight can be adjusted to some extent by changing polymerization conditions such as polymerization temperature and catalyst molar ratio, it is effectively carried out by adding hydrogen to the polymerization system. Of course, using the catalyst of the present invention, a two-step or more multi-step polymerization reaction with different polymerization conditions such as hydrogen temperature and polymerization temperature can be carried out without any problem.

The method of the present invention is applicable to the polymerization of all olefins that can be polymerized with Ziegler's catalyst, such as the homopolymerization of a-olefins such as ethylene, propylene, butene-1,4-methylpentene-1, and ethylene and propylene, It is suitably used for random and block copolymerization of ethylene and butene-1, propylene and butene-1, etc. However, for the purpose of modifying polyolefins, copolymerization with dienes, such as copolymerization of ethylene and butadiene, ethylene and 1,4-hexadiene, etc., is also preferably carried out.

In the present invention, in particular, the α-olefin intermer 50 having 6 to 8 carbon atoms can be effectively used for stereoregular polymerization or copolymerization.

Examples are given below, and these are for illustrative purposes in carrying out the present invention, and the present invention is not intended to be limited to these examples.

Example 1 (a) Production of solid catalyst component [1] 10 f (105 mmol) of anhydrous magnesium chloride and 1.52 r (8 mmol) of vinyltriethoxysilane,
1.517 (16 mmol) of phenol was placed in a 9400 ml stainless steel pot containing 251 stainless steel balls having a diameter of % inch, and ball milling was performed at room temperature under a nitrogenous atmosphere for 24 hours. 200 m7 of the obtained solid powder 6y, 50 m1 of titanium tetrachloride and 307 m of 1,2-dichloroethane! The mixture was placed in a round bottom flask and stirred at 80° C. for 2 hours under nitrogen atmosphere. After removing excess titanium tetrachloride, the mixture was washed with hexane to remove unreacted titanium tetrachloride. Thereafter, it was dried under reduced pressure to obtain solid catalyst component [I]. The obtained solid catalyst component (j) 1y contained 25q of titanium.

(b) Polymerization A 6-ton stainless steel autoclave with a stirrer was purged with nitrogen, and 1500 m/! of hexane was added. 2.5 mmol of triethylaluminum, 1.4 mmol of phenyltriethoxysilane and 20 mg of the above-mentioned isocatalyst component [I)], and further hydrogen was added at a gas phase partial pressure of 0.05 Kz~. After charging the mixture, the temperature was raised to 50° C. while stirring. At the vapor pressure of hexane, the system is [1,
When the pressure reached 5Kg/cm2.G, propylene was then charged until the total pressure reached 7 to 9/Cm2.G to start polymerization. Propylene was continuously introduced so that the total pressure was 7 K9//cm2·G, and polymerization was carried out for 2 hours.

After the polymerization was completed, excess propylene was discharged, cooled, and the contents were taken out and dried; white polypropylene 2207 was obtained.

This is the total amount of the product, including the amorphous material. Catalyst activity: 8502 polypropylene/7 solid/hr-C3H6 pressure,
34 to 7 polypropylene/9 Ti-hr-C3H
It was 6 pressure. The total extraction residue (total ■) with non-n-hebutane, including the solvent-labile polymer, was 97.6 wt %, and the melt flow index (MFI) was 8.1.

Compared to Comparative Example 1 and Comparative Example 2, both the catalyst activity and the total ◯ were higher.

Comparative Example 1 In Example 1, a solid catalyst component was synthesized in the same manner as in Example 1, except that vinyltriethoxysilane was not used, and when polymerization was carried out in the same manner as in Example 1, polypropylene was obtained. 1517 were obtained. Catalytic activity is 5
80 polypropylene/2 solid・hr' C3H
I got it with 6 pressure. Total ■ is 8D, 4wt%, and MFI is a
It was 3.

Comparative Example 2 In Example 1, a solid catalyst component was synthesized in the same manner as in Example 1 except that phenol was not used, and heavy apricot was synthesized in the same manner as in Example 1. 167 polypropylene was obtained. It was done. The catalyst activity was 60g polypropylene/2MFI Z5.

Using each compound shown in Table 1, a solid catalyst component was synthesized in the same manner as in Example 1, and a propylene M (alloy) was prepared in the same manner as in Example 1. Example 11 A 6-ton stainless steel autoclave equipped with a 441-liter stirrer was heated with nitrogen, 150 mA of hexane was added, 25 mmol of triethylaluminum and 1.4 mmol of phenyltriethquinsilane were added, and the autoclave was stirred. The mixture was heated to 80°C and reacted for 60 minutes.Then, it was cooled to room temperature, and 207 ng of the catalyst of Example 2 was added, and the mixture was charged and stirred so that the hydrogen gas phase partial pressure was 0.05 Kg/C1n2. The temperature was raised to 50℃ while the vapor pressure of hexane was 0, sKμ box 2・G, but the total pressure of propylene was 7
KL//cM?・Polymerization was started by filling until GK. The following steps were carried out in the same manner as in Example 1.

Polypropylene 2287 was obtained. Catalytic activity is 877
7 voliglopile//7 solid/hr-C3H6 pressure, 38.
1 Kg Polypropyref/IT i-hr-C
The pressure was 3H6.

The whole shredded material was 9S, 2 wt%, and the MFI was al.

Procedural amendment April 1, 1980 Kazuo Wakasugi, Commissioner of the Patent Office1, Indication of the case, Patent Application No. 3558, filed in 19822, Name of the invention, Process for producing polyolefin3, Person making the amendment Relationship to the case Patent applicant 5, subject of amendment Detailed explanation of the invention in the specification column 6
, content of correction

Claims (1)

[Scope of Claims] [1] (1) Magnesium halide, I t represents a hydrocarbon residue having 1 to 24 carbon atoms, an alkoxy group, or a halogen atom after hydrogen removal, and R4 is a hydrocarbon having 1 to 24 carbon atoms. Show remaining funds. n is 1≦n≦60. ) represents a carbon atom or a hydrocarbon residue having 1 to 24 carbon atoms, and R' represents a hydrocarbon residue having 1 to 24 carbon atoms. r,
p and q are integers, 1≦r≦5.0≦P<6.
0≦q〈6.1≦r→−p+q (6).
(4) a solid catalyst component on which a titanium compound is supported on the solid vJ substance obtained by contacting the compound with
0 Organometallic compound, and 1 G represents a hydrocarbon residue having 1 to 24 carbon atoms, an alkoxy group, hydrogen or a halogen atom, and R4 represents a hydrocarbon residue having 1 to 24 carbon atoms. n is 1≦n≦60. ) A method for producing a polyolefin, which comprises polymerizing or copolymerizing an α-olefin using a catalyst formed by combining the compounds represented by the following.