JP3279345B2 - α-Olefin polymerization method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for polymerizing an α-olefin. More specifically, the present invention makes it possible to obtain a poly-α-olefin having high stereoregularity in a high yield.

[0002]

2. Description of the Related Art There have been many proposals for a method for producing a solid titanium catalyst component containing magnesium, titanium, halogen and an electron donating compound as essential components (JP-A-57-63310 and JP-A-58-63310). 3260
4, 58-83006, 60-130607, 6
2-1705 each gazette). These production methods have made it possible to obtain a polymer of an α-olefin having 3 or more carbon atoms with high stereoregularity and high activity. Further, the step of deashing the catalyst, which was required for the conventional titanium trichloride-based catalyst having relatively low activity, was omitted, and the production process could be simplified and streamlined.

[0003]

However, in order to maintain the stereoregularity of the resulting polymer at a sufficiently high level, these methods are required separately from the preparation of the solid titanium catalyst component.
It was necessary to use an electron donating compound together with the organoaluminum compound during the polymerization. The electron donating compound used in the polymerization is used in a substantial amount in order to reduce the polymerization activity by reaction with an organoaluminum compound or to obtain a highly stereoregular polymer. There was a problem that odor was generated in the coalescence. Therefore, solving such problems, maintaining high polymerization activity,
An object of the present invention is to develop a polymerization method for producing a poly-α-olefin having high stereoregularity.

[0004]

Means for Solving the Problems The present inventors have intensively studied a polymerization method for producing a poly-α-olefin having a high stereoregularity while maintaining a high polymerization activity and solving the above problems. Was completed. That is, the present invention provides (1) a solid titanium catalyst component containing magnesium, titanium, halogen and an electron donating compound (a) as essential components, (2) an organoaluminum compound, (3) an aromatic carboxylic acid ester, Si -OC or
Silicon compound having Si-NC bond, acetalization
Compound, a germanium compound having a Ge—O—C bond,
Heterocyclic compounds of nitrogen or oxygen having alkyl substituents
(4) pre-contact with a polymerization catalyst component formed from at least one electron donating compound (b) selected from the group consisting of (4) an olefin monomer having 4 or more carbon atoms.
100 mg or less per gram of the solid titanium catalyst component.
Α characterized in that it comprises a step you prepolymerization in the range below
-An olefin polymerization method. Hereinafter, the present invention will be described specifically.

Solid titanium catalyst component The solid titanium catalyst component used in the present invention is prepared by contacting a magnesium compound, a titanium compound, a halogen-containing compound, and an electron donating compound (a) as described below. . In the present invention, the magnesium compound used in the preparation of the solid titanium catalyst component is not particularly limited, and a magnesium compound used as a raw material for preparing a highly active catalyst for ordinary olefin polymerization and copolymerization can be used. . That is, magnesium halides such as magnesium chloride, magnesium bromide and magnesium iodide; alkoxymagnesiums such as dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium and diphenoxymagnesium; magnesium laurate, stearic acid Examples thereof include carboxylate salts such as magnesium and magnesium acetate; alkyl magnesium such as dimethyl magnesium, diethyl magnesium, and butyl ethyl magnesium. These various magnesium compounds can be used alone or in combination of two or more. Preferably, magnesium halide or alkoxymagnesium is used, or magnesium halide is formed during catalyst formation. Particularly preferably,
The halogen is chlorine.

The titanium compounds used in the present invention include titanium halides such as titanium tetrachloride, titanium trichloride, titanium tetrabromide and titanium tetraiodide; tetramethoxytitanium, tetraethoxytitanium, tetrapropoxytitanium, Examples include alkoxytitanium such as tetrabutoxytitanium and tetraphenoxytitanium; alkoxytitanium halides such as ethoxytitanium chloride, butoxytitanium chloride, phenoxytitanium chloride, dibutoxytitanium dichloride, and tributoxytitanium chloride. it can. These various titanium compounds can be used alone or in combination of two or more. Preferred are tetravalent titanium compounds containing halogenation, and particularly preferred is titanium tetrachloride. The halogen-containing compound used in the present invention,
Halogen is fluorine, chlorine, bromine, or iodine, preferably chlorine, and specific compounds actually exemplified depend on the catalyst preparation method, but include titanium halides such as titanium tetrachloride, titanium tetrabromide, and the like. Silicon chloride, silicon halides such as silicon tetrabromide, phosphorus trichloride, phosphorus halides such as phosphorus pentachloride can be exemplified, but depending on the catalyst preparation method, halogenated hydrocarbons, halogen molecules, hydrohalic acid may be used. May be used.

As the electron donating compound (a) used in the present invention, known compounds can be used, and generally include oxygen-containing compounds, nitrogen-containing compounds, phosphorus-containing compounds, and sulfur-containing compounds. Examples of the oxygen-containing compound include alcohols, ethers, esters, acid halides, and acid anhydrides. More specifically,
Methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, 2-ethyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, phenol, cresol −
Alcohols such as methyl, ethylphenol and naphthol; ethers and diethers such as methyl ether, ethyl ether, propyl ether, butyl ether, amyl ether, hexyl ether, tetrahydrofuran, anisole and diphenyl ether; ethyl acetate;
Ethyl chloroacetate, ethyl propionate, ethyl butyrate,
Ethyl acrylate, ethyl crotonate, ethyl oleate, ethyl stearate, ethyl phenylacetate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, methyl toluate, ethyl toluate, propyl toluate, toluic acid Butyl, methyl ethyl benzoate, methyl anisate, ethyl anisate, methyl ethoxy benzoate, ethyl ethoxy benzoate, ethyl cinnamate, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, di-n-butyl phthalate, phthalate Esters such as diisobutyl acid, dihexyl phthalate, dioctyl phthalate, γ-butyrolactone, δ-valerolactone, ethylene carbonate; acid chlorides such as acetyl chloride, benzoyl chloride, toluic acid chloride, phthalic chloride; maleic anhydride Acid anhydrides such as formic acid and phthalic anhydride are exemplified. These electron donating compounds (a) can be used alone or in combination of two or more. Preferred are esters, and particularly preferred are phthalic esters.

The amount of each of the above components is arbitrary as long as the effects of the present invention are recognized, but the following ranges are generally preferred. The amount of the titanium compound used is 0.000 in molar ratio with respect to the amount of the magnesium compound used.
It is good to be in the range of 1 to 1000, preferably 0.01 to 1
00 is within the range. If necessary, a halogen compound is used, but if used, the amount used is such that the titanium compound and the magnesium compound contain a halogen,
Regardless of whether or not it is contained, the molar ratio is preferably in the range of 0.01 to 1000, more preferably 0.1 to 100, based on the amount of magnesium used. The amount of the electron donating compound used is preferably in the range of 0.001 to 10 in terms of molar ratio with respect to the amount of the magnesium compound, and more preferably in the range of 0.01 to 5.

The method for preparing the solid catalyst component used in the present invention comprises contacting a magnesium compound, a titanium compound, an electron-donating compound and, if necessary, an auxiliary agent such as a halogen-containing compound temporarily or stepwise. A conventionally known method for preparing a solid catalyst component obtained by the reaction can be applied. The following production method is a specific example of the known method. (1) A method of contacting a magnesium halide with an electron-donating compound and a titanium compound as required. (2) A method of contacting a titanium halide compound and / or a silicon halide compound with a solid component obtained by contacting a magnesium halide with a tetraalkoxytitanium and a specific polymer-silicon compound. (3) A method in which a magnesium compound is dissolved with tetraalkoxytitanium and an electron-donating compound, and the titanium compound is brought into contact with a solid component precipitated with a halogenating agent or a titanium halide compound. (4) A method in which alumina or magnesia is treated with a phosphorus halide compound, and a magnesium halide, an electron-donating compound, and a titanium halide compound are brought into contact therewith. (5) A method in which a Grignard reagent represented by an organomagnesium compound is allowed to act on a reducing agent, a halogenating agent, or the like, and then the electron-donating compound is brought into contact with a titanium compound. (6) A method in which a halogenating agent and / or a titanium compound is brought into contact with an alkoxymagnesium compound in the presence or absence of an electron donating compound. (7) A method of dissolving a magnesium compound with tetraalkoxytitanium, treating with a polymer silicon compound, and then treating with a halogen compound of silicon and an organometallic compound. (8) A method of treating a spherical magnesium compound / alcohol complex with an electron donating compound, a titanium halide compound, and the like.

Organoaluminum compound The organoaluminum compound used in the present invention is typically a trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum; Alkyl aluminum hydrides such as aluminum hydride, diethyl aluminum hydride, dibutyl aluminum hydride; dimethyl aluminum chloride, diethyl aluminum chloride,
Examples thereof include alkylaluminum halides such as diethylaluminum bromide and ethylaluminum sesquichloride; alkylaluminum alkoxides such as diethylaluminum ethoxide and diethylaluminum phenoxide; and aluminoxanes such as methylaluminoxane, ethylaluminoxane and propylaluminoxane. In addition, these organoaluminum compounds can be used alone, or
Two or more types can be used in combination. Preferably, it is a trialkylaluminum.

Electron-donating compound (b) Representative electron-donating compound (b) used in the present invention
Is an aromatic carboxylic acid ester, Si-OC or S
a silicon compound having an i-N-C bond, an acetal compound, and a germanium compound having a Ge-OC bond,
Examples include a nitrogen or oxygen heterocyclic compound having an alkyl substituent. Specific examples of these compounds include aromatic carboxylic esters such as ethyl benzoate, ethyl p-toluate and ethyl p-anisate; phenyltrimethoxysilane, diphenyldimethoxysilane, di-n
-Propyldimethoxysilane, di-i-propyldimethoxysilane, di-t-butyldimethoxysilane, dicyclohexyldimethoxysilane, dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane,
silicon compounds such as t-butyltrimethoxysilane, cyclohexyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane; benzophenonedimethoxyacetal, benzophenonediethoxyacetal,
Acetal compounds such as acetophenone dimethoxyacetal and acetophenonediethoxydiethoxyacetal; germanium compounds such as diphenyldimethoxygermane and phenyltriethoxygermane;
Heterocyclic compounds such as 6,6-tetramethylpiperidine and 2,2,6,6-tetramethylpyran can be exemplified. These electron donating compounds (b) are
One type may be used alone, or two or more types may be used in combination. Preferably, a silicon compound,
Acetal compound, particularly preferably Si—O—
It is a silicon compound having a C bond.

Olefins having 4 or more carbon atoms The olefin monomers having 4 or more carbon atoms used in the present invention include 1-butene, 3-methyl-1-butene, 1-pentene, 1-hexene, 3-methyl-1-pentene, 4
-Methyl-1-pentene, 1-heptene, 1-octene and the like can be exemplified. Among these olefin monomers, those which produce a crystalline polymer when polymerized alone are more preferable, and 1-butene and 3-methyl-
1-butene, 4-methyl-1-pentene and the like can be preferably used, and 4-methyl-1-pentene is particularly preferable.

Preliminary contact with olefin monomer having 4 or more carbon atoms Solid magnesium catalyst component containing magnesium, titanium, halogen and electron donating compound (a) as essential components, organoaluminum compound catalyst component, electron donating property When the polymerization catalyst component formed from the compound (b) is pre-contacted with an olefin monomer having 4 or more carbon atoms, the olefin monomer having 4 or more carbon atoms is usually saturated with hexane, heptane, cyclohexane, toluene or the like. It can be dissolved in an aliphatic or aromatic hydrocarbon alone or in a mixture. Further, not only a batch method but also a continuous method directly connected to a polymerization reactor can be used. The temperature of the pre-contact is preferably -70 to 40 ° C, more preferably -20.
-20 ° C. Pre-contact time is preferably 10 minutes
Within , more preferably within 5 minutes. If the temperature exceeds 40 ° C. or the time exceeds 10 minutes in the pre-contacting step, undesired polymerization proceeds excessively, and the effect of the present invention may be reduced. The amount of the olefin monomer having 4 or more carbon atoms to be used per 1 g of the solid titanium catalyst component is preferably 0.01 to 10 g, and more preferably 0.1 to 5 g. If the amount of the olefin monomer having 4 or more carbon atoms exceeds 10 g with respect to 1 g of the solid titanium catalyst component, undesired polymerization proceeds excessively, and the effect of the present invention may be reduced. The effect of the present invention is considered to be in the modification of the catalyst surface by preliminary contact of the catalyst with an olefin monomer having 4 or more carbon atoms, unlike the conventionally known prepolymerization,
If the polymerization proceeds too much, the effect of the present invention will be reduced. Based on the solid titanium catalyst component 1g, polymerization of C 4+ olefin monomers carbon, Ru der below 100 mg. More preferably, it is 50 mg or less. A solid titanium catalyst component, an organoaluminum compound, and an electron donating compound (b) for an olefin monomer having 4 or more carbon atoms at the time of preliminary contact;
Is usually in the range of 0.00005 to 0.2 mol / l, and preferably in the range of 0.005 to 0.05 mol / l, for the titanium component in the solid titanium catalyst component. . The amount of the organoaluminum compound to be used is in a molar ratio of 0.1 to the titanium component of the solid titanium catalyst component.
The range is preferably from 1 to 1,000, and more preferably from 1 to 200. The amount of the electron donating compound (b) used is 0.001 to 1 in a molar ratio with respect to the organoaluminum compound.
It is preferably in the range of 0, and more preferably in the range of 0.01 to 2.

The polymerization in the present invention, the solid titanium catalyst component described above, an organic aluminum compound, a polymerization catalyst component formed from an electron-donating compound (b) were pre-contacted by the number 4 or more olefin monomers carbon contact The mixture can be used to polymerize α-olefins. Since the contact mixture contains an organoaluminum compound and an electron-donating compound (b), it is not necessary to newly use these catalyst components when polymerizing an α-olefin, but they are used according to the catalyst performance. You may. The polymerization method in the production method of the present invention is not particularly limited, and a known method can be used. In addition to a liquid phase polymerization method such as slurry polymerization or bulk polymerization, the polymerization method can be applied to a gas phase polymerization method. Also, not only batch polymerization, but also continuous polymerization,
It is also applicable to a method of performing batch polymerization. As a polymerization solvent in the case of slurry polymerization, a single or a mixture of saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, cyclohexane, and toluene is used. The polymerization temperature is about −20 to 200 ° C., preferably 40 to 150 ° C.
And the polymerization pressure is from atmospheric pressure to 100 kg / cm ² G,
Preferably, it is 3 to 50 Kg / cm ² G. In addition, the molecular weight can be adjusted by adding an appropriate amount of hydrogen during the polymerization. Α- used in the production method of the present invention
Olefins of the general formula R-CH = CH ₂ (the R is a hydrocarbon residue having 1 to 18 hydrogen atoms or carbon atoms, a branched group or) is represented by. Specific examples include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, and the like. Preferably, they are ethylene, propylene, and 1-butene. Further, copolymerization between olefins can also be performed. Furthermore, copolymerization with another copolymerizable monomer (for example, a diene or the like) can also be performed.

[0015]

The present invention will be described below in detail with reference to examples. Example 1 Preparation of Solid Titanium Catalyst Component Under a nitrogen atmosphere, 4.76 g of anhydrous magnesium chloride (50
mmol), 25 ml of decane and 23.4 ml (150 mmol) of 2-ethylhexyl alcohol at 130 ° C.
After performing a heating reaction for 2 hours to obtain a homogeneous solution, 1.11 g (7.5 mmol) of phthalic anhydride was added to the solution, and the mixture was further stirred and stirred at 130 ° C. for 1 hour to remove the phthalic anhydride into the homogeneous solution. Dissolved in the solution. After cooling the obtained homogeneous solution to room temperature, the whole amount was dropped into 200 ml (1.8 mol) of titanium tetrachloride kept at -20 ° C over 1 hour. After completion of the dropwise addition, the temperature of the mixed solution was raised to 110 ° C. over 4 hours. When the temperature reached 110 ° C., 2.68 ml (12.5 mmol) of diisobutyl phthalate was obtained.
Was added, and the mixture was stirred and reacted at 110 ° C. for 2 hours. After completion of the reaction, a solid portion was collected by hot filtration, and titanium tetrachloride 20
After resuspending in 0 ml, the reaction was performed again at 110 ° C. for 2 hours. After the completion of the reaction, a solid portion was collected again by hot filtration, and sufficiently washed with decane at 110 ° C and hexane at room temperature. The titanium content in the obtained solid titanium catalyst component was measured and found to be 2.35% by weight. Preliminary contact with olefin monomer having 4 or more carbon atoms Under a nitrogen atmosphere, 35 ml of heptane, 15 mg of the above-mentioned solid titanium catalyst component, and 2.4 g of triethylaluminum
(21 mmol), 1.3 g (7.0 mmol) of cyclohexylmethyldimethoxysilane, and 60 mg of 4-methyl-1-pentene were stirred and reacted at 10 ° C. for 5 minutes. The entire amount of the preliminarily contacted catalyst component mixture was charged into a 6.0-liter autoclave equipped with a stirrer in a propylene polymerization nitrogen atmosphere. Then, 1835 g of propylene (43.6 mo
l) Hydrogen was charged so as to be 0.13 mol% with respect to propylene, and the temperature was raised to 70 ° C. to perform polymerization for 1 hour. One hour later, unreacted propylene was removed to terminate the polymerization. As a result, 731 g of polypropylene was obtained. The polymerization activity was 48.7Kg / g- solid titanium catalyst component, the molecular weight distribution M _W / M _n by GPC of the resulting polypropylene 5.1, ¹³ shown isotacticity
Isotactic triad fraction [m
m] was 97.4% and the MFR was 10.0 g / 10 minutes. In the molecular weight distribution ( _Mw / _Mn ), _Mw is a weight average molecular weight, and _Mn is a number average molecular weight. Further, the isotactic triad fraction [mm] is a fraction of propylene monomer units at the center of a chain in which three propylene monomer units are consecutively connected to meso-linked methyl groups of propylene. The method for determining the absorption assignment of the NMR spectrum is as follows.
acromolecules, 8 , 687 (1975)
Based on

Example 2 In the pre-contact with 4-methyl-1-pentene, all the procedures were carried out except that diphenyldimethoxysilane was used in place of cyclohexylmethyldimethoxysilane as the electron-donating compound (b). Propylene polymerization was carried out under the same conditions and method as in Example 1. as a result,
707 g of polypropylene were obtained. Polymerization activity is 4
7.1 Kg / g-solid titanium catalyst component, _Mw / _Mn of the produced polypropylene is 5.0, and [mm] is 98.1.
%, MFR was 6.4 g / 10 min.

Example 3 A polypropylene was obtained in the same manner as in Example 1 except that the preliminary contact time with 4-methyl-1-pentene was changed to 2 minutes.
Table 1 shows the results.

Example 4 Preliminary contact temperature with 4 -methyl-1-pentene was -10 ° C.
Example 1 except that the preliminary contact amount was 10 mg.
A polypropylene was obtained in the same manner as described above. Table 1 shows the results.

[0019]

Comparative Example 1 Propylene polymerization was carried out under the same conditions and in the same manner as in Example 1, except that the pre-contact operation with 4-methyl-1-pentene in hexane was not carried out. Done. As a result, 368 g of polypropylene was obtained. The polymerization activity was 24.5 Kg / g-a solid titanium catalyst component, and _Mw / _Mn of the produced polypropylene was 5.
0, [mm] was 97.3%, and MFR was 9.8 g / 10 min.

[0021]

[Table 1]

[0022]

According to the present invention, a poly-α-olefin having a high stereoregularity can be produced at a high yield at a low cost, which is industrially useful.

[Brief description of the drawings]

FIG. 1 is a flow chart showing an outline of a method for polymerizing α-olefin of the present invention.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-3-265610 (JP, A) JP-A-2-43204 (JP, A) JP-A-4-202510 (JP, A) JP-A-4-202510 202505 (JP, A) JP-A-6-56924 (JP, A) JP-A-6-25341 (JP, A) JP-A-6-80719 (JP, A) JP-A-6-41229 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08F 4/64-4/658

Claims (5)

(57) [Claims] 1. A solid titanium catalyst component containing (1) magnesium, titanium, a halogen and an electron donating compound (a) as essential components, (2) an organoaluminum compound, (3) an aromatic carboxylic acid ester, Si -OC or
Silicon compound having Si-NC bond, acetalization
Compound, a germanium compound having a Ge—O—C bond,
Heterocyclic compounds of nitrogen or oxygen having alkyl substituents
(4) pre-contact with a polymerization catalyst component formed from at least one electron donating compound (b) selected from the group consisting of (4) an olefin monomer having 4 or more carbon atoms.
And 100 mg or less per 1 g of the solid titanium catalyst component.
Polymerization of α- olefins comprising the step you prepolymerization range. 2. 5 g / g of the solid titanium catalyst component
Α-characterized in that prepolymerization is performed in a range of 0 mg or less.
Olefin polymerization method. 3. The step of pre-contacting with an olefin monomer having 4 or more carbon atoms, the olefin monomer having 4 or more carbon atoms is present in an amount of 0.01 to 4 g per 1 g of the solid titanium catalyst component.
The method for polymerizing an α-olefin according to claim 1 or 2 , wherein the amount is 10 g. 4. The method of claim 1, 2 temperature to be pre-contacted by the number 4 or more olefin monomers carbon is -70～40 ° C.,
3. The method for polymerizing an α-olefin according to any one of 3 . 5. The time for pre-contacting the number 4 or more olefin monomers of carbon is within 10 minutes according to claim 1-4 noise
The method for polymerizing an α-olefin described in any of the above.