JPH0449293A - Aluminoxane solution and polymerization catalyst using the same - Google Patents

Abstract

PURPOSE:To obtain the subject solution useful as a catalyst for production of various polymers without separating out gel-like granules even in preserving for a long time, having excellent uniformity, comprising an aluminoxane, an aromatic hydrocarbon and a polar compound. CONSTITUTION:The objective solution is composed of an aluminoxane, an aro matic hydrocarbon and a polar compound. Said aluminoxane is obtained as a product by contact of various organic aluminum compounds with water. As the aromatic hydrocarbon, benzene, toluene or xylene, etc., are exemplified. As the polar compound, a halogenated hydrocarbon such as chlorobenzene or a compound having at least a sort of atom of oxygen, S, N and P without containing active hydrogen, e.g., ethyl ether, acetonitrile or dimethyl sulfoxide is preferable. To prepare the objective solution, e.g., aluminoxane is dissolved in the mixed solution of an aromatic hydrocarbon and a polar compound.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an aluminoxane solution suitable as a catalyst component for producing various polymers, and a polymerization catalyst comprising this aluminoxane solution and a transition metal compound.

[Prior art and problems to be solved by the invention] Conventionally, glass reflexine and styrene are polymerized in the presence of a catalyst,
BACKGROUND ART In producing olefin polymers or styrene polymers, it is widely known that a catalyst consisting of aluminoxane and a transition metal compound is used to produce high-performance polymers in good yield.

However, although aluminoxane compounds dissolve in aromatic hydrocarbon solvents such as toluene, when stored for a long period of time, viscous gel-like aluminoxane particles precipitate, and these gel-like aluminoxane particles are deposited on the walls of storage containers. There were problems in that the aluminoxane concentration in the solution might change.

Therefore, as a method to eliminate this phenomenon, a method of adding alkyl aluminum (Japanese Patent Application Laid-Open No. 1-258686) has been proposed.
As proposed in Japanese Patent Publication No. 2003-121033, the aluminoxane is also modified by alkylation due to the addition of alkyl aluminum, which has the drawback of changing the activity or limiting the physical properties of the resulting polymer.

The present invention solves these conventional drawbacks, does not change the activity or limit the physical properties of the produced polymer, and even when stored for a long period of time, it produces viscous gel-like aluminoxane particles. The purpose of this invention is to provide a homogeneous aluminoxane solution that does not precipitate and is suitable as a catalyst component for the production of various polymers.

[Means to solve the problem]

That is, the present invention provides an aluminoxane solution comprising aluminoxane, an aromatic hydrocarbon, and a polar compound.

The aluminoxane used in the present invention is obtained as a contact product of various organoaluminum compounds and water.

Specifically, as such an aluminoxane component, alkylaluminoxane, particularly alkylaluminoxane having an alkyl group having 1 to 6 carbon atoms, such as methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, etc., is suitably used, and methylaluminoxane is particularly preferred.

The organoaluminum compound used as a raw material for this aluminoxane component usually has the general formula % (%) [wherein R1 represents an alkyl group having 1 to 8 carbon atoms]. ] Examples include organoaluminum compounds represented by the following.

Examples of the organoaluminum compound represented by the general formula CI) include alkyl aluminum compounds, specifically trialkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, and dialkylaluminum monochloride, among which trimethylaluminum is the most preferable.

The water that is brought into contact with such organoaluminum compounds is
Ordinary water, ice or various hydrous compounds, such as solvent saturated water, inorganic adsorbed water, or copper sulfate pentahydrate (CuS
04/5H20), crystal water containing a metal salt such as aluminum sulfate hexahydrate, etc. may be used.

An example of a reaction product of an organoaluminum compound such as alkyl aluminum as a representative of the aluminoxane component and water is specifically the general formula C, in which R1 is the same as above. Further, k indicates the degree of polymerization. ] A chain alkylaluminoxane represented by the general formula [wherein R' is the same as above]. Further, k indicates the degree of polymerization.

] There are cyclic alkylaluminoxanes having a repeating unit represented by the following. Usually it is 4-52.

Generally, the contact product of an organoaluminum compound such as trialkylaluminum and water is a mixture of unreacted trialkylaluminum, various condensation products, as well as the above-mentioned chain alkylaluminoxane and cyclic alkylaluminoxane, as well as a mixture of these condensation products. are molecules that are complexly associated, and these produce various products depending on the contact conditions between trialkylaluminium and water.

There is no particular restriction on the reaction between the organoaluminum compound and water at this time, and the reaction may be carried out according to a known method. For example, ■ a method in which an organoaluminum compound is dissolved in an organic solvent and brought into contact with water or water vapor, ■ a method in which water is dissolved in an organic solvent and an organoaluminum compound is added to the solution; There are methods such as reacting the contained water of crystallization and water adsorbed on inorganic or organic substances with an organoaluminum compound.

Although this reaction proceeds without a solvent, it is preferably carried out in a solvent, and suitable solvents include hexane,
Examples include aliphatic hydrocarbons such as heptane and decane, and aromatic hydrocarbons such as benzene, toluene and xylene.

Next, in the present invention, aromatic hydrocarbons are used.

Here, the aromatic hydrocarbons include benzene, toluene,
Examples include xylene.

Furthermore, in the present invention, a polar compound is used.

There are various types of polar compounds, but they include halogenated hydrocarbons, or compounds that do not contain active hydrogen and have at least one kind of atom among oxygen atoms, sulfur atoms, nitrogen atoms, and phosphorus atoms. preferable.

First, as the halogenated hydrocarbon, aliphatic halogenated hydrocarbons, aromatic halogenated hydrocarbons, etc. are used, and aromatic halogenated hydrocarbons, more specifically, tetralobenzene, dichlorobenzene, trichlorobenzene, etc. are used. etc. are preferred.

In addition, examples of compounds having an oxygen atom that do not contain active hydrogen and have at least one kind of atom among an oxygen atom, a sulfur atom, a nitrogen atom, and a phosphorus atom include ethyl ether, isopropyl ether, isoamyl ether, Examples include ethers such as tetrahydrofuran, dioxane and anisole, ketones such as methyl ethyl ketone and acetone, and esters such as dimethyl carbonate and methyl acetate.

Furthermore, examples of compounds that do not contain active hydrogen and have a nitrogen atom include nitriles such as acetonitrile and benzonitrile, and amines such as triethylamine.

In addition, examples of compounds that do not contain active hydrogen and have a sulfur atom include dimethyl sulfoxide.

The aluminoxane solution of the present invention comprises the above-mentioned aluminoxane, an aromatic hydrocarbon, and a polar compound.

The aluminoxane solution of the present invention can be prepared by, for example, using the aluminoxane synthesized as described above in the form of a solution.
Alternatively, it may be concentrated or dried to a solid state and then dissolved in a mixed solution of an aromatic hydrocarbon and a polar compound.

Here, the amount of aromatic hydrocarbon used is 1g of aluminoxane.
0.5g to 100g, preferably 1g to 50g
Let it be g.

Also, the polar compound is aluminoxane AI! Atomic Imo
0.1 mo1% or more, preferably 1 to 50
When added at a mo of 1%, a homogeneous solution can be obtained.

Next, the present invention also provides a polymerization catalyst comprising the above aluminoxane solution and a transition metal compound.

There is no particular restriction on the transition metal compound component that is one component of the catalyst, but it is usually selected from periodic table IVB,
It is made of a transition metal compound containing a transition metal belonging to group VB, WB, WB, or group II.

Specifically, the transition metal is preferably titanium, zirconium, hafnium, chromium, manganese, nickel, palladium, platinum, etc., with zirconium, nickel, and palladium being particularly preferred.

There are various types of such transition metal compounds, but compounds represented by the general formula % (%) are particularly desirable.

Here, M in maximum (IV) represents a transition metal belonging to groups IVB, VB, VIB, ■B, and ■ of the periodic table as described above, and a, b, c, and d are integers from 0 to 7. shows. Further, R2-R5 may be the same or different, and a plurality of R2-R5 may be bonded to each other to form a ring.

In the above-maximum CIV), R2-R5 are each a hydrogen atom; a halogen atom such as fluorine, chlorine, bromine, or iodine;
Oxygen atom; methyl group, ethyl group, n-propyl group, 1s
o-propyl group, n-butyl group.

Alkyl groups having 1 to 20 carbon atoms such as t-butyl group, 1so-butyl group, octyl group, 2-ethylhexyl group; methoxy group, ethoxy group, propoxy group.

Alkoxy groups with 1 to 20 carbon atoms such as butoxy and phenoxy groups; aryl groups with 6 to 20 carbon atoms such as phenyl, tolyl, xylyl, and benzyl; alkylaryl or arylalkyl groups; heptadecylcarbonyloxy an acyloxy group having 1 to 20 carbon atoms; such as an indenyl group;

Fluorenyl group; cyclopentadienyl group: methylcyclopentadienyl group, ethylcyclopentadienyl group,
1.2-dimethylcyclopentadienyl group, tetramethylcyclopentadienyl group.

Substituted cyclopentagenyl groups such as pentamethylcyclopentadienyl group; π-allyl group: substituted allyl group; acetylacetonate group; substituted acetylacetonato group; containing silicon atoms such as trimethylsilyl group and (trimethylsilyl)methyl group Substituted silyl group; carbonyl group, oxygen molecule, nitrogen molecule.

Ethylene; diethyl ether, tetrahydrofuran (T
HF), ethers such as dimethyl ether, esters such as ethyl benzoate, nitriles such as acetonitrile and benzonitrile, triethylamine, 2.
Amines such as 2°-bipyridine and phenanthroline,
Lewis bases such as phosphines such as triethylphosphine and triphenylphosphine, isocyanides, phosphonic acids, and thiocyanates: benzene, toluene, xylene, cyclohebutatriene, cyclooctadiene,
Indicates cyclic unsaturated hydrocarbons such as cyclooctatriene, cyclooctatetraene, or their derivatives.

In the above examples of R2 to R5, when it has a substituent, it is preferably an alkyl group.

Incidentally, other transition metal compounds derived from the above-mentioned compound (IV) can also be effectively used as the catalyst component of the present invention.

Specifically, such a transition metal compound component includes bis(cyclopentagenyl) as a zirconium compound.
Zirconium dichloride, j-bis(cyclopentagenyl)zirconium monohydride monochloride,
bis(cyclopentadienyl)dimethylzirconium,
Bis(cyclopentagenyl)dibenzylzirconium, bis(cyclopentagenyl)zirconium dimethoxide, bis(methylcyclopentagenyl)zirconium dichloride, bis(pentamethylcyclopentagenyl)zirconium dichloride, (pentamethylcyclopentadienyl) zirconium trichloride, (pentamethylcyclopentagenyl) zirconium trimethoxide.

(pentamethylcyclopentagenyl)tribenzylzirconium, (cyclopentagenyl)zirconium trichloride, (cyclopentagenyl)zirconium tribromide, ethylenebis(indenyl)zirconium dichloride, ethylenebis(tetrahydroindenyl)zirconium dichloride, Dimethylsilylbis(cyclopentagenyl)zirconium dichloride, dichlorozirconiumbis(acetylacetonate), and the like can be mentioned.

Specific examples of titanium compounds or hafnium compounds include those in which zirconium in the above zirconium compounds is replaced with titanium or hafnium.

Next, specific examples of chromium compounds include tetramethylchromium and tetra(t-butoxy)chromium.

Bis(cyclopentagenyl)chromium, hydridotricarbonyl(cyclopentagenyl)chromium.

Hexacarbonyl (cyclopentagenyl) chromium, bis (benzene) chromium, tricarbonyl tris (triphenyl phosphonate) chromium, tris (allyl) chromium,
Examples include triphenyltris(tetrahydrofuran)chromium and chromiumtris(acetylacetonate).

Furthermore, specific examples of manganese compounds include tricarbonylpentacarbonylmethylmanganese, bis(cyclopentagenyl)manganese, manganese bis(acetylacetonate), and the like.

Specific examples of nickel compounds include dicarbonylbis(triphenylphosphine)nickel, dibromobis(triphenylphosphine)nickel, and dinitrogenbis(triphenylphosphine)nickel.
bis(tricyclohexylphosphine)nickel, chlorohydridobis(tricyclohexylphosphine)nickel, chloro(phenyl)bis(triphenylphosphine)nickel, dimethylbis(trimethylphosphine)nickel, diethyl(2,2'-bipyridyl)nickel,
Bis(allyl) nickel, bis(cyclopentadienyl) nickel, bis(methylcyclopentadienyl) nickel, bis(pentamethylcyclopentadienyl) nickel, allyl(cyclopentadienyl) nickel, (
cyclopentadiene) (cyclooctadiene) nickel tetrafluoroborate, bis(cyclooctadiene) nickel, nickel bisacetylacetonate, allyl nickel chloride, tetrakis(triphenylphosphine) nickel, nickel chloride.

(C,Hs)Ni (DC(C,1t)CH=P(C6
Hs)z ) (P(Cg)Is)2) and the like.

Further, specific examples of palladium compounds include dichlorobis(benzonitrile)palladium, carbonyltris(triphenylphosphine)palladium, dichlorobis(triethylphosphine)palladium, bis(t-butylisocyanide)palladium, palladium bis(acetylacetonate). , dichloro(tetraphenylcyclobutadiene)palladium, dichloro(1,5-cyclooctadiene)palladium, allyl(cyclopentagenyl)palladium, bis(allyl)palladium.

Allyl (1,5-cyclooctadiene) palladium tetrafluoroborate, (acetylacetonate) (1,
5-cyclooctadiene) palladium tetrafluoroborate, tetrakis(acetonitrile) palladium tetrafluoroborate, and the like.

In the present invention, the aluminoxane solution described above is used as the other component (organometallic compound component) of the catalyst.

This aluminoxane solution can of course be used alone,
Add organic aluminum compound (
The aluminoxane solution may be mixed with other organometallic compounds, or the aluminoxane solution may be adsorbed or supported on an inorganic substance.

The catalyst of the present invention has the above-described transition metal compound component and the above-described aluminoxane solution as main components,
In addition to this, other catalyst components, such as other organometallic compounds, may be added if desired.

When using the catalyst of the present invention, the ratio of the transition metal compound component in the catalyst to the aluminoxane solution varies depending on various conditions and cannot be unambiguously determined. The ratio to the transition metal in the compound component, that is, the aluminum/transition metal (molar ratio) is 1 to 106, preferably 1O to
It may be set to 104.

The catalyst of the present invention as described above exhibits high activity in the production of styrenic polymers (especially styrene polymers mainly having a syndiotactic structure) and olefin polymers.

In order to produce the styrenic polymer, styrene and/or styrene derivatives (alkyl styrene, alkoxystyrene, halogenated styrene, vinyl benzoate, etc.) are used in the presence of the above-mentioned polymerization catalyst of the present invention. A styrene monomer may be polymerized or copolymerized.

In addition, in order to produce an olefinic polymer, various olefins, such as ethylene; propylene:butene-1; hexene-1:octene-1;4-methylpentene-1 In addition to α-olefins such as, butadiene; isoprene; norbornadiene; acetylene; methylacetylene, etc. may be polymerized or copolymerized.

The polymerization may be carried out in bulk, or may be carried out in an aliphatic hydrocarbon solvent such as pentane, hexane, heptane, an alicyclic hydrocarbon solvent such as cyclohexane, or an aromatic hydrocarbon solvent such as benzene, toluene, or xylene. good.

In addition, the polymerization temperature is not particularly limited, but is generally -30°
C to +150°C1, preferably -10°C to +120°C.

Further, the molecular weight of the obtained polymer can be adjusted by selecting the amount of transition metal used and the polymerization temperature depending on the purpose, or by carrying out the polymerization reaction in the presence of hydrogen.

Various polymers can be produced in this way.

〔Example〕

Next, the present invention will be explained in detail with reference to examples.

Example 1 (1) Preparation of aluminoxane solution Toluene 200- and copper sulfate pentahydrate (CLISO4.5Hz
35.0 g of O) was added, cooled to 5°C, and 9.6 g (133 mmol) of trimethylaluminum was added dropwise. Thereafter, the reaction was carried out at 40°C for 8 hours, the solid portion was removed, and the resulting solution was stirred at 50°C under reduced pressure, while toluene was distilled off. Once the solution was removed, the temperature was raised to 110°C and drying was performed until no distillate remained. As a result, 4.7 g of contact product aluminoxane was obtained.

This was dissolved in a mixture of 20 ml of toluene and 0.9 ml of 0-dichlorobenzene to make an aluminoxane solution, and the solution was left in a dry nitrogen atmosphere for a period of time, but no gel precipitate was formed. .

(2) Polymerization of ethylene In a nitrogen-substituted autoclave with an internal volume of 11, 400 m7' of toluene, 1 mm01 aluminum atom of the aluminoxane solution obtained in (1) above, and 5 μmol biscyclopentadienylzirconium dichloride were added.
were added one after another, and the temperature was raised to 80°C. Next, ethylene was continuously introduced into the autoclave and polymerization was carried out at 8 kg/ad for 1 hour.

After the reaction is complete, add methanol to decompose the catalyst,
After drying, 127 g of polyethylene was obtained. Catalytic activity is 27
8kg-PE/g-Zr.

(3) Inner volume of styrene substituted with polymerized nitrogen II! In an autoclave, 200 yd of styrene, 2 m of lysobutyl aluminum
mol, the aluminoxane solution obtained in (1) above was added sequentially at a ratio of 2 mmol as aluminum atoms,
The temperature was raised to 70°C. Next, 10 μmol of pentamethylcyclopentadienyl titanium trimethoxide was introduced into the autoclave, and polymerization was carried out for 1 hour.

After the reaction was completed, it was dried to obtain 85 g of a polymer.

The racemic pentad syndiotacticity of this polymer was 97% by C-NMR measurement.The catalyst activity was 177.5 kg-3PS/g-Ti.

Comparative Example 1 An aluminoxane solution was prepared in the same manner as in Example 1 (1) except that 0-dichlorobenzene was not used, and the solution was left in a dry nitrogen atmosphere for one month. , a gel-like precipitate was formed.

Example 2 (1) Preparation of aluminoxane solution The procedure was repeated in the same manner as in Example 1 (1) except that 0.81 nI of dioxane was used instead of 0-dichlorobenzene in Example 1 (1). 4.3 g of product aluminoxane was obtained.

This was dissolved in a mixture of 2(W) toluene and 0.9-0-dichlorobenzene to make an aluminoxane solution,
Although the sample was allowed to stand for a period of time in a dry nitrogen atmosphere, no gel precipitate was formed.

(2) Polymerization of ethylene In Example 1 (2), as an aluminoxane solution,
Ethylene polymerization was carried out in the same manner as in Example 1 (2) except that the aluminoxane solution obtained in (1) above was used. Catalytic activity is 246 kg-PE/g-Z
It was r.

(3) Polymerization of styrene In Example 1 (3), as an aluminoxane solution,
Styrene polymerization was carried out in the same manner as in Example 1 (3) except that the aluminoxane solution obtained in (1) above was used. Catalytic activity was 82 kg-3PS/g-Ti.

〔Effect of the invention〕

The aluminoxane solution of the present invention has excellent uniformity,
There is no risk of precipitation of gel-like particles even after long-term storage.

Moreover, since the aluminoxane solution of the present invention does not contain aluminum alkyl, etc., the activity may change or
There is no fear of limiting the physical properties of the produced polymer.

Moreover, the aluminoxane solution of the present invention can improve the catalytic activity by using it as a catalyst component for polymerization.

Therefore, a catalyst obtained by combining this with a transition metal compound can be used extremely effectively as a catalyst for various polymerizations.

Procedural amendment (marshal) August 21, 1991

Claims (5)

[Claims] (1) An aluminoxane solution consisting of aluminoxane, an aromatic hydrocarbon, and a polar compound. (2) The aluminoxane solution according to claim 1, wherein the aluminoxane is methylaluminoxane. (3) The aluminoxane solution according to claim 1, wherein the polar compound is a halogenated hydrocarbon. (4) The polar compound does not contain active hydrogen and contains at least one of an oxygen atom, a sulfur atom, a nitrogen atom, and a phosphorus atom.
The aluminoxane solution according to claim 1, which is a compound having a seed atom. (5) A polymerization catalyst comprising the aluminoxane solution according to claim 1 and a transition metal compound.