JPH08127611A - Compound containing boron - Google Patents

Abstract

PURPOSE: To obtain a boron-containing compound, represented by a specific formula, readily supportable on a carrier, excellent in immobilizing ability, hardly separating, capable of immobilizing a promoter itself on the carrier or a polymer without losing the promoter actions on the olefin polymerization and useful as the promoter for a metallocene catalyst. CONSTITUTION: This compound of the formula (B is boron atom; C is carbon atom; R<1> to R<6> are each H, a 1-10C hydrocarbon, a hydrocarbon containing Si or a hydrocarbon containing a halogen; Y is a 1-10C alkylene, an arylene, an alkylarylene, silylene or an alkylsilylene; (n) is 0-2; X is a monovalent cation such as carbonium, ammonium, anilinium, ferrocenium, phosphonium, Na, Li or K), e.g. N,N-dimethylanilinium tris(pentafluorophenyl)4-vinylphenyl borate. Furthermore, the objective compound is preferably synthesized from, e.g. pentafluorophenylborane and an alkyl-Grignard reagent.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a boron-containing compound useful as a cocatalyst for olefin polymerization, particularly a metallocene catalyst.

[0002]

2. Description of the Related Art Group 18 elements (Ti,
In order to make the metallocene compound (main catalyst) having Zr, Hf) a central metal have an olefin polymerization catalytic action, the following co-catalysts have been required.

The halogen-containing organoaluminum compound is
Polymerization of ethylene in combination with the above metallocene compounds in toluene solution has been reported (Adv. Organometal
licChemistry, VOL. 18, p130) has a remarkably low activity.

Aluminoxanes, especially methylaluminoxane, are known as typical cocatalysts for forming metallocene catalysts in combination with metallocene compounds.
Since it is used in a large excess with respect to metallocene compounds, the activity per cocatalyst is low (H.Sinn, W. Kaminsky, Adv.
Organometallic Chem., 18. 99 (1980).). Further, studies have been made to support this methylaluminoxane on a carrier (Japanese Patent Publication No. 6-39496, JP-A-61-10861).
However, 0) has a drawback that complete immobilization is difficult because methylaluminoxane is partially released from the carrier during the polymerization. Attempts have been made to solidify the methylaluminoxane itself by insolubilizing it with a small amount of water, but there is a problem that the activity per methylaluminoxane is further reduced (JP-A-2-167302).

In recent years, it was found by Jordan that a boron compound exhibits a cocatalyst action on a metallocene compound (RF Jordan, J. Am. Chem. Soc., 109,
4111 (1987)). The tetraphenylborate used by Jordan et al. Is more efficient than aluminoxanes because the usage ratio to metallocene is close to 1, but its activity is low because coordinating protons are present in the molecule. Since tetrakis (pentafluorophenyl) borate is a non-coordinating anion that does not have a coordinating proton in the molecule, it has been known that it has higher activity (Japanese Patent Laid-Open No. 3-207703). 207704). Utilizing this fact, attempts have been made to immobilize it on a carrier to form a solid catalyst (Japanese Patent Laid-Open No. 5-155926, Japanese Laid-Open Patent Publication No. 3-155926).
-234709) is inherently non-coordinating, so that it is not sufficiently fixed and easily detached from the carrier.

When the metallocene catalyst is applied to a continuous polymerization process such as a slurry process or a gas process in the olefin polymerization, the immobilization of the cocatalyst component is insufficient, regardless of whether it is an aluminoxane type or a boron type. Causes sticking to reactor. Therefore, there is a demand for a highly active cocatalyst that can be immobilized on a carrier or a polymer.

[0007]

As a cocatalyst for a metallocene catalyst, without losing the olefin polymerization cocatalyst function,
Provided is a boron-containing compound capable of fixing the cocatalyst itself to a carrier or a polymer.

[0008]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a carbon-carbon double bond as a functional group capable of forming a coordination bond and polymerization in a molecule. A new boron-containing compound incorporated was synthesized, and it was discovered that this compound was easily supported on a carrier, had excellent immobilization ability, and had little detachment, and that this compound itself could be polymerized or copolymerized as a monomer. Further, they have found that this compound has a high performance as a polymerization catalyst for olefins in combination with a metallocene compound, and completed the present invention.

The boron compound of the present invention is represented by the general formula (1).

Embedded image In the formula (1), B means a boron atom and C means a carbon atom. R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are hydrogen atoms, hydrocarbon groups having 1 to 10 carbon atoms, silicon-containing hydrocarbon groups, or halogen-containing carbon atoms such as fluorine, chlorine, and bromine. It means a hydrogen group and may be the same or different. Y is an alkylene group having 1 to 10 carbon atoms, an arylene group, an alkylarylene group, a silylene group,
It is an alkylsilylene group. n is an integer of 0 to 2. X ⁺ means a monovalent cation and means a cation such as carbonium, ammonium, anilinium, ferrocenium, phosphonium, sodium, lithium or potassium.

The structure of the more preferred boron-containing compound (1) of the present invention will be described. R ¹ , R ² and R ³ are hydrogen atoms or hydrocarbon groups having 1 to 3 carbon atoms, preferably hydrogen. . R ⁴ , R ⁵ and R ⁶ are hydrogen atoms or
A hydrocarbon group having 1 to 10 carbon atoms or a halogenated hydrocarbon, preferably a phenyl group, a pentafluorophenyl group, a 2,4,6-trifluoromethylphenyl group,
It is a 3,5-bistrifluoromethylphenyl group, and more preferably a pentafluorophenyl group. Y
Is an alkylene group having 1 to 6 carbon atoms, preferably a methylene group, an ethylene group, a propylene group, a butylene group, a p-phenylene group, a m-phenylene group, an o-phenylene group, and more preferably p. A phenylene group. n is an integer of 0 to 2, and is preferably 1. X
⁺ Means a monovalent cation, carbonium, ammonium, anilinium, ferrocenium, sodium,
It means a cation such as lithium or potassium, preferably a carbocation such as triphenylcarbonium, a trialkylammonium such as trimethylammonium, triethylammonium, tripropylammonium, triphenylammonium, N, N-dimethylanilinium or ferrocenium. , Dimethylferrocenium. More preferred are trimethylammonium, triphenylcarbonium and N, N-dimethylanilinium.

A more preferable boron-containing compound of the present invention is represented by the general formula (2).

[Chemical 4] [In Formula (2), B means a boron atom and C means a carbon atom. X ⁺ represents a monovalent cation and means carbonium, ammonium, anilinium, ferrocenium, phosphonium, sodium, potassium, lithium and the like. ]

The specific boron-containing compound of the present invention can be exemplified as follows, but the invention is not limited thereto. For example, N, N-dimethylanilinium tris (pentafluorophenyl) -4-vinylphenyl borate, N, N-dimethylanilinium tris (pentafluorophenyl) -3-vinylphenyl borate,
N, N-dimethylanilinium tris (pentafluorophenyl) -2-vinylphenyl borate, N, N-dimethylanilinium triphenyl-4-vinylphenyl borate, methyldiphenylammonium tris (pentafluorophenyl) -4-vinylphenyl Borate,
Methyldiphenylammonium tris (pentafluorophenyl) -3-vinylphenylborate, methyldiphenylammonium tris (pentafluorophenyl)
2-vinylphenyl borate, methyldiphenylammonium bis (pentafluorophenyl) bis (4-vinylphenyl) borate, methyldiphenylammonium bis (pentafluorophenyl) bis (3-vinylphenyl) borate, methyldiphenylammonium bis (pentafluoro Phenyl) bis (2-vinylphenyl) borate, methyldiphenylammonium triphenyl-4-vinylphenylborate, trimethylammonium tris (pentafluorophenyl) -4-vinylphenylborate, trimethylammonium tris (pentafluorophenyl) -3-vinyl Phenyl borate, trimethylammonium tris (pentafluorophenyl) -4-vinylphenyl borate, trimethylammonium triphenyl -4-Vinylphenylborate, tri (n-butyl) ammonium tris (pentafluorophenyl) -4-vinylphenylborate, triphenylcarbonium tris (pentafluorophenyl) -4-vinylphenylborate, triphenylcarbonium tris ( Pentafluorophenyl) -3-vinylphenyl borate, triphenylcarbonium tris (pentafluorophenyl) -2-vinylphenyl borate, triphenylcarbonium triphenyl-4-vinylphenyl borate, ferrocenium tris (pentafluorophenyl) -4-Vinylphenyl borate, the most preferred boron containing compound is trimethylammonium tris (pentafluorophenyl) -4-vinylphenyl borate.

The boron-containing compound of the present invention is, for example, synthesized from pentafluorophenylborane and alkyl grignard, and can be prepared by ion-exchange of the cation moiety as necessary. For example, trimethylammonium tris (pentafluorophenyl) -4-vinylphenyl borate can be synthesized by the route shown in the following formula.

Embedded image

The carrier and method for supporting the boron-containing compound of the present invention are not particularly limited, but examples of the carrier include silica, magnesium chloride, calcium carbonate, alumina and the like. Examples of the supporting method include a method of dissolving in an organic solvent for impregnation and a co-grinding method. As means for polymerizing or copolymerizing the boron-containing compound of the present invention,
Radical initiators such as azobisisobutyronitrile can be used. It is also possible to use a Ziegler catalyst. Further, a metallocene catalyst can also be used. When it is copolymerized with the boron compound of the present invention, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, styrene, p-methylstyrene, p-chlorostyrene, divinylbenzene, etc.
Methyl methacrylate, ethyl methacrylate, acrylonitrile, acrylic ester, butadiene, 1,5
Hexadiene, vinyl acetate, etc. can be mentioned. Preferred are ethylene, styrene and divinylbenzene.

[0015]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. The synthesis operation was performed under a nitrogen atmosphere as needed. The instruments used for the analysis were nuclear magnetic resonance spectrum (EX-400 manufactured by JEOL Ltd.), GPC (Wate).
rs-150C), elemental analyzer (HeraensCH)
N-O-PAPID) was used.

Example 1 [Synthesis of trimethylammonium tris (pentafluorophenyl) -4-vinylphenylborate] 4 prepared from dry magnesium and 4-bromostyrene
-Vinylphenyl magnesium bromide (7.0 mm
ol) to trispentafluorophenylborane (3.4
% Isopar-E solution 75.3 ml; 5.0 mmo
It was added to 1) and stirred as it was for 17 hours. The obtained suspension was transferred to a NaCl aqueous solution (100 ml), and the aqueous layer was extracted with tetrahydrofuran. The organic layer was separated, the solvent was evaporated under reduced pressure and sodium tris (pentafluorophenyl)-
A white solid of 4-vinylphenyl borate was obtained. The obtained sodium salt (2.91 mmol) in water (5
Solution (50 ml) of trimethylammonium hydrochloride (2.91 mmol) was added dropwise to 0 ml) at room temperature under nitrogen.
The mixture was stirred as it was at room temperature for 40 minutes. After completion of the reaction, the produced solid was filtered off, and the solid was washed with distilled water and hexane and dried under reduced pressure to obtain the target compound. <Elemental analysis> (molecular formula _{C 29 H 17 BF 15 N)} C H N calc (%) 51.58 2.54 2.26 Found (%) 51.36 2.71 2.07 ^<1 H- NMR> Figure -2 ^<19 F-NMR> Figure 3

Example 2 [Support of Trimethylammonium Tris (pentafluorophenyl-4-vinylphenyl) borate on Alumina] 2 g of alumina calcined at 600 ° C. for 5 hours under nitrogen, 30 ml of dry toluene and 30 ml of trimethylammonium tris (pentafluoro). A toluene solution (10 ml) of phenyl) -4-vinylphenyl borate (0.67 g) was added, and the mixture was stirred at room temperature for 3 hours. Hexane 20m except the supernatant
It was washed 5 times with 1 and dried under reduced pressure to obtain a white solid. 27 wt% of trimethylammonium tris (pentafluorophenyl) -4-vinylphenylborate due to weight change
(0.54 g) was included.

Comparative Example 1 [Support of dimethylanilinium tetrakis (pentafluorophenyl) borate] Dimethylanilinium tetrakis (pentafluorophenyl) was used instead of trimethylammonium tris (pentafluorophenyl-4-vinylphenyl) borate in Example 2. When borate was used, it was found that the solid content of the solid was 0.
It contained 5 wt% of dimethylanilinium tetrakis (pentafluorophenyl) borate and was difficult to support.

Example 3 [Copolymerization of trimethylammonium tris (pentafluorophenyl) -4-vinylphenyl borate with styrene] Trimethylammonium tris (pentafluorophenyl) -4-vinylphenyl borate (1.3505 g; 2.0 mmol), styrene (2.
29 ml; 20 mmol), azobisisobutyronitrile (0.109 g) and acetonitrile (3.4 ml)
Was charged and heated at 80 ° C. for 20 hours. After the reaction was completed, the content of the ampoule was dissolved in acetone and reprecipitated with n-hexane to obtain a white solid (1.18 g). This solid ¹
As a result of identification by H-, ¹⁹ F-NMR, elemental analysis and GPC, the composition ratio of trimethylammonium (4-vinylphenyl) tris (pentafluorophenyl) borate and styrene was 1:10 in molar ratio, and the molecular weight was Mw = 6700. It was a polymer. The elemental analysis values are shown below. <Elemental analysis value> CHN calculated value (%) 76.26 5.70 0.82 Measured value (%) 76.94 6.05 1.13

Comparative Example 2 [Copolymerization experiment of dimethylanilinium tetrakis (pentafluorophenyl) borate with styrene] Radical polymerization was tried by the method described in Example 3, but dimethylanili was found in the obtained polymer. Almost no polystyrene tetrakis (pentafluorophenyl) borate was detected, and simple polystyrene was obtained.

Example 4 [Polymerization of ethylene with metallocene catalyst using trimethylammonium tris (pentafluorophenyl) -4-vinylphenylborate as a cocatalyst] 10 ml of dry toluene and 100 ml of triisobutylaluminum in a 100 ml two-necked flask under a nitrogen atmosphere. Of toluene solution (0.5 mol / l), dimethylsilylenebis (1-indenyl) zirconium dichloride toluene solution (0.98 mmol / l) 2.4 ml, trimethylammonium tris (pentafluorophenyl) -4-
Toluene solution of vinyl phenyl borate (1.43mm
ol / l) (2.5 ml) was charged in this order, and atmospheric pressure ethylene gas was blown in at room temperature. The reaction solution immediately began to turn cloudy with polyethylene and polymerized for 10 minutes. The yield of the obtained polyethylene was 520 mg, which was 2.9 kgPE / g metallocene in terms of 1 g of the zirconium complex.

[0022]

INDUSTRIAL APPLICABILITY The boron-containing compound of the present invention is useful as a novel cocatalyst capable of fixing the cocatalyst itself to a carrier or a polymer because it has a polymerizable functional group without losing the olefin polymerization cocatalyst function.

[Brief description of drawings]

1 is an example of a nuclear magnetic resonance spectrum ( ¹ H-NMR) chart of the boron-containing compound shown in Example 1. FIG.

2 is an example of a nuclear magnetic resonance spectrum ( ¹⁹ F-NMR) chart of the boron-containing compound shown in Example 1. FIG.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shintaro Inazawa, Oita City, Oita Prefecture, No. 2 Nakasu, Showa Denko K.K.

Claims (2)

[Claims] 1. A boron-containing compound represented by the general formula (1): [In the formula (1), B means a boron atom and C means a carbon atom. R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are hydrogen atoms or hydrocarbon groups having 1 to 10 carbon atoms, or
It means a silicon-containing hydrocarbon group or a halogen-containing hydrocarbon group such as fluorine, chlorine and bromine, which may be the same or different. Y is an alkylene group having 1 to 10 carbon atoms, an arylene group, an alkylarylene group, a silylene group, or an alkylsilylene group. n is an integer of 0 to 2. X
⁺ Means a monovalent cation, and means a cation such as carbonium, ammonium, anilinium, ferrocenium, phosphonium, sodium, lithium or potassium. ] 2. A boron-containing compound represented by the general formula (2): [In Formula (2), B means a boron atom and C means a carbon atom. X ⁺ represents a monovalent cation and means carbonium, ammonium, anilinium, ferrocenium, phosphonium, sodium, potassium, lithium and the like. ]