JPH0680679A - New organosilicon compound - Google Patents

Abstract

PURPOSE:To provide the subject new compound useful as an electron donating compound in producing alpha-olefin polymers in the magnesium chloride-carrying type Ziegler-Natta catalytic system. CONSTITUTION:The objective compound, 2-trimethoxysilyladamanthane of the formula, which can be obtained, for example, by reaction of tetrachlorosilane with a 2-adamanthyl Grignard reagent (e.g. a 2-adamanthyl magnesium halide) and removing the magnesium salt formed through filtration followed by distilling the solvent off the filtrate and then reaction of the filtrate with methanol in the presence of a dehydrohalogenating agent pref. at 60-80 deg.C for 2-6hr.

Description

Detailed Description of the Invention

[0001]

The present invention relates to 2-trimethoxysilyladamantane, a novel organosilicon compound which has not been published in the literature.
(Trimethoxytricyclo (3.3.1.13,7) dec-2-ylsilane). This silane compound can be used as an electron donating compound when producing an α-olefin polymer in a magnesium chloride-supported Ziegler-Natta catalyst system, and can also be used as a silane coupling agent or a resin modifier.

[0002]

2. Description of the Related Art Supported Zieg for producing α-olefin polymers
It is well known that the use of an organosilicon compound as an electron-donating compound of the ler-Natta catalyst system, for example, a trialkoxysilane compound such as phenyltriethoxysilane improves the stereoregularity of the polymer produced. Are
(For example, JP-A-57-63310, JP-A-57-63311, JP-A-2-
17803, JP-A-2-229807). However, the conventionally used trialkoxysilane compounds are economically disadvantageous to use industrially in order to significantly deactivate the catalytic activity, and the stereoregularity of the obtained α-olefin polymer is not always required. It did not meet the current requirements. Further, silane compounds are expected to be used as silane coupling agents, resin modifiers, etc. Therefore, the emergence of new silane compounds has long been desired.

[0003]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention
Provided 2-trimethoxysilyladamantane, a novel organosilicon compound not yet published in the literature, which is useful as an electron-donating compound in a Ziegler-Natta catalyst system supporting magnesium chloride, which is a catalyst for producing olefin polymers, and a silane coupling agent. It is to be.

[0004]

Means for Solving the Problems As a result of various investigations by the present inventors to develop a novel electron-donating compound, the formula

[Chemical 2] 2-trimethoxysilyl adamantane represented by is a phenyl group, a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a cyclopentyl group or a cyclohexyl group which is often used as a hydrocarbon ligand of a conventionally known electron donating compound. It has a 2-adamantyl group instead of, and this one can produce an α-olefin polymer having high stereoregularity without lowering the polymerization activity as compared with a conventionally known electron donating compound. It was possible and was found to be extremely useful as an electron-donating compound for a magnesium chloride-supported Ziegler-Natta type catalyst system, and the present invention has been completed. Since the above effect is not observed with 1-trimethoxysilyladamantane having a similar structure, it is considered that the above effect is exhibited only when the trimethoxysilyl group is bonded to the 2-position of the adamantyl group. The novel silane compound can also be used as a silane coupling agent or a resin modifier.

Adamantane is the formula

[Chemical 3] , Which is produced by reacting tetrachlorosilane with 2-adamantyl magnesium halide as a 2-adamantyl Grignard reagent or 2-adamantyl lithium as an organolithium reagent, and then producing magnesium. The salt or lithium salt can be removed by filtration, the solvent is distilled off, and this is then reacted with methanol in the presence of a dehydrohalogenating agent.

Further, trichlorosilane or dichlorosilane is reacted with 2-adamantylmagnesium halide as a 2-adamantyl grignard reagent or 2-adamantyllithium as an organolithium reagent, and then a magnesium salt or a lithium salt is formed. Is removed by filtration, the solvent is distilled off, and then this is reacted with methanol in the presence of a dehydrohalogenating agent, followed by dehydrogenation in the presence of methanol and a catalyst. be able to.

Alternatively, tetramethoxysilane and 2-adamantylmagnesium halide as a 2-adamantyl Grignard reagent or 2 as an organolithium reagent.
-After the reaction with adamantyllithium, the magnesium salt or lithium salt produced is removed by filtration, and the solvent is distilled off. Furthermore, after reacting trimethoxysilane and 2-adamantyl magnesium halide as a 2-adamantyl Grignard reagent or 2-adamantyl lithium as an organic lithium reagent, the magnesium salt or lithium salt produced is removed by filtration. The solvent can be distilled off, and this can be synthesized by a dehydrogenation reaction in the presence of methanol and a catalyst.

The tetrachlorosilane, trichlorosilane, dichlorosilane, tetramethoxysilane, and trimethoxysilane used here may be used as they are in a gas or liquid state, but they include tetrahydrofuran, diethyl ether, dibutyl ether, etc. It may be used as an ether solution. Further, the halogen atom used as the Grignard reagent used here is 2- or 1-containing Cl or Br.
The adamantyl magnesium halide and 2-adamantyl lithium as the organic lithium reagent may be used as an ether solution of tetrahydrofuran, diethyl ether, dibutyl ether, or the like.

This reaction is carried out by adding the above tetrachlorosilane to an ether solution of 2-adamantylmagnesium halide as the Grignard reagent or an ether solution of 2-adamantyllithium as the organolithium reagent in the form of a liquid or ether. It is added in the form of a solution and reacted at a temperature not exceeding room temperature, or the above-mentioned tetrachlorosilane ether solution is treated with 2-adamantylmagnesium halide as the Grignard reagent.
Tellurium solution or an ether solution of 2-adamantyllithium as an organolithium reagent is reacted at a temperature not exceeding room temperature to remove magnesium salt or lithium salt produced by filtration, and the solvent is distilled off. 2-Trimethoxysilyladamantane can be easily obtained by a method of reacting with methanol in the presence of a dehydrohalogenating agent.

Alternatively, the reaction is the above-mentioned Grignard
Solution of 2-adamantylmagnesium halide as an ether reagent or an ether solution of 2-adamantyllithium as an organolithium reagent, the above-mentioned trichlorosilane or dichlorosilane is added in the form of gas or liquid or ether solution. Then, the reaction is carried out at a temperature not exceeding room temperature, or an ether solution of 2-adamantyl magnesium halide as the Grignard reagent described above in an ether solution of the above-mentioned trichlorosilane or dichlorosilane or an organolithium reagent as an organolithium reagent is used. After reacting an ether solution of 2-adamantyllithium at a temperature not exceeding room temperature, the magnesium salt or lithium salt formed is removed by filtration, the solvent is distilled off, and then this is removed in the presence of a dehydrohalogenating agent. After reacting with methanol, The presence of a catalyst, can be easily 2- trimethoxysilyl adamantane in a way that is dehydrogenation.

This reaction is carried out by adding the above-mentioned tetramethoxysilane to an ether solution of 2-adamantylmagnesium halide as the Grignard reagent or an ether solution of 2-adamantyllithium as the organolithium reagent in a liquid or It is added in the form of an ether solution and reacted at a temperature not exceeding room temperature, or an ether solution of 2-adamantylmagnesium halide as the Grignard reagent is added to the ether solution of tetramethoxysilane described above. Or 2- as an organolithium reagent
By reacting an ether solution of adamantyllithium at a temperature not exceeding room temperature, 2-trimethoxysilyladamantane can be easily obtained.

Furthermore, this reaction is based on the above-mentioned Grignard.
Solution of 2-adamantylmagnesium halide as an ether reagent or an ether solution of 2-adamantyllithium as an organolithium reagent, the above trimethoxysilane is added in a liquid or ether solution state,
The reaction is carried out at a temperature not exceeding room temperature, or the above-mentioned ether solution of trimethoxysilane is added to the above-mentioned ether solution of 2-adamantylmagnesium halide as a Grignard reagent or 2-as an organolithium reagent.
After reacting the ether solution of adamantyllithium at a temperature not exceeding room temperature, the magnesium salt or lithium salt formed is removed by filtration, the solvent is distilled off, and then the dehydrogenation reaction is carried out in the presence of methanol and a catalyst. If so, 2-trimethoxysilyl adamantane can be easily obtained.

When tetrachlorosilane, trichlorosilane or dichlorosilane is added to an ether solution of 2-adamantylmagnesium halide as the Grignard reagent in a gas or liquid or ether solution, the reaction is accelerated. Cyan, a thiocyan compound or the like may be used as a catalyst to be present in the solution system during the reaction.
Examples of the dehydrohalogenating agent include tertiary amine, urea, nitrogen-containing heterocyclic compounds such as pyridine, quinoline, isoquinoline, and among these, urea is preferably used.

The catalyst used for the dehydrogenation reaction is a Group VIII or alkali metal, preferably VIII.
Group transition metal complexes or K and Na are used. In carrying out this dehydrogenation reaction, the above-mentioned catalyst for dehydrogenation reaction is used in an amount of 1.0 to 1.2 times the molar amount of the silane compound, and the temperature is 20 to 100 ° C, preferably 60 to 80 ° C for 1 hour. It is preferable to carry out the reaction for 24 hours, preferably for 2 hours to 6 hours.

The 2-trimethoxysilyl adamantane thus obtained is as follows: Gas chromatography mass spectrometry (CI method)
・ Figure 1 Molecular ion peak (M + 1): 257 ・ Mass analysis by gas chromatography (EI method) ・ ・
・ Figure 2 m / e (spectral intensity ratio (%)): 256 (40.37), 134 (32.34),
121 (100), 91 (40.46) ・¹ H-NMR analysis value measured using deuterated chloroform as a solvent ・
..Fig. 3 δ ( ¹ H / ppm): 1.224 (s, 1H), 1.492 (d, 2H), 1.736 (d, 2
H), 1.550 to 1.700 (s, 2H; s, 1H; s, 1H; d, 2H), 1.879 (s, 2
H), 1.900 (d, 2H), 3.516 (s, 9H) ¹³ C-NMR measured using deuterated chloroform as a solvent ...
Fig. 4 δ ( ¹³ Si / ppm): 27.805, 28.317, 28.390, 32.085, 34.8
09, 37.772, 40.150 ・²⁹ Si-NMR measured using deuterated chloroform as a solvent ...
Figure 5 δ ( ²⁹ Si / ppm): -46.699 (with tetramethylsilane as an external standard)

[Chemical 4] It was confirmed that the compound was 2-trimethoxysilyladamantane, which had a trimethoxysilyl group at the 2-position of the adamantyl group as described above. -
It is said to be useful as an electron donating compound when producing an α-olefin polymer in a Natta catalyst system.
This silane compound can also be used as a silane coupling agent or a resin modifier.

[0016]

EXAMPLES Examples of the present invention will be given below. (Example 1) 14.96 g (69.58 mmo) of 2-bromoadamantane was added to a 500 ml three-necked flask equipped with a cooling tube and a dropping funnel.
l), 25.36 g (1.04 mol) of magnesium chips and 100 ml of dried diethyl ether were charged to prepare a diethyl ether solution of 2-adamantyl magnesium bromide. Then to a dry 100 ml of diethyl ether placed in a 500 ml three-necked flask equipped with a magnetic stirrer, a condenser and a dropping funnel, a solution of 2-adamantylmagnesium bromide in diethyl ether prepared by the above-mentioned method was added. Dichlorosilane 30.00g (0.30m
ol) was added and the mixture was stirred overnight at room temperature to remove the magnesium salt produced at the time of reaction, and diethyl ether was removed by a rotary evaporator. The obtained liquid colorless transparent substance was treated with methanol (150 m).
A solution of 12.4 g of urea in 1 l was added dropwise and reacted under reflux conditions, and the end point of the reaction was confirmed by gas chromatography. The reaction solution was extracted with hexane, and the rotary evaporation was performed.
Hexane was distilled off with a tap. The obtained liquid colorless transparent substance was added to 30 ml of methanol and a catalytic amount of sodium without purification and reacted under reflux conditions, and the end point of the reaction was confirmed by gas chromatography. When the liquid colorless transparent substance obtained by removing the methanol by a rotary evaporator was distilled under reduced pressure at 20 mmHg and 156 ° C., 7.53 g of a liquid colorless transparent substance was obtained. Next, when it was analyzed by gas chromatography, it was shown to be a single component. This product was analyzed by mass spectrometry by gas chromatography, ¹ H-NMR, ¹³ C { ¹ H} -NMR, ²⁹ Si-NMR, and the above results were obtained. -Trimethoxysilyl adamantane was confirmed.

(Example 2) 2-bromoadamantane 15.0 was added to a 500 ml three-necked flask equipped with a cooling tube and a dropping funnel.
3g (70.00mmol) and 25.48g (1.05mol) magnesium chips
And 100 ml of dried diethyl ether.
-Adamantyl magnesium bromide diethyl ether-
A tell solution was prepared. Then dry 100 m in a 500 ml three-necked flask equipped with a magnetic stirrer, condenser and dropping funnel.
l diethyl ether and tetramethoxysilane 12.1
6 g (80.00 mmol) was charged, and a solution of 2-adamantylmagnesium bromide in diethyl ether prepared by the above-mentioned method was added dropwise at room temperature, and the mixture was stirred at room temperature for one day to react. The produced magnesium salt was removed by filtration, and the diethyl ether was removed by a rotary evaporator. When the obtained liquid colorless transparent substance was distilled under reduced pressure at 20 mmHg and 156 ° C., 7.17 g of a liquid colorless transparent substance was obtained. Next, when it was analyzed by gas chromatography, it was shown to be a single component. Gas chromatography-mass spectrometry of this product, ¹ H-NMR, ¹³ C { ¹ H} -NMR,
^{When 29} Si-NMR was measured, the above results were obtained, and it was confirmed that this was 2-trimethoxysilyl adamantane.

Example 3 2-Bromoadamantane 15.0 was added to a 500 ml three-necked flask equipped with a cooling tube and a dropping funnel.
6g (70.05mmol) and 25.42g (1.05mol) magnesium chips
And 100 ml of dried diethyl ether.
-Adamantyl magnesium bromide diethyl ether-
A tell solution was prepared. Then dry 100 m in a 500 ml three-necked flask equipped with a magnetic stirrer, condenser and dropping funnel.
8.5 g of diethyl ether and trimethoxysilane
(70.08 mmol) was charged, and a solution of 2-adamantylmagnesium bromide in diethyl ether prepared by the above-mentioned method was added dropwise at room temperature, and the mixture was stirred at room temperature for one day to react. The produced magnesium salt was removed by filtration, and the diethyl ether was removed by a rotary evaporator.
Removed by. 100 ml of methanol and a catalytic amount of sodium were added to the obtained liquid colorless transparent substance and the mixture was reacted under reflux conditions, and the end point of the reaction was confirmed by gas chromatography. 20 mm of liquid colorless transparent substance obtained by removing methanol with a rotary evaporator
After vacuum distillation under the conditions of Hg and 156 ° C., 6.45 g of a colorless colorless transparent substance was obtained. Next, when it was analyzed by gas chromatography, it was shown to be a single component. Gas chromatography mass spectrometry of this product, ¹ H-NMR, ¹³ C { ¹ H} -NMR, ²⁹ Si-N
When MR was measured, the above results were obtained, and therefore it was confirmed that this was 2-trimethoxysilyl adamantane.

[0019]

INDUSTRIAL APPLICABILITY The present invention relates to a novel 2-trimethoxysilyladamantane which has not been published in the literature,

[Chemical 5] Which is obtained by the reaction of tetrachlorosilane with 2-adamantyl magnesium halide as a 2-adamantyl Grignard reagent or 2-adamantyl lithium as an organolithium reagent. A simple method of reacting with methanol in the presence of a hydrogenating agent or trichlorosilane, dichlorosilane and 2-adamantylmagnesium halide as 2-adamantylgrignard reagent or 2-adamantyllithium as organolithium reagent. A simple method of reacting the product obtained by the reaction with methanol with methanol in the presence of a dehydrohalogenating agent and then dehydrogenating in methanol, or tetramethoxysilane and 2-adamantyl glycol 2 as a Neil reagent
-A simple method of reacting with adamantyl magnesium halide or 2-adamantyl lithium as an organolithium reagent, and further with trimethoxysilane and 2-
To obtain a product obtained by the reaction with 2-adamantylmagnesium halide as an adamantyl Grignard reagent or 2-adamantyllithium as an organolithium reagent by a dehydrogenation reaction in excess methanol It was confirmed that it is a novel organosilicon compound that has not been published in the literature because it shows the measured values as described above, but this compound has a trimethoxysilyl group at the 2-position of the adamantyl group. From having
This is useful as an electron-donating compound when producing an α-olefin polymer in a magnesium chloride-supported Ziegler-Natta catalyst system. This silane compound can also be used as a silane coupling agent or a resin modifier.

[Brief description of drawings]

FIG. 1 is a gas chromatography-mass spectrometry (CI method) spectrum diagram of 2-trimethoxysilyladamantane of the present invention.

FIG. 2 is a gas chromatography-mass spectrometry (EI method) spectrum diagram of 2-trimethoxysilyladamantane of the present invention.

FIG. 3: 2-trimethoxysilyl adamantane of the present invention
^{It is a 1} H-NMR spectrum diagram.

FIG. 4: 2-trimethoxysilyl adamantane of the present invention
^{It is a 13} C { ¹ H} -NMR spectrum diagram.

FIG. 5 is a ²⁹ Si-NMR spectrum diagram of 2-trimethoxysilyladamantane of the present invention.

Claims (1)

[Claims] 1. The formula: 2-trimethoxysilyl adamantane represented by: