JPH11222491A - Production of di(polycyclic amino)dialkoxysilane - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a di(polycyclic amino) dialkoxysilane from easily handleable raw materials in a high yield, wherein the di(polycyclic amino)dialkoxysilane is useful as an auxiliary catalyst component effective for producing an α-olefin polymer having high stereoregularity and a wide mol.wt. distribution by the polymerization of an α-olefin in the presence of a catalyst. SOLUTION: This method for producing a di(polycyclic amino)dialkoxysilane comprises reacting an organic magnesium compound of the formula: RMgX (R is a hydrocarbon group; X is a sigma-binding ligand) with a secondary polycyclic amine in an ether solvent and subsequently reacting the obtained polycyclic amide magnesium compound with a tetraalkoxysilane in a mixed solvent comprising an ether solvent and an inert hydrocarbon solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel method for producing di (polycyclic amino) dialkoxysilane.

[0002]

2. Description of the Related Art An α-olefin is converted into a solid catalyst component containing magnesium, titanium, halogen, and an electron donor (internal electron donor), an organoaluminum compound component, and an external electron donor in the presence of a catalyst composition. The technology of polymerizing to produce an α-olefin polymer is better known than before. Recent studies have revealed that it is effective to use an aminosilane compound as an auxiliary catalyst component in order to increase the stereoregularity of an α-olefin polymer produced by polymerization of an α-olefin. There have been many proposals for aminosilane compounds exhibiting such effects. For example, Japanese Patent Laid-Open No. 3-7
No. 4393, No. 7-118320, No. 7-17321
Nos. 2 and 8-100019 disclose alkyl (hydrocarbon amino) dialkoxysilanes which are effective as cocatalyst components for the polymerization of α-olefins.

JP-A-8-120021 and JP-A-8-120021
No. 143621 discloses a method for polymerizing an α-olefin using a mono (cyclic amino) alkylalkoxysilane or a di (cyclic amino) dialkoxysilane compound, which is an aminosilane compound containing a cyclic amino group.

As a method for synthesizing an aminosilane compound, a reaction between an alkyl (trialkoxy) silane and a lithium amide obtained by a reaction between an organic lithium compound and an amine is described in JP-A-3-74393.

[0005] JP-A-8-120021 discloses that a mono (cyclic amino) alkylalkoxysilane compound is obtained by reacting a secondary cyclic amine compound with a silicon halide compound or a silicon compound containing a Si-O bond. A method is described.

The above-mentioned JP-A-8-143621 discloses a reaction between a secondary cyclic amine compound and a silicon halide compound, or an alkali metal salt or an alkaline earth metal salt of a secondary cyclic amine compound and a tetraalkoxy compound. A method for obtaining a di (cyclic amino) dialkoxysilane compound by reaction with silane is described.

Japanese Patent Application Laid-Open No. 9-67379 discloses a reaction between lithium amide obtained by reacting dialkylamine and butyllithium with tetraalkoxysilane, or the reaction of tetraalkoxysilane with a Grignard reagent such as diethylamide magnesium chloride and diethyl ether. A method for producing diaminoalkoxysilane by reacting in a solution is described.

[0008]

Recently, a study by the present inventors revealed that a catalyst composition comprising a solid catalyst component containing magnesium, titanium, halogen, and an internal electron donor, an organoaluminum compound component, and an external electron donor. When an α-olefin is polymerized in the presence of a to produce an α-olefin polymer, by using di (polycyclic amino) dialkoxysilane as an auxiliary catalyst component,
It has been found that an α-olefin polymer having a high degree of stereoregularity and a wide molecular weight distribution can be obtained (Japanese Patent Application No. 8-294231 and its domestic priority application No. 9-300579). Specification (Japanese Unexamined Patent Application Publication No. 10-2
No. 18926).

Japanese Patent Application No. 8-294231 discloses a method for producing di (perhydroisoquinolino) dimethoxysilane, which comprises reacting perhydroisoquinoline with butyllithium to obtain perhydroisoquinoline. A method utilizing a reaction between a lithium salt and tetramethoxysilane is described.

The above-mentioned process for producing di (perhydroisoquinolino) dimethoxysilane using butyllithium as a raw material has the disadvantage that special care must be taken in handling butyllithium, since butyllithium is ignitable. .

[0011]

The present invention relates to an organomagnesium compound represented by RMgX (where R is a hydrocarbon group and X is a sigma-binding ligand) and a second compound.
Reaction of a magnesium polycyclic amide compound with an ethereal solvent and an inert hydrocarbon solvent in a mixed solvent of an ether solvent and an inert hydrocarbon solvent. And a method for producing di (polycyclic amino) dialkoxysilane.

That is, according to the present invention, an organomagnesium compound (RMgX) is reacted with a secondary polycyclic amine to produce a polycyclic amide magnesium compound having a polycyclic amino group (first step). A novel method for producing a di (polycyclic amino) dialkoxysilane, comprising reacting a cyclic amide magnesium compound with a tetraalkoxycyan (second step). However, the reaction (first step) between the organomagnesium compound and the secondary polycyclic amine in the method for producing a di (polycyclic amino) dialkoxysilane of the present invention is carried out in an ether solvent and with the polycyclic amide magnesium compound. The reaction with the tetraalkoxysilane (second step) must be performed in a mixed solvent of an ether solvent and an inert hydrocarbon solvent. When only one of the ether solvent and the inert hydrocarbon solvent is used during the execution of the second step, separation of the target compound, di (polycyclic amino) dialkoxysilane, is not easy,
Since the yield also decreases, it is disadvantageous for an industrial production method.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION In the organomagnesium compound represented by RMgX of the present invention, R is a hydrocarbon group, preferably a hydrocarbon group having 1 to 24 carbon atoms, and examples thereof include methyl, ethyl and propyl. Isopropyl, butyl, isobutyl, hexyl, octyl, phenyl, benzyl and the like.

X is a sigma-binding ligand, examples of which include halogen, hydrocarbon oxy, hydrocarbon amide, carboxy and the like.

Examples of the organomagnesium compound represented by RMgX include alkyl magnesium chloride,
Alkyl magnesium bromide, alkyl magnesium iodide, alkyl magnesium methoxide,
Examples thereof include alkylmagnesium ethoxide, alkylmagnesium isopropoxide, and alkylmagnesium butoxide (an alkyl group such as methyl, ethyl, propyl, butyl, hexyl, and octyl).

Since the usual organomagnesium compound exists stably as an ether solution, it can be used at the time of production or
During storage, it is often stored as an ether solution.
Examples of the ether solvent include dialkyl ethers such as diethyl ether, diisopropyl ether, dibutyl ether and diisoamyl ether, and cyclic ethers such as tetrahydrofuran, tetrahydropyran and dioxane.

In the present invention, the reaction of the organomagnesium compound with the secondary polycyclic amine (first step) is carried out in an ether solvent. Examples of the ether solvent used as the reaction solvent include the same ether solvents as the various ether solvents used for storage described above. As the reaction solvent, it is particularly preferable to use a combination of a dialkyl ether solvent such as isopropyl ether and a cyclic ether such as tetrahydrofuran. The preferred ratio (volume ratio) in this case is dialkyl ether: cyclic ether = 20: 1 to 1: 1. When using an ether solvent for this reaction, an inert hydrocarbon solvent described later may be used in combination.

In the present invention, in the second step, the polycyclic amide magnesium compound obtained in the first step is reacted with tetraalkoxysilane. The reaction in the second step is carried out by reacting an ether solvent with an inert hydrocarbon solvent. Must be performed in a mixed solvent of When either the ether solvent or the inert hydrocarbon solvent is used in the production of the polycyclic magnesium compound of the present invention, the di (polycyclic amino) dialkoxysilane of the target compound from the reaction mixture is used. It is difficult to separate and recover the compound, and the yield decreases, which is disadvantageous for an industrial production method. When an ether solvent and an inert hydrocarbon solvent are used as a mixed solvent, the mixing ratio (volume ratio) is in the range of ether solvent: inert hydrocarbon solvent = 1: 10 to 1: 0.5 (former: latter), particularly It is preferably in the range of 1: 5 to 1: 0.5.

As the ether solvent in the second step, the ether solvent used as the reaction solvent in the first step may be used as it is, or an ether solvent may be added or replaced.

Examples of the inert hydrocarbon solvent used in combination with the ether solvent include pentane, hexane, heptane, octane, cyclohexane, mineral oil, benzene, toluene, xylene and the like. Particularly preferred are low boiling hydrocarbon solvents such as pentane, hexane and heptane.

The secondary polycyclic amine used in the present invention is preferably a perhydro secondary polycyclic amine. Specific examples of perhydro secondary polycyclic amines include perhydroindole, perhydroisoindole, perhydroquinoline, perhydroisoquinoline, perhydrocarbazole, perhydroiminostilbene, perhydroacridine, and perhydrobenzo [f]. Amine compounds such as quinoline, perhydrobenzo [g] quinoline, perhydrobenzo [g] isoquinoline and perhydrophenanthridine which are condensed with a cyclohexyl ring, and hydrogen atoms bonded to carbon atoms of these amine compounds And an amine compound in which a part thereof is substituted with an alkyl group, a phenyl group or a cycloalkyl group. Particularly preferred compounds as secondary polycyclic amines used in the present invention are perhydroindole, perhydroisoindole, perhydroquinoline, perhydroisoquinoline and substituted derivatives thereof, cis and trans isomers.

Although amines generally have water absorption,
The water content of the secondary polycyclic amine used in the reaction of the present invention is usually 1% by weight or less, preferably 0.1% by weight or less, particularly preferably 0.03% by weight or less. Also,
In general, amines are liable to be oxidized in the presence of oxygen and cause coloration. Therefore, before use in the reaction of the first step of the present invention, dissolved oxygen in the reaction system is replaced with an inert gas such as nitrogen and deoxygenated. It is preferred that

Examples of the tetraalkoxysilane used in the present invention include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetraisobutoxysilane, tetra-t-butoxysilane, and mixtures thereof. Particularly preferred is tetramethoxysilane.

The organic magnesium compound of the first step and the second
In the reaction with the secondary polycyclic amine, the contact of each component is usually carried out at -30C to 100C, preferably at -10C to 80C
At a temperature of 1 to 360 minutes. In order to shorten the reaction time, the amount of each component is usually 20 to 0.05, preferably 3 to 0.1, and particularly preferably 1 to 2 in terms of the molar ratio of the secondary polycyclic amine to the organomagnesium compound. ０．５0.5. The order of contact of the components is not particularly limited.

The organic magnesium compound of the first step and the second
By reacting with a higher polycyclic amine, a polycyclic amide magnesium compound (or, alternatively, referred to as a polycyclic amino magnesium compound) can be obtained. Examples of the polycyclic magnesium amide compound include perhydropolycyclic magnesium amide.

The reaction of the polycyclic magnesium amide magnesium compound with the tetraalkoxysilane in the second step produces di (polycyclic amino) dialkoxysilane which is the target compound of the present invention. In this reaction, a magnesium alkoxy compound is by-produced in addition to the desired reaction product [di (polycyclic amino) dialkoxysilane]. Therefore, it is preferable that the by-product magnesium alkoxy compound is filtered or centrifuged as an insoluble solid product, and di (polycyclic amino) dialkoxysilane is isolated from the remaining reaction solution by a method such as distillation.

In the above reaction, the order of contact of each component is not particularly limited, but it is preferable to add tetraalkoxysilane to the polycyclic magnesium amide compound.
The contact of each reaction component is carried out usually at -20 ° C to 140 ° C, preferably at 0 ° C to 100 ° C for 1 to 600 minutes. The amount of each component used is usually 20 to 0.1 in a molar ratio of the polycyclic amide magnesium compound / tetraalkoxysilane,
Preferably it is 5-0.5. In order to shorten the reaction time, the molar ratio is preferably set to 1 or more. However, in this case, since the loss of the unreacted polycyclic amide magnesium compound becomes large, the polycyclic amide magnesium compound is expensive. In some cases, there is the disadvantage that the manufacturing costs are high. Therefore, in order to avoid loss of the polycyclic amide magnesium compound, it is preferable to charge the reaction components under the condition that the molar ratio is less than 1 so that the unreacted polycyclic amide magnesium compound does not remain. In this case, the polycyclic aminotrialkoxysilane produced as a by-product is separated and recovered, and is reacted with a newly introduced polycyclic amide magnesium compound to be converted into di (polycyclic amino) dialkoxysilane. can do.

[0028]

According to the present invention, α- in the presence of a catalyst
Easy handling of di (polycyclic amino) dialkoxysilane, which is an effective cocatalyst component for producing α-olefin polymers having a high degree of stereoregularity and a wide molecular weight distribution by olefin polymerization. It can be produced in a high yield by using suitable raw materials.

[0029]

[Example 1] Capacity 100 with dropping funnel
A stirrer piece was placed in a flask with a glass filter of 0 mL, and the inside of the flask was replaced with nitrogen using a vacuum pump.
mL, n-heptane 300 mL, and 53.7 g of perhydroisoquinoline (trans / cis = 1 / 3.2)
(0.36 mol). The dropping funnel was charged with 220 mL (0.42 mol) of a 1.68 mol / L butylmagnesium chloride isopropyl ether solution. After slowly adding a solution of butylmagnesium chloride in isopropyl ether to the flask at room temperature, the mixture was stirred at room temperature for 1 hour and further at 60 ° C. for 3 hours to obtain a reaction solution. Next, 27.4 g (0.18 mol) of tetramethoxysilane was put into the empty dropping funnel. After slowly adding tetramethoxysilane to the reaction solution in the flask at room temperature, the mixture was stirred at 60 ° C. for 3 hours and further at 80 ° C. for 8 hours. During this time, about 200 mL of a mixed solvent of tetrahydrofuran and isopropyl ether was distilled off, and 200 mL of n-heptane was added in two portions. The solid of methoxymagnesium chloride produced by the reaction is separated by filtration, and the filtrate is distilled to obtain di (perhydroisoquinolino) dimethoxysilane (trans-trans, trans-cis, cis-cis isomer). About 6/36/58). Boiling point is 181 ° C / lmmHg
And the purity in gas chromatography was 96.
6%, yield was 90.7%.

Example 2 The reaction was carried out in the same manner as in Example 1 except that the amount of tetrahydrofuran was changed to 200 mL and the amount of n-heptane was changed to 250 mL. The filtrate was distilled to obtain di (perhydroisoquinolino) dimethoxysilane as a target substance. The boiling point is 181 ° C./lmmHg, and the purity in gas chromatography is 96.1%.
And the yield was 90.2%.

Comparative Example 1 A reaction was carried out in the same manner as in Example 1 except that tetrahydrofuran was not used and the amount of n-heptane used was changed to 450 mL. The filtrate was distilled to obtain di (perhydroisoquinolino) dimethoxysilane as a target substance. The boiling point is 181 ° C./lmmHg, the purity by gas chromatography is 95.9%, and the yield is 8
2.5%.

Comparative Example 2 A reaction was carried out in the same manner as in Example 1 except that n-heptane was not used and the amount of tetrahydrofuran was changed to 450 mL. N is added to the reaction mixture containing the solid of methoxymagnesium chloride formed in the reaction.
-After adding heptane (300 mL), the solid was separated by filtration, and the filtrate was distilled to obtain di (perhydroisoquinolino) dimethoxysilane as a target substance. Boiling point is 181 ° C / l
mmHg, the purity by gas chromatography was 95.5%, and the yield was 85.3%.

Example 3 Capacity 10 with Dropping Funnel
A stirrer piece was put into a 00 mL flask, and the inside of the flask was replaced with nitrogen using a vacuum pump. Then, 35 mL of tetrahydrofuran and 185 toluene were placed in the flask.
mL, and 50.8 mL (0.34 mol) of perhydroisoquinoline (trans / cis = 1 / 3.2). 211 mL of 1.69 mol / L butylmagnesium chloride isopropyl ether solution was added to the dropping funnel.
(0.357 mol). An isopropyl ether solution of butylmagnesium chloride was slowly dropped into the flask at room temperature, and then at room temperature for 1 hour and 60 hours.
The mixture was stirred at a temperature of 3 hours to obtain a reaction solution. Next, 25.1 m of tetramethoxysilane was added to the empty dropping funnel.
L (0.17 mol) was charged. After tetramethoxysilane was slowly dropped into the reaction solution (heated to 60 ° C.) in the flask, the mixture was stirred at 85 ° C. for 8 hours. The solid of methoxymagnesium chloride produced by the reaction was separated by filtration through a G4 glass filter, and the filtrate was distilled to obtain di (perhydroisoquinolino) dimethoxysilane (trans-trans, trans-cis, cis) as the target substance. The -cis isomer was obtained about 6/36/58). The above filtration operation was completed in a short time, and almost no residue was observed after the filtrate was distilled. The boiling point of the main component of the fraction is 181 ° C / lmm
Hg, and the purity by gas chromatography is 9
6.6%, yield was 90.7.

Example 4 A reaction was carried out in the same manner as in Example 3 except that the amount of tetrahydrofuran was changed to 20 mL and the amount of toluene was changed to 200 mL. The filtrate was distilled to obtain di (perhydroisoquinolino) dimethoxysilane as a target substance. Also in this case, the filtration operation is completed in a short time,
Also, almost no residue was observed after the filtrate was distilled.
The boiling point of the main component of the fraction was 181 ° C./lmmHg, the purity by gas chromatography was 96.1%, and the yield was 89.2%.

Example 5 The reaction was carried out in the same manner as in Example 3 except that trans / cis = 1/1 was used as perhydroisoquinoline. The filtrate was distilled to obtain the desired product, di (perhydroisoquinolino) dimethoxysilane (trans-trans, trans-cis, cis-cis isomers: about 25/50/25). Also in this case, the filtration operation was completed in a short time, and almost no residue was observed after the filtrate was distilled. The boiling point of the main component of the fraction is 181 ° C / lm
mHg, the purity by gas chromatography was 96.8%, and the yield was 91.3%.

Example 6 Instead of a solution of butylmagnesium chloride in isopropyl ether, a solution of butylmagnesium chloride in n-butylether 162 m
The reaction was carried out in the same manner as in Example 3 except that L (0.357 mol) was used. The filtrate was distilled to obtain the target substance, di (perhydroisoquinolino) dimethoxysilane. Also in this case, the filtration operation was completed in a short time, and almost no residue was observed after the filtrate was distilled. The boiling point of the main component of the fraction was 181 ° C / lmmHg, the purity by gas chromatography was 94.9%, and the yield was 88.8%.

Comparative Example 3 A reaction was carried out in the same manner as in Example 3 except that tetrahydrofuran was not used and the amount of toluene used was changed to 220 mL. The filtrate was distilled to obtain di (perhydroisoquinolyl) dimethoxysilane as a target substance. The boiling point is 181 ° C./lmmHg, the purity by gas chromatography is 95.9%, and the yield is 8
1.6%.

Comparative Example 4 A reaction was carried out in the same manner as in Example 3, except that toluene was not used and the amount of tetrahydrofuran was changed to 220 mL. The reaction mixture containing the solid of methoxymagnesium chloride formed in the reaction was added with n-
After adding 100 mL of heptane, the solid was separated by filtration,
The filtrate was distilled to obtain di (perhydroisoquinolino) dimethoxysilane as a target substance. Boiling point is 181 ° C / lmm
Hg, and the purity by gas chromatography is 9
At 5.4%, the yield was 78.4%.

Claims (9)

[Claims] 1. An organic magnesium compound represented by RMgX (where R is a hydrocarbon group and X is a sigma-binding ligand) is reacted with a secondary polycyclic amine in an ether solvent. And obtaining a polycyclic magnesium amide compound by reacting the polycyclic amide magnesium compound with a tetraalkoxysilane in a mixed solvent of an ether solvent and an inert hydrocarbon solvent. Method for producing dialkoxysilane. 2. The mixing ratio of the ether solvent and the inert hydrocarbon solvent in the mixed solvent is determined by volume ratio of the ether solvent:
The method for producing a di (polycyclic amino) dialkoxysilane according to claim 1, wherein the inert hydrocarbon solvent is in the range of 1:10 to 1: 0.5. 3. The di (polycyclic amino) dialkoxysilane according to claim 1, wherein the ether solvent used in the reaction between the organomagnesium compound and the secondary polycyclic amine is a mixture of a dialkyl ether and a cyclic ether. Production method. 4. An ether solvent used for the reaction between the organomagnesium compound and the secondary polycyclic amine, and the ether solvent in the mixed solvent is diethyl ether, diisopropyl ether, dibutyl ether, diisoamyl ether,
The method for producing a di (polycyclic amino) dialkoxysilane according to any one of claims 1 to 2, wherein the solvent is at least one ether solvent selected from the group consisting of tetrahydrofuran, tetrahydropyran, and dioxane. 5. The inert hydrocarbon solvent is one or more inert hydrocarbon solvents selected from the group consisting of pentane, hexane, heptane, octane, cyclohexane, mineral oil, benzene, toluene, and xylene. Item 3. The method for producing a di (polycyclic amino) dialkoxysilane according to Item 1 or 2. 6. The di (polycyclic amino) dialkoxysilane according to claim 1, wherein R in RMgX is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, and phenyl groups. Manufacturing method. 7. The production of di (polycyclic amino) dialkoxysilane according to claim 1, wherein X in RMgX is an atom or group selected from the group consisting of halogen, hydrocarbon oxy, hydrocarbon amide, and carboxy. Method. 8. The method of claim 8, wherein the secondary polycyclic amine is a perhydro secondary
The method for producing a di (polycyclic amino) dialkoxysilane according to claim 1, which is a secondary polycyclic amine. 9. The perhydro-secondary polycyclic amine has a hydrogen atom bonded to a carbon atom of perhydroquinoline, perhydroisoquinoline, or a compound thereof substituted with an alkyl group, a phenyl group, or a hydroalkyl group. 9. The di (polycyclic amino) according to claim 8, which is a derivative.
Method for producing dialkoxysilane.