DE69723208T2 - Process for the polymerization of olefins, poly-alpha-olefins produced by this process and aminosilane compounds which can be used as a catalyst component for this process - Google Patents

Description

background the invention

Field of the Invention

The present invention relates to a process for producing a homopolymer from an α-olefin or a copolymer of an α-olefin with other α-olefins, that's a high activity and a high stereochemical regularity in connection with a has a broad molecular weight distribution, using a novel aminosilane compound with a specific molecular structure as one of the components of a novel catalyst; The invention also relates to the α-olefin polymers produced by the process (including Homopolymers and copolymers) and the novel method used for the process Aminosilane compound as a catalyst component.

State of the art

Over the past few years in JP-A-57-63310, JP-A-58-83016, JP-A-59-58010, JP-A-60-44507 and other references highly active catalyst systems support-supported type for polymerization of α-olefins suggested that include solid components that are imperatively magnesium, Titanium, a halogen and an electron donor, an organometallic compound a metal of groups I-III of the periodic table and an electron donor contain. Furthermore, JP-A-62-11705, JP-A-63-259807, JP-A-2-84404, JP-A-4-202505 and JP-A-4-370103 other polymerization catalysts which are characterized in that they have a special Contain organosilicon compound as electron donor.

Using a catalyst system Carrier-based type manufactured propylene polymers that contain the organosilicon compound contain, but generally have a narrow molecular weight distribution and low viscoelasticity when you melt the polymers. For these reasons point such polymers depending their use often has disadvantages in terms of molding properties as well as the external appearance the molded article. To counteract these disadvantages, have been disclosed in JP-A-63-245408, JP-A-2-232207 and JP-A-4-370103 Method for broadening the polymer molecular weight distribution proposed by polymerizing propylene in a variety of polymerization containers or by using a multi-stage polymerization.

However, such procedures require complicated process steps so that the production speed inevitably diminished, these procedures are therefore due to the existing problems, including production costs, not preferred on an industrial scale. In the event of the manufacture of a low molecular weight propylene polymer and a broad molecular weight distribution using one Variety of polymerization tanks should also be a low molecular weight polymer by using an excess amount a chain transfer agent, for example hydrogen gas, produced in one of the polymerization tanks become, resulting in a higher polymerization pressure leads. Since the polymerization temperature in the case of a polymerization tank, the inevitably has limited pressure resistance should be able to such processes adversely affect the manufacturing speed cause.

Furthermore, JP-A-8-120021 discloses a process for polymerizing an α-olefin, in which a cyclic alkylaminosilane compound of the general formula R ¹ Si (OR ² ) ₂ R ³ (in which R ^{1 is} an alkyl group and R ^{3 represents} a cyclic amino group) can be used. However, only compounds in which R ^{1 represents} a methyl group are disclosed as illustrative compounds of the cyclic aminosilane compound. In addition, there is no mention of the molecular weight distribution of the propylene polymers thus produced using these compounds as catalyst components.

Furthermore, JP-A-8-143621 a method of polymerizing an α-olefin using a bicyclic aminosilane compound with two cyclic amino groups on the silicon atom, which is specifically disclosed there. specially revealed to this cyclic compound is a bis-aminosilane compound with two piperidino groups each having a single ring as cyclic amino groups. According to what has been said above no concrete description regarding the molecular weight distribution of using these compounds as catalyst components produced propylene polymers.

Furthermore, EP-A-410443 a bis (4-methylpiperidyl) dimethoxysilane disclosed for a process useful for polymerizing an α-olefin is. However, there is also no concrete description in terms of the molecular weight distribution of a poly-α-olefin obtainable therefrom.

Furthermore, JP-A-7-90012 and JP-A-7-97411 describe processes for polymerizing a α-olefins, in which a silane compound is used which has a substituent from a nitrogen atom-containing heterocyclic group in which each of the carbon atoms of the heterocyclic structure is bonded directly to the silicon atom. However, there is no concrete description regarding the molecular weight distribution of the polymers made using these compounds.

On the other hand, it is suggested that a propylene polymer with a broad molecular weight distribution and high crystallizability by melt mixing one Low molecular weight and high propylene polymer Crystallizability and a propylene polymer with a large molecular weight and high crystallizability in a predetermined ratio can be; each of the propylene polymers used as starting materials made by conventional methods prior to use in melt blending has been. In the case of producing a propylene polymer with a relatively low molecular weight and a broad molecular weight distribution it is practically very difficult to melt melt the process a low molecular weight propylene polymer with a Can perform high molecular weight propylene polymer, besides that thereby further gel formation in polymers thus obtained Problem caused.

Summary the invention

It is a task of the present Invention, having an α-olefin polymer high stereochemical regularity and a broad molecular weight distribution, at which a high melting point is maintained and a new one Aminosilane compound used as a catalyst component for manufacturing of the α-olefin polymer is useful to provide.

• (A) eine feste Katalysatorkomponente, die zwingend Magnesium, Titan, ein Halogen und einen Elektronendonor enthält,
• (B) eine Organoaluminiumverbindung und
• (C) eine Aminosilanverbindung gemäß der allgemeinen Formel (1), die weiter unten gezeigt ist.

First of all, the present invention relates to a process for polymerizing an α-olefin in the presence of a catalyst which consists of the following catalyst components (A), (B) and (C):

• (A) a solid catalyst component which contains magnesium, titanium, a halogen and an electron donor,
• (B) an organoaluminum compound and
• (C) an aminosilane compound according to general formula (1) shown below.

By the method according to the invention becomes an α-olefin polymer, especially a propylene polymer with a relatively low molecular weight, high stereochemical regularity and high melting point combined with a broad molecular weight distribution provided.

Furthermore, the present concerns Invention a novel, useful as a catalyst component with high polymerization activity Aminosilane compound used to make a homopolymer an α-olefin or a copolymer of an α-olefin with other α-olefins is used, each of these polymers having a high stereochemical regularity and has a broad molecular weight distribution.

Brief explanation of the drawings

1 shows chromatograms obtained from gas permeation chromatography (hereinafter referred to as GPC) for the molecular weight distributions of the propylene polymers obtained from Preparative Example 1 and Comparative Example 1.

2 shows a GPC chromatogram for the molecular weight distributions of the propylene polymers obtained from Preparative Example 26 and Comparative Example 11.

Full Description of the preferred embodiments

• (A) eine feste Komponente, die zwingend Magnesium, Titan, ein Halogen und einen Elektronendonor enthält,
• (B) eine Organoaluminiumverbindung und
• (C) eine Aminosilanverbindung gemäß der folgenden allgemeinen Formel (1):
  
  (worin R¹ für einen Kohlenwasserstoffrest mit 1 bis 8 Kohlenstoffatomen steht; und
  
  für eine polycyclische Aminogruppe mit 7 bis 40 Kohlenstoffatomen steht, die das an das Stickstoffatom gebundene polycyclische Gerüst bilden).

First of all, the present invention relates to a process for polymerizing an α-olefin in the presence of a catalyst which contains the following components (A), (B) and (C):

• (A) a solid component which contains magnesium, titanium, a halogen and an electron donor,
• (B) an organoaluminum compound and
• (C) an aminosilane compound according to the following general formula (1):
  
  (wherein R ^{1 represents} a hydrocarbon radical having 1 to 8 carbon atoms; and
  
  represents a polycyclic amino group with 7 to 40 carbon atoms, which form the polycyclic skeleton bonded to the nitrogen atom).

In the present invention a solid catalyst component that necessarily contains magnesium, titanium, contains a halogen and an electron donor, used as component (A). Because no particular limitation regarding the manufacturing process of the solid catalyst component , it can be used using, for example, in JP-A-54-94590, JP-A-56-55405, JP-A-56-45909, JP-A-56-163102, JP-A-57-63310, JP-A-57-115408, JP-A-58-83006, JP-A-58-83016, JP-A-58-138707, JP-A-59-149905, JP-A-60-23404, JP-A-60-32805, JP-A-61-18300, JP-A-61-55104, JP-A-2-77413, JP-A-2-117905 proposed methods as well be made by other processes.

Regarding a representative Processes for producing component (A) can be shown by way of example become (i) a process involving the simultaneous grinding of a magnesium compound (e.g. magnesium chloride), an electron donor and a titanium halide compound (e.g. titanium tetrachloride) or (ii) a process that the Solve one Magnesium compound and an electron donor in a solvent and the addition of a titanium halide compound to the resulting one solution for precipitation of a solid catalyst.

To achieve the object of the invention are those in JP-A-60-152511, JP-A-61-31402 and JP-A-62-81405 disclosed solid catalysts particularly preferred as component (A). According to the one in this The method disclosed in the prior art is an aluminum halide compound implemented with a silicon compound, then the reaction product further implemented with a Grignard connection so that a firm Substance precipitated becomes. The for the above reaction useful aluminum compound is preferred an anhydrous aluminum halide. The use of a completely anhydrous However, aluminum halide is extremely difficult due to its hygroscopic property, it is possible, to use an aluminum halide containing a small amount of water. Specific examples of the aluminum halide include aluminum trichloride, Aluminum tribromide, aluminum triiodide. Particularly preferred is aluminum trichloride.

Specific examples of those for the above Implementation of usable silicon compounds include tetramethoxysilane, Tetraaethoxysilane, tetrabutoxysilane, methyltriethoxysilane, ethyltributoxysilane, Phenyltrimethoxysilane, phenyltributoxysilane, dimethyldiethoxysilane, Diphenyldimethoxysilane, methylphenyldimethoxysilane, diphenyldiethoxysilane, Trimethylmonoethoxysilane and trimethylmonobutoxysilane.

In particular, methyldimethoxysilane, Tetraethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane and Dimethyldiethoxysilane preferred.

When implementing the aluminum halide with the silicon compound The relationship the amount of these compounds used is generally 0.4 to 1.5; preferably 0.7 to 1.3; expressed as atomic ratio (Al / Si). For the Reaction is preferably an inert solvent, such as hexane, Toluene or the like. The reaction temperature is generally 10 to 100 ° C, preferably 20 to 80 ° C, and the response time is generally 0.2 to 5 hours, preferably 0.5 to 3 hours.

Specific examples of those for the above Useful magnesium compounds include ethyl magnesium chloride, Propyl magnesium chloride, butyl magnesium chloride, hexyl magnesium chloride, Octylmagnesium chloride, ethylmagnesium bromide, propylmagnesium bromide, Butyl magnesium bromide and ethyl magnesium iodide. As a solvent for the Magnesium compound can for example aliphatic ethers, such as diethyl ether, dibutyl ether, Diisopropyl ether, diisoamyl ether and the like; cyclic aliphatic ethers, such as tetrahydrofuran and the like can be used.

The amount of magnesium compound used is generally in the range from 0.5 to 3, preferably 1.5 to 2.3; expressed as an atomic ratio (Mg / Al) of a magnesium compound to an aluminum halide, the for the preparation of the reaction product of an aluminum halide can be used with a silicon compound. The reaction temperature is generally -50 ° C to 100 ° C, preferably -20 ° C to 50 ° C, and the Response time is generally in the range of 0.2 to 5 hours, preferably 0.5 to 3 hours.

A white solid substance obtained by reacting an aluminum halide with a silicon compound and then reacting with a Grignard compound is contacted with an electron donor and a titanium halide compound. The contacting can be carried out by conventional methods known in the art, for example (i) a method in which the solid substance is treated with a titanium halide compound, then treated with an electron donor and again with the titanium halide compound; or (ii) a method in which the solid substance is coated with a Titanha treated in the presence of an electron donor and treated again with the titanium halide compound.

Contacting is for example executed by placing the above solid substance in an inert solvent dispersed and an electron donor and / or a titanium halide compound there so that the electron donor and / or the titanium halide compound solved in it or by placing the solid substance in an electron donor or / and a liquid Titanium halide compound dispersed without using an inert solvent is used. In this case, contacting the fixed Substance with an electron donor and / or a titanium halide compound with stirring accomplished are, generally at a temperature of 50 to 150 ° C, for 0.2 to 5 hours; however, there is no specific contact time Restriction. This contacting can be repeated several times.

Specific examples of those for contacting usable titanium halide compounds include carbon tetrachloride, titanium tetrabromide, Trichloromonobutoxytitanium, tribromomonoethoxytitanium, trichloromonoisopropoxytitanium, Dichlorodiethoxytitanium, dichlorodibutoxytitanium, monochlorotriethoxytitanium and monochloro tributoxytitanium. In particular, carbon tetrachloride and trichloromonobutoxytitan is preferred.

One usable for contacting Electron donor is preferred, a compound acting as a Lewis base an aromatic diester, especially an orthophthalic diester prefers. Specific examples of the orthophthalic diester include diethyl orthophthalate, Di-n-butylorthophthalat, Diisobutyl orthophthalate, dipentyl orthophthalate, di-n-hexyl orthophthalate, Di-2-ethylhexyl orthophthalate, di-n-heptyl orthophthalate, di-n-octyl orthophthalate and the like. Furthermore, a connection with two or more ether groups such as those described in JP-A-3-706, JP-A-3-62805, JP-A-4-270705 and JP-A-6-25332 are preferably used as the electron donor become.

After being brought into contact the resulting solid substance generally from the reaction mixture separated and thorough with an inert solvent washed, then the solid substance thus obtained can be regarded as the solid Catalyst component (A) used to polymerize an α-olefin become.

For the present invention useful as a catalyst component (B) Organoaluminum compounds can an alkyl aluminum, an alkyl aluminum halide or the like his. Among these compounds, an alkyl aluminum is preferred trialkyl aluminum is particularly preferred. Specific examples of the Close trialkyl aluminum Trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum, triisobutyl aluminum, Trihexyl aluminum and trioctyl aluminum. These organoaluminum compounds can used individually or in mixtures thereof. Also through implementation polyaluminoxanes obtained from an alkyl aluminum with water can also be used become.

The amount of as a catalyst component (B) for polymerizing an α-olefin Organoaluminum compound used is 0.1 to 500, preferably 0.5 to 150, expressed as an atomic ratio (Al / Ti) of aluminum atoms of the organoaluminum compound to titanium atoms in the solid catalyst component (A).

(worin R¹ für einen Kohlenwasserstoffrest mit 1 bis 8 Kohlenstoffatomen steht; und

für eine polycyclische Aminogruppe mit 7 bis 40 Kohlenstoffatomen steht, die das an das Stickstoffatom gebundene polycyclische Gerüst bilden).The catalyst component (C) used in the present invention is an aminosilane compound represented by the following general formula (1):

(wherein R ^{1 represents} a hydrocarbon radical having 1 to 8 carbon atoms; and

represents a polycyclic amino group with 7 to 40 carbon atoms, which form the polycyclic skeleton bonded to the nitrogen atom).

In the above general formulas, R ^{1 represents} a hydrocarbon residue having 1 to 8 carbon atoms, and an unsaturated or saturated aliphatic hydrocarbon having 1 to 8 carbon atoms can be exemplified. Specific examples of the hydrocarbon group include methyl group, ethyl group, n-propyl, iso-propyl group, n-butyl group, iso-butyl group, butyl group, sec-butyl group, n -Pentylgruppe, iso -Pentylgruppe, iso -Pentylgruppe, cyclopentyl group, n tert - Hexyl group, cyclohexyl group and the like. Among them, the methyl group is particularly preferred.

steht für eine polycyclische Aminogruppe mit 7 bis 40, bevorzugt 7 bis 20, Kohlenstoffatomen, die das an das Stickstoffatom gebundene polycyclische Gerüst bilden. Die polycyclische Aminogruppe kann eine gesättigte polycyclische Aminogruppe oder eine teilweise oder vollständig ungesättigte polycyclische Aminogruppe sein. Das Stickstoffatom der polycyclischen Aminogruppe ist ebenfalls direkt an das Siliziumatom der Aminosilanverbindung gebunden. Somit kann die der Formel

entsprechende polycyclische Aminogruppe als ein Substituent definiert werden, der durch chemische Bindung des Ring-N-Atoms an das Si-Atom unter Entfernung des Wasserstoffatoms von dem sekundären Amin

gebildet wird. In der allgemeinen Formel (1) können die zwei

gleich oder verschieden sein.

stands for a polycyclic amino group with 7 to 40, preferably 7 to 20, carbon atoms which form the polycyclic skeleton bonded to the nitrogen atom. The polycyclic amino group can be a saturated polycyclic amino group or a partially or completely unsaturated polycyclic amino group. The nitrogen atom of the polycyclic amino group is also bonded directly to the silicon atom of the aminosilane compound. So that of the formula

Corresponding polycyclic amino group can be defined as a substituent which is formed by chemical bonding of the ring N atom to the Si atom with removal of the hydrogen atom from the secondary amine

is formed. In the general formula (1), the two

be the same or different.

schließen Aminverbindungen, wie durch die folgenden chemischen Strukturformeln erfasst, ein: Perhydroindol, Perhydroisoindol, Perhydrochinolin, Perhydrocarbazol, Perhydroacrydin, Perhydrophenanthridin, Perhydrobenzo(g)chinolin, Perhydrobenzo(h)chinolin, Perhydrobenzo(f)chinolin, Perhydrobenzo(g)isochinolin, Perhydrobenzo(h)isochinolin, Perhydrobenzo(f)isochinolin, Perhydroacechinolin, Perhydroaceisochinolin, Perhydroiminostilben und dergleichen. Bezüglich der oben genannten Aminverbindungen können weitere Aminverbindungen beispielhaft dargestellt werden, bei denen einige der Was serstoffatome, die nicht an das Stickstoffatom gebunden sind, durch Alkylgruppen, Phenylgruppen oder Cycloalkylgruppen substituiert sind:Specific examples of polycyclic secondary amine compounds

include amine compounds as captured by the following chemical structural formulas: perhydroindole, perhydroisoindole, perhydroquinoline, perhydrocarbazole, perhydroacrydin, perhydrophenanthridine, perhydrobenzo (g) quinoline, perhydrobenzo (h) quinoline, perhydrobenzo (f) quinoline, perhydrobenzo (g) (h) isoquinoline, perhydrobenzo (f) isoquinoline, perhydroacequinoline, perhydroaceisoquinoline, perhydroiminostilbene and the like. With regard to the amine compounds mentioned above, further amine compounds can be exemplified in which some of the hydrogen atoms which are not bonded to the nitrogen atom are substituted by alkyl groups, phenyl groups or cycloalkyl groups:

wie etwa 1,2,3,4-Tetrahydrochinolin, 1,2,3,4-Tetrahydroisochinolin, wie in den folgenden chemischen Strukturformeln erwähnt, bei denen ein Teil des cyclischen Gerüsts ungesättigt ist, und weitere Aminverbindungen, bei denen ein Teil der Wasserstoffatome, die nicht an das Stickstoffatom des cyclischen Gerüsts gebunden sind, durch eine Alkylgruppe, Phenylgruppe, oder Cycloalkylgruppe substituiert sind, beispielhaft dargestellt werden.Furthermore, polycyclic secondary amine compounds of the formula

such as 1,2,3,4-tetrahydroquinoline, 1,2,3,4-tetrahydroisoquinoline, as mentioned in the following chemical structural formulas in which part of the cyclic skeleton is unsaturated, and other amine compounds in which part of the hydrogen atoms which are not attached to the nitrogen atom of the cyclic skeleton, are substituted by an alkyl group, phenyl group, or cycloalkyl group can be exemplified.

schließen Perhydrochino lin, Perhydroisochinolin, 1,2,3,4-Tetrahydrochinolin, 1,2,3,4-Tetrahydroisochinolin und deren Derivate ein.Specific preferred examples of the polycyclic secondary amine compounds of the general formula

include perhydroquinoline, perhydroisoquinoline, 1,2,3,4-tetrahydroquinoline, 1,2,3,4-tetrahydroisoquinoline and their derivatives.

(worin R⁴ für einen substituierten Rest am cyclischen Gerüst der allgemeinen Formel

steht und R¹ ein Wasserstoffatom oder ein gesättigter aliphatischer Kohlenwasserstoffrest mit 1 bis 24 Kohlenstoffatomen oder ungesättigter aliphatischer Kohlenwasserstoffrest mit 2 bis 24 Kohlenstoffatomen ist; bevorzugte Beispiele von R⁴ schließen das Wasserstoffatom, die Methylgruppe, Ethylgruppe, n-Propylgruppe, iso-Propylgruppe, n-Butylgruppe, iso-Butylgruppe, tert-Butylgruppe, sec-Butylgruppe und dergleichen ein; des Weiteren kann die Anzahl der Kohlenwasserstoffreste, die in der gesättigten cyclischen Struktur

substituiert sind, 1 oder mehr betragen).With respect to the aminosilane compounds of the general formula (1), examples can be given: a perhydroquinolino compound of the general formula (3), a perhydroisoquinolino compound of the general formula (4), a (perhydroquinolino) / (perhydroisoquinolino) compound of the general formula (5) , a 1,2,3,4-tetrahydroquinolino compound of the general formula (6), a 1,2,3,4-tetrahydroisoquinolino compound of the general formula (7), a (1,2,3,4-tetrahydroquinolino) (1, 2,3,4-tetrahydroisoquinolino) compound represented by the general formula (8) and the like:

(wherein R ^{4 represents} a substituted radical on the cyclic skeleton of the general formula

and R ^{1 is} a hydrogen atom or a saturated aliphatic hydrocarbon residue having 1 to 24 carbon atoms or unsaturated aliphatic hydrocarbon residue having 2 to 24 carbon atoms; preferred examples of R ⁴ include the hydrogen atom, methyl group, ethyl group, n -propyl group, iso -propyl group, n -butyl group, iso- butyl group, tert -butyl group, sec -butyl group and the like; Furthermore, the number of hydrocarbon residues in the saturated cyclic structure

are substituted, amount to 1 or more).

Regarding a specific example the compound of the general formula (3) is bis (perhydroquinolino) dimethoxysilane to mention.

Specific examples of the bis (methyl substituted perhydroquinolino) dimethoxysilane compounds include
Bis (2-methylperhydrochinolino) dimethoxysilane,
Bis (3-methylperhydrochinolino) dimethoxysilane,
Bis (4-methylperhydrochinolino) dimethoxysilane,
Bis (5-methylperhydrochinolino) dimethoxysilane,
Bis (6-methylperhydrochinolino) dimethoxysilane,
Bis (7-methylperhydrochinolino) dimethoxysilane,
Bis (8-methylperhydrochinolino) dimethoxysilane,
Bis (9-methylperhydrochinolino) dimethoxysilane,
Bis (10-methylperhydroquinolino) dimethoxysilane and the like.

Specific examples of bis (dimethyl substituted perhydroquinolino) dimethoxysilane compounds include
Bis (2,3-dimethylperhydrochinolino) dimethoxysilane,
Bis (2,4-dimethylperhydrochinolino) dimethoxysilane,
Bis (2,5-dimethylperhydrochinolino) dimethoxysilane,
Bis (2,6-dimethylperhydrochinolino) dimethoxysilane,
Bis (2,7-dimethylperhydrochinolino) dimethoxysilane,
Bis (2,8-dimethylperhydrochinolino) dimethoxysilane,
Bis (2,9-dimethylperhydrochinolino) dimethoxysilane,
Bis (2,10-dimethylperhydrochinolino) dimethoxysilane,
Bis (3,4-dimethylperhydrochinolino) dimethoxysilane,
Bis (3,5-dimethylperhydrochinolino) dimethoxysilane,
Bis (3,6-dimethylperhydrochinolino) dimethoxysilane,
Bis (3,7-dimethylperhydrochinolino) dimethoxysilane,
Bis (3,8-dimethylperhydrochinolino) dimethoxysilane,
Bis (3,9-dimethylperhydrochinolino) dimethoxysilane,
Bis (3,10-dimethylperhydrochinolino) dimethoxysilane,
Bis (4,5-dimethylperhydrochinolino) dimethoxysilane,
Bis (4,6-dimethylperhydrochinolino) dimethoxysilane,
Bis (4,7-dimethylperhydrochinolino) dimethoxysilane,
Bis (4,8-dimethylperhydrochinolino) dimethoxysilane,
Bis (4,9-dimethylperhydrochinolino) dimethoxysilane,
Bis (4,10-dimethylperhydrochinolino) dimethoxysilane,
Bis (5,6-dimethylperhydrochinolino) dimethoxysilane,
Bis (5,7-dimethylperhydrochinolino) dimethoxysilane,
Bis (5,8-dimethylperhydrochinolino) dimethoxysilane,
Bis (5,9-dimethylperhydrochinolino) dimethoxysilane,
Bis (5,10-dimethylperhydrochinolino) dimethoxysilane,
Bis (6,7-dimethylperhydrochinolino) dimethoxysilane,
Bis (6,8-dimethylperhydrochinolino) dimethoxysilane,
Bis (6,9-dimethylperhydrochinolino) dimethoxysilane,
Bis (6,10-dimethylperhydrochinolino) dimethoxysilane,
Bis (7,8-dimethylperhydrochinolino) dimethoxysilane,
Bis (7,9-dimethylperhydrochinolino) dimethoxysilane,
Bis (7,10-dimethylperhydrochinolino) dimethoxysilane,
Bis (8,9-dimethylperhydrochinolino) dimethoxysilane,
Bis (8,10-dimethylperhydrochinolino) dimethoxysilane,
Bis (9,10-dimethylperhydroquinolino) dimethoxysilane and the like.

Specific examples of bis (trimethyl-substituted-perhydroquinolino) dimethoxysilane compounds include
Bis (2,3,4-timethylperhydrochinolino) dimethoxysilane,
Bis (3,4,5-trimethylperhydrochinolino) dimethoxysilane,
Bis (4,5,6-trimethylperhydrochinolino) dimethoxysilane,
Bis (5,6,7-trimethylperhydrochinolino) dimethoxysilane,
Bis (6,7,8-trimethylperhydrochinolino) dimethoxysilane,
Bis (7,8,9-trimethylperhydrochinolino) dimethoxysilane,
Bis (8,9,10-trimethylperhydroquinolino) dimethoxysilane and the like.

Compounds of (perhydroquinolino) (monomethylperhydroquinolino) dimethoxysilane can also be listed by way of example:
(Perhydroquinolino) (2-methylperhydrochinolino) dimethoxysilane,
(Perhydroquinolino) (3-methylperhydrochinolino) dimethoxysilane,
(Perhydroquinolino) (4-methylperhydrochinolino) dimethoxysilane,
(Perhydroquinolino) (5-methylperhydrochinolino) dimethoxysilane,
(Perhydroquinolino) (6-methylperhydrochinolino) dimethoxysilane,
(Perhydroquinolino) (7-methylperhydrochinolino) dimethoxysilane,
(Perhydroquinolino) (8-methylperhydrochinolino) dimethoxysilane,
(Perhydroquinolino) (9-methylperhydrochinolino) dimethoxysilane,
(Perhydroquinolino) (10-methylperhydroquinolino) dimethoxysilane and the like.

Among these compounds is bis (perhydroquinolino) dimethoxysilane prefers.

As examples of compounds of the general Formula (4) can Called bis (perhydroisoquinolino) dimethoxysilane and the like become.

Examples of the compounds of bis (methyl-substituted-perhydroisoquinolino) dimethoxysilanes include
Bis (1-methylperhydroisochinolino) dimethoxysilane,
Bis (3-methylperhydroisochinolino) dimethoxysilane,
Bis (4-methylperhydroisochinolino) dimethoxysilane,
Bis (5-methylperhydroisochinolino) dimethoxysilane,
Bis (6-methylperhydroisochinolino) dimethoxysilane,
Bis (7-methylperhydroisochinolino) dimethoxysilane,
Bis (8-methylperhydroisochinolino) dimethoxysilane,
Bis (9-methylperhydroisochinolino) dimethoxysilane,
Bis (10-methylperhydroisoquinolino) dimethoxysilane and the like.

Examples of compounds of bis (dimethyl-substituted-perhydroisoquinolino) dimethoxysilane include
Bis (1,3-dimethylperhydroisochinolino) dimethoxysilane,
Bis (1,4-dimethylperhydroisochinolino) dimethoxysilane,
Bis (1,5-dimethylperhydroisochinolino) dimethoxysilane,
Bis (1,6-dimethylperhydroisochinolino) dimethoxysilane,
Bis (1,7-dimethylperhydroisochinolino) dimethoxysilane,
Bis (1,8-dimethylperhydroisochinolino) dimethoxysilane,
Bis (1,9-dimethylperhydroisochinolino) dimethoxysilane,
Bis (1,10-dimethylperhydroisochinolino) dimethoxysilane,
Bis (3,4-dimethylperhydroisochinolino) dimethoxysilane,
Bis (3,5-dimethylperhydroisochinolino) dimethoxysilane,
Bis (3,6-dimethylperhydroisochinolino) dimethoxysilane,
Bis (3,7-dimethylperhydroisochinolino) dimethoxysilane,
Bis (3,8-dimethylperhydroisochinolino) dimethoxysilane,
Bis (3,9-dimethylperhydroisochinolino) dimethoxysilane,
Bis (3,10-dimethylperhydroisochinolino) dimethoxysilane,
Bis (4,5-dimethylperhydroisochinolino) dimethoxysilane,
Bis (4,6-dimethylperhydroisochinolino) dimethoxysilane,
Bis (4,7-dimethylperhydroisochinolino) dimethoxysilane,
Bis (4,8-dimethylperhydroisochinolino) dimethoxysilane,
Bis (4,9-dimethylperhydroisochinolino) dimethoxysilane,
Bis (4,10-dimethylperhydroisochinolino) dimethoxysilane,
Bis (5,6-dimethylperhydroisochinolino) dimethoxysilane,
Bis (5,7-dimethylperhydroisochinolino) dimethoxysilane,
Bis (5,8-dimethylperhydroisochinolino) dimethoxysilane,
Bis (5,9-dimethylperhydroisochinolino) dimethoxysilane,
Bis (5,10-dimethylperhydroisochinolino) dimethoxysilane,
Bis (6,7-dimethylperhydroisochinolino) dimethoxysilane,
Bis (6,8-dimethylperhydroisochinolino) dimethoxysilane,
Bis (6,9-dimethylperhydroisochinolino) dimethoxysilane,
Bis (6,10-dimethylperhydroisochinolino) dimethoxysilane,
Bis (7,8-dimethylperhydroisochinolino) dimethoxysilane,
Bis (7,9-dimethylperhydroisochinolino) dimethoxysilane,
Bis (7,10-dimethylperhydroisochinolino) dimethoxysilane,
Bis (8,9-dimethylperhydroisochinolino) dimethoxysilane,
Bis (8,10-dimethylperhydroisochinolino) dimethoxysilane,
Bis (9,10-dimethylperhydroisoquinolino) dimethoxysilane and the like.

Examples of compounds of bis (trimethyl-substituted-perhydroisoquinolino) dimethoxysilane include
Bis (1,3,4-trimethylperhydroisochinolino) dimethoxysilane,
Bis (3,4,5-trimethylperhydroisochinolino) dimethoxysilane,
Bis (4,5,6-trimethylperhydroisochinolino) dimethoxysilane,
Bis (5,6,7-trimethylperhydroisochinolino) dimethoxysilane,
Bis (6,7,8-trimethylperhydroisochinolino) dimethoxysilane,
Bis (7,8,9-trimethylperhydroisochinolino) dimethoxysilane,
Bis (8,9,10-trimethylperhydroisoquinolino) dimethoxysilane and the like.

Furthermore, examples of compounds of (perhydroisoquinolino) (monomethyl-substituted-perhydroisoquinolino) include dimethoxysilane
(Perhydroisoquinolino) (2-methyl-perhydroisoquinolino) dimethoxysilane,
(Perhydroisoquinolino) (3-methyl-perhydroisoquinolino) dimethoxysilane,
(Perhydroisoquinolino) (4-methyl-perhydroisoquinolino) dimethoxysilane,
(Perhydroisoquinolino) (5-methyl-perhydroisoquinolino) dimethoxysilane,
(Perhydroisoquinolino) (6-methyl-perhydroisoquinolino) dimethoxysilane,
(Perhydroisoquinolino) (7-methyl-perhydroisoquinolino) dimethoxysilane,
(Perhydroisoquinolino) (8-methyl-perhydroisoquinolino) dimethoxysilane,
(Perhydroisoquinolino) (9-methyl-perhydroisoquinolino) dimethoxysilane,
(Perhydroisoquinolino) (10-methyl-perhydroisoquinolino) dimethoxysilane and the like.

Among these compounds is bis (perhydroisoquinolino) dimethoxysilane prefers.

Examples of compounds of general Close formula (5) (Perhydroquinolino) (perhydroisoquinolino) dimethoxysilane, (perhydroquinolino) (1-methylperhydroisoquinolino) dimethoxysilane, (Perhydroquinolino) (3-methylperhydroisochinolino) dimethoxysilane, (Perhydroquinolino) (4-methylperhydroisochinolino) dimethoxysilane, (Perhydroquinolino) (5-methylperhydroisochinolino) dimethoxysilane, (Perhydroquinolino) (6-methylperhydroisochinolino) dimethoxysilane, (Perhydroquinolino) (7-methylperhydroisoquinolino) dimethoxysilane, (perhydroquinolino) (8-methylperhydroisoquinolino) dimethoxysilane, (Perhydroquinolino) (9-methylperhydroisochinolino) dimethoxysilane, (Perhydroquinolino) (10-methylperhydroisochinolino) dimethoxysilane, (2-Methylperhydrochinolino) (perhydroisoquinolino) dimethoxysilane, (3-Methylperhydrochinolino) (perhydroisoquinolino) dimethoxysilane, (4-Methylperhydrochinolino) (perhydroisoquinolino) dimethoxysilane, (5-Methylperhydrochinolino) (perhydroisoquinolino) dimethoxysilane, (6-methylperhydroquinolino) (perhydroisoquinolino) dimethoxysilane, (7-methylperhydroquinolino) (perhydroisoquinolino) dimethoxysilane, (8-Methylperhydrochinolino) (perhydroisoquinolino) dimethoxysilane, (9-Methylperhydrochinolino) (perhydroisoquinolino) dimethoxysilane, (10-Methylperhydrochinolino) (perhydroisoquinolino) dimethoxysilane, (2-Methylperhydrochinolino) (1-Methylperhydroisochinolino) dimethoxysilane, (3-Methylperhydrochinolino) (3-Methylperhydroisochinolino) dimethoxysilane, (4-Methylperhydrochinolino) (4-Methylperhydroisochinolino) dimethoxysilane, (5-Methylperhydrochinolino) (5-Methylperhydroisochinolino) dimethoxysilane, (6-methylperhydroquinolino) (6-methylperhydroisoquinolino) dimethoxysilane, (7-methylperhydroquinolino) (7-methylperhydroisoquinolino) dimethoxysilane, (8-Methylperhydrochinolino) (8-Methylperhydroisochinolino) dimethoxysilane, (9-Methylperhydrochinolino) (9-Methylperhydroisochinolino) dimethoxysilane, (10-Methylperhydrochinolino) (10-Methylperhydroisochinolino) dimethoxysilane and the like.

Among these compounds, (perhydroquinolino) (perhydroisoquinolino) is dimethoxysilane prefers.

Examples of compounds of the general formula (6) include bis (1,2,3,4-tetrahydroquinolino) di methoxysilane and the like.

Examples of compounds of bis (methyl-substituted-1,2,3,4-tetrahydroquinolino) dimethoxysilane include
Bis (2-methyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane,
Bis (3-methyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane,
Bis (4-methyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane,
Bis (6-methyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane,
Bis (7-methyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane,
Bis (8-methyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane,
Bis (9-methyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane and the like.

Examples of compounds of bis (dimethyl-substituted-1,2,3,4-tetrahydroquinolino) dimethoxysilane include
Bis (2,3-dimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane,
Bis (2,4-dimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane,
Bis (2,6-dimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane,
Bis (2,7-dimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane,
Bis (2,8-dimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane,
Bis (2,9-dimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane,
Bis (3,4-dimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane,
Bis (3,6-dimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane,
Bis (3,7-dimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane,
Bis (3,8-dimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane,
Bis (3,9-dimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane,
Bis (4,6-dimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane,
Bis (4,7-dimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane,
Bis (4,8-dimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane,
Bis (4,9-dimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane,
Bis (6,7-dimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane,
Bis (6,8-dimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane,
Bis (6,9-dimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane,
Bis (7,8-dimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane,
Bis (7,9-dimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane,
Bis (8,9-dimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane and the like.

Examples of compounds of bis (trimethyl-substituted-1,2,3,4-tetrahydroquinolino) dimethoxysilane conclude Bis (2,3,4-trimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, Bis (2,3,6-trimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, Bis (2,3,7-trimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, Bis (2,3,8-trimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, Bis (2,3,9-trimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, Bis (3,4,6-trimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, Bis (3,4,7-trimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, Bis (3,4,8-trimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, Bis (3,4,9-trimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, Bis (4,6,7-trimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, Bis (4,6,8-trimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, Bis (4,6,9-trimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, Bis (6,7,8-trimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, Bis (6,7,9-trimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, Bis (7,8,9-trimethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane and the like.

Examples of compounds of bis (tetramethyl-substituted-1,2,3,4-tetrahydroquinolino) dimethoxysilane shoot Bis (2,3,4,6-tetramethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, Bis (2,3,4,7-tetramethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, Bis (2,3,4,8-tetramethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, Bis (2,3,4,9-tetramethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, Bis (3,4,6,7-tetramethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, Bis (3,4,6,8-tetramethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (3,4,6,9-tetramethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, Bis (4,6,7,8-tetramethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, Bis (4,6,7,9-tetramethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane, bis (6,7,8,9-tetramethyl-1,2,3,4-tetrahydroquinolino) dimethoxysilane and the like.

Among these compounds is bis (1,2,3,4-tetrahydroquinolino) dimethoxysilane prefers.

Regarding the connections of the general formula (7) can Bis (1,2,3,4-tetrahydroisoquinolino) dimethoxysilane and the like exemplified become.

Examples of the compound of bis (methyl-substituted-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane include
Bis (1-methyl-1,2,3,4-tetrahydroisochinolino) dimethoxysilane,
Bis (3-methyl-1,2,3,4-tetrahydroisochinolino) dimethoxysilane,
Bis (4-methyl-1,2,3,4-tetrahydroisochinolino) dimethoxysilane,
Bis (6-methyl-1,2,3,4-tetrahydroisochinolino) dimethoxysilane,
Bis (7-methyl-1,2,3,4-tetrahydroisochinolino) dimethoxysilane,
Bis (8-methyl-1,2,3,4-tetrahydroisochinolino) dimethoxysilane,
Bis (9-methyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane and the like.

Examples of the compound of bis (dimethyl-substituted-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane conclude Bis (1,3-dimethyl-1,2,3,4-tetrahydroisochinolino) dimethoxysilane, Bis (1,4-dimethyl-1,2,3,4-tetrahydroisochinolino) dimethoxysilane, Bis (1,6-dimethyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, bis (1,7-dimethyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, Bis (1,8-dimethyl-1,2,3,4-tetrahydroisochinolino) dimethoxysilane, Bis (1,9-dimethyl-1,2,3,4-tetrahydroisochinolino) dimethoxysilane, Bis (3,4-dimethyl-1,2,3,4-tetrahydroisochinolino) dimethoxysilane, Bis (3,6-dimethyl-1,2,3,4-tetrahydroisochinolino) dimethoxysilane, Bis (3,7-dimethyl-1,2,3,4-tetrahydroisochinolino) dimethoxysilane, Bis (3,8-dimethyl-1,2,3,4-tetrahydroisochinolino) dimethoxysilane, Bis (3,9-dimethyl-1,2,3,4-tetrahydroisochinolino) dimethoxysilane, Bis (4,6-dimethyl-1,2,3,4-tetrahydroisochinolino) dimethoxysilane, Bis (4,7-dimethyl-1,2,3,4-tetrahydroisochinolino) dimethoxysilane, Bis (4,8-dimethyl-1,2,3,4-tetrahydroisochinolino) dimethoxysilane, Bis (4,9-dimethyl-1,2,3,4-tetrahydroisochinolino) dimethoxysilane, Bis (6,7-dimethyl-1,2,3,4-tetrahydroisochinolino) dimethoxysilane, Bis (6,8-dimethyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, Bis (6,9-dimethyl-1,2,3,4-tetrahydroisochinolino) dimethoxysilane, Bis (7,8-dimethyl-1,2,3,4-tetrahydroisochinolino) dimethoxysilane, Bis (7,9-dimethyl-1,2,3,4-tetrahydroisochinolino) dimethoxysilane, Bis (8,9-dimethyl-1,2,3,4-tetrahydroisochinolino) dimethoxysilane and the like.

Examples of compounds of bis (trimethyl-substituted-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane conclude Bis (1,3,4-trimethyl-1,2,3,4-tetrahydroisochinolino) dimethoxysilane, Bis (1,3,6-trimethyl-1,2,3,4-tetrahydroisochinolino) dimethoxysilane, Bis (1,3,7-trimethyl-1,2,3,4-tetrahydroisochinolino) dimethoxysilane, Bis (1,3,8-trimethyl-1,2,3,4-tetrahydroisochinolino) dimethoxysilane, Bis (1,3,9-trimethyl-1,2,3,4-tetrahydroisochinolino) dimethoxysilane, Bis (3,4,6-trimethyl-1,2,3,4-tetrahydroisochinolino) dimethoxysilane, Bis (3,4,7-trimethyl-1,2,3,4-tetrahydroisochinolino) dimethoxysilane, Bis (3,4,8-trimethyl-1,2,3,4-tetrahydroisochinolino) dimethoxysilane, Bis (3,4,9-trimethyl-1,2,3,4-tetrahydroisochinolino) dimethoxysilane, Bis (4,6,7-trimethyl-1,2,3,4-tetrahydroisochinolino) dimethoxysilane, Bis (4,6,8-trimethyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, bis (4,6,9-trimethyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, Bis (6,7,8-trimethyl-1,2,3,4-tetrahydroisochinolino) dimethoxysilane, Bis (6,7,9-trimethyl-1,2,3,4-tetrahydroisochinolino) dimethoxysilane, Bis (7,8,9-trimethyl-1,2,3,4-tetrahydroisochinolino) dimethoxysilane and the like.

Examples of the bis (tetramethyl-substituted-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane compounds conclude Bis (1,3,4,6-tetramethyl-1,2,3,4-tetrahydroisochinolino) dimethoxysilane, Bis (1,3,4,7-tetramethyl-1,2,3,4-tetrahydroisochinolino) dimethoxysilane, Bis (1,3,4,8-tetramethyl-1,2,3,4-tetrahydroisochinolino) dimethoxysilane, Bis (1,3,4,9-tetramethyl-1,2,3,4-tetrahydroisochinolino) dimethoxysilane, Bis (3,4,6,7-tetramethyl-1,2,3,4-tetrahydroisochinolino) dimethoxysilane, Bis (3,4,6,8-tetramethyl-1,2,3,4-tetrahydroisochinolino) dimethoxysilane, Bis (3,4,6,9-tetramethyl-1,2,3,4-tetrahydroisochinolino) dimethoxysilane, Bis (4,6,7,8-tetramethyl-1,2,3,4-tetrahydroisochinolino) dimethoxysilane, Bis (4,6,7,9-tetramethyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, Bis (6,7,8,9-tetramethyl-1,2,3,4-tetrahydroisochinolino) dimethoxysilane and the like.

Among these compounds is bis (1,2,3,4-tetrahydroisoquinolino) dimethoxysilane prefers.

Examples of the compounds of the general Close formula (8) (1,2,3,4-tetrahydroquinolino) (1,2,3,4-tetrahydroisochinolino) dimethoxysilane, (2-methyl-1,2,3,4-tetrahydroquinolino) (1-methyl-1,2,3,4-tetrahydroisochinolino) dimethoxysilane, (3-methyl-1,2,3,4-tetrahydroquinolino) (3-methyl-1,2,3,4-tetrahydroisochinolino) dimethoxysilane, (3-methyl-1,2,3,4-tetrahydroquinolino) (4-methyl-1,2,3,4-tetrahydroisochinolino) dimethoxysilane, (4-methyl-1,2,3,4-tetrahydroquinolino) (4-methyl-1,2,3,4-tetrahydroisoquinolino) dimethoxysilane, (4-methyl-1,2,3,4-tetrahydroquinolino) (6- methyl-1,2,3,4-tetrahydroisochinolino) dimethoxysilane, (6-methyl-1,2,3,4-tetrahydroquinolino) (6-methyl-1,2,3,4-tetrahydroisochinolino) dimethoxysilane, (6-methyl-1,2,3,4-tetrahydroquinolino) (7-methyl-1,2,3,4-tetrahydroisochinolino) dimethoxysilane, (7-methyl-1,2,3,4-tetrahydroquinolino) (7-methyl-1,2,3,4-tetrahydroisochinolino) dimethoxysilane, (7-methyl-1,2,3,4-tetrahydroquinolino) (8-methyl-1,2,3,4-tetrahydroisochinolino) dimethoxysilane, (8-methyl-1,2,3,4-tetrahydroquinolino) (8-methyl-1,2,3,4-tetrahydroisochinolino) dimethoxysilane, (8-methyl-1,2,3,4-tetrahydroquinolino) (9-methyl-1,2,3,4-tetrahydroisochinolino) dimethoxysilane, (9-methyl-1,2,3,4-tetrahydroquinolino) (9-methyl-1,2,3,4-tetrahydroisochinolino) dimethoxysilane and the like.

Among these compounds, (1,2,3,4-tetrahydroquinolino) (1,2,3,4-tetrahydroisoquinolino) is dimethoxysilane prefers.

Specific examples of the aminosilane compounds of the general formula (1) conclude by the following chemical structural formulas shown:

hergestellt werden.An aminosilane compound which is the catalyst component (C) of the general formula (1) can be obtained by reacting tetramethoxysilane or dichlorodimethoxysilane with 2 equivalent amounts of the magnesium salt or lithium salt of the secondary amine of the formula

getting produced.

Some aminosilane compounds of the Formula (1) have geometric isomers because of the polycyclic amino group a cis or a trans isomer may include. This means, that isomers such as (trans-polycycloamino) (trans-polycycloamino) dialkoxysilane, (Cis-polycyclic) (cis-polycyclic) dialkoxysilane and (trans-polycycloamino) (cis-polycycloamino) dialkoxysilane exist.

Illustrative examples of this conclude Bis (trans-perhydroquinolino) dimethoxysilane, bis (cis-perhydroquinolino) dimethoxysilane, Bis (trans-perhydroisoquinolino) dimethoxysilane, bis (cis-perhydroisoquinolino) dimethoxysilane, (Trans-perhydro (iso) quinolino) (cis-perhydro (iso) quinolino) dimethoxysilane or the like.

Each of these isomers can act as a catalyst component (C) can be used both individually and in the form of a Mixture or a racemate.

The quantitative ratio of the catalyst component (C) to the catalyst component (B) is preferably 0.01 to 1.0; particularly preferably 0.05 to 0.33; expressed as atomic ratio (Si / Al) the silicon atoms of the aminosilane compound to the aluminum atoms the organoaluminum compound.

In the present invention can a chain transfer agent, such as hydrogen or the like can be used. The for Production of an α-olefin polymer with the ones you want Degrees of stereochemical regularity, melting points and Molecular weights needed The amount of hydrogen can be suitably depending on the polymerization method and the polymerization conditions are determined. In general hydrogen is introduced into the polymerization system in such a way that a hydrogen partial pressure in the range from 0.005 MPa to 3 MPa, preferably 0.01 MPa to 1 MPa is maintained.

In the present invention no particular limitation regarding the order of contacting the individual Catalyst components for polymerizing α-olefins, but it is preferred first the catalyst component (A) with the catalyst component (B) and then to contact with the catalyst component (C) or first the catalyst component (B) with the catalyst component (C) and then to contact with the catalyst component (A).

One for the subject of the present Α-olefin useful in the invention includes Propylene, 1-butene, 1-hexene, 4-methylpentene-1, 1-octene and the like on. In the present invention, the polymerization of an α-olefin can also by copolymerization with a small amount of ethylene or other α-olefins accomplished the melting point to lower the heat seal temperature of the film cut of interest and to reduce transparency to improve the slide.

Regarding the subject of the present Polymerization methods useful in the invention are, for example Slurry polymerization using a non-polar solvent; Gas phase polymerization, which is the contacting of a monomer in the gas state with a catalyst; bulk polymerization, which is a slurry polymerization in a liquid, as a solvent serving monomer. To perform the aforementioned procedures can be either a continuous polymerization or a batch Polymerization can be used.

Bulk polymerization is preferred executed under temperature and pressure conditions in which an α-olefin or a mixture of monomers from α-olefins in the liquid Condition can be maintained. The polymerization temperature is generally 30 to 90 ° C, preferably 50 to 80 ° C, the polymerization time is generally 5 minutes to 5 hours.

The gas phase polymerization will executed under temperature and pressure conditions in which an α-olefin or a mixture of monomers from α-olefins in the liquid Condition can be maintained.

In gas phase polymerization the pressure is generally between atmospheric pressure and 3 MPa, preferably between atmospheric pressure and 2 MPa; the polymerization temperature is generally 30 to 120 ° C, preferred 40 to 100 ° C; the polymerization time is generally 30 minutes to 10 hours, preferably 1 to 7 hours.

The slurry polymerization is through Introduce an α-olefin or a monomer mixture of α-olefins in the presence of an inert solvent executed. Specific examples of the inert solvent include propane, Butane, pentane, hexane, heptane, octane and the like.

The catalyst of the present invention shows high polymerization activity when the polymerization is carried out specifically at a temperature of over 70 ° C, and an α-olefin polymer with great stereochemical regularity and a wide molecular weight distribution can be obtained by using the catalyst. To carry out gas phase polymerization, a prepolymer is preferably used as the solid catalyst component (A), which is prepared by the processes described below. Furthermore, a non-polar solvent such as propane, butane, hexane, heptane, octane or the like, in part together with an α-olefin monomer, can be used in a gas phase polymerization to remove the heat of polymerization and to eliminate static electricity that the product vity of the polymerization is increased.

Regarding the subject of the present Invention leads prepolymerization is preferred of ethylene or an α-olefin according to one of the various polymerization processes mentioned above and then the main polymerization. The effects of prepolymerization consist in improvements in the polymerization activity, the stereochemical regularity of the polymer and in a stabilization of the particle shapes of the Polymer. In terms of the prepolymerization process a pretreated solid catalyst can be prepared by one first a solid catalyst component (A) with an organoaluminum compound the catalyst component (B) and an aminosilane compound of the catalyst component (C) in contact and then washes the resulting solid, so that the pretreated solid catalyst for prepolymerization is obtained. Furthermore, a certain amount of ethylene or an α-olefin is added Use of the catalyst component (A) or the above pretreated solid catalyst in the presence of the catalyst components (B) and (C) polymerized so that the pretreated polymerization solid is obtained.

If for the present invention the above pretreated solid catalyst or pretreated polymerization solid as a solid catalyst component for the main polymerization is used, the catalyst component (C) in the polymerization be omitted.

With regard to the contacting according to the invention the catalyst components (A), (B) and (C) are mixed and generally at 0 to 100 ° C 0.1 to 10 hours implemented. For there is no order of mixing the individual components certain limitation, the order component (A), component (B) and component (C) is generally preferred. After contacting the resulting solid with an inert hydrocarbon solvent, such as n-heptane, washed and by filtration for use in the solid catalyst component for polymerization or prepolymerization separated.

The prepolymerization according to the invention can be carried out by the gas phase process, slurry process, bulk polymerization process or the like become. The one in prepolymerization solid obtained after the separation or without such for the Main polymerization used.

The prepolymerization time is generally 0.1 to 10 hours, the prepolymerization is preferably continued until a prepolymer in an amount of 0.1 to 100 g per g of the solid catalyst component is formed. If the amount of polymer formed is less than 0.1 g per g of solid catalyst component, is the activity of the main polymerization not good enough, a big one Amount of catalyst residue remains in the polymer and the stereochemical regularity of the α-olefin polymer obtained insufficient. If the amount of prepolymer obtained larger than 100 g, the polymerization activity tends to decrease and the introduction of prepolymers into a polymerization tank difficult rig. The prepolymerization is at 0 to 100 ° C, preferably at 10 to 90 ° C carried out in the presence of the individual catalyst components. If the polymerization is carried out at a temperature of more than 50 ° C., is preferably a low concentration of ethylene or an α-olefin one or you choose a short prepolymerization time. Otherwise, it is difficult to set the amount of the prepolymer in the range of 0.1 to control up to 100 g per g of the solid catalyst component, and the stereochemical regularity of the α-olefin polymer tends to decrease.

The amount of prepolymerization used organoaluminum compound of the catalyst component (B) is generally 0.5 to 1000, preferably 1 to 100, expressed as Atomic ratio (Al / Ti) from aluminum atoms of the organoaluminum compound to titanium atoms the solid catalyst component (A). The amount of aminosilane compound used the catalyst component (C) is generally 0.01 to 1, preferably 0.08 to 0.5; expressed as atomic ratio (Si / Al) from silicon atoms of the aminosilane compound to aluminum atoms of the Organoaluminum compound. During prepolymerization, depending on Need to also have hydrogen gas.

That with the present invention catalyst system used has high catalytic activities, furthermore, the α-olefin polymer thus obtained has a high stereochemical regularity and a high melting point as well as a broad molecular weight distribution in a wide range of molecular weights. The molecular weight distribution, expressed as the Mw / Mn ratio, is more than 10, preferably more than 12, particularly preferably more than 15, obtained by calculation from the weight average molecular weight (Mw) and number average molecular weight (Mn), both using GPC (gas permeation chromatography) measured and converted Values of polystyrene can be obtained.

Therefore, since the α-olefin polymer related to the subject matter of the invention has high stereochemical regularity and a broad molecular weight distribution, the molded article has excellent stability, heat resistance and mechanical properties such as tensile strength and the like; moreover, the molded article made therefrom has no problem in poor external appearance such as flow marks because the polymer has a high strand expansion value at the shear rate when it is melted. The α-olefin polymer according to the invention can be used not only individually, but also as a compounding material be used by mixing it with other plastics and / or elastomers. Furthermore, the polymer can be used together with inorganic fillers, such as glass fibers, talc or the like, and with organic fillers made of reinforcing materials, as well as with nucleating agents. Thus, the α-olefin polymer has excellent properties as a construction material for automobiles and household electrical appliances; however, its use is not so limited.

By polymerizing an α-olefin using the catalyst of the invention, the one high polymerization activity possesses, an α-olefin polymer with a high stereochemical regularity, high melting point and broad molecular weight distribution. Of Further, by polymerizing an α-olefin such as, for example Propylene, with ethylene or another α-olefin using the catalyst according to the invention an α-olefin copolymer manufactured with good statistical distribution and high viscoelasticity become.

Since the α-olefin polymer produced according to the invention has a molecular weight distribution that is similar Area like that using a conventional one Titanium trichloride type catalyst used as the second catalyst Generation and has a low polymerization activity, lies, the α-olefin polymer produced according to the invention good shaping properties, and exist with the shaped objects no problems such as poor appearance including the Formation of flow marks. Therefore, the catalyst system according to the invention as replacement for conventional Titanium trichloride type catalysts are needed. The one polymerization Moreover compared to that of more conventional ones Catalysts of the titanium trichloride type is significantly larger, is the catalyst system according to the invention therefore quite useful to simplify the polymerization process and the production costs to reduce by the previously used to remove the catalyst residue needed from the polymer Step, d. H. a method of removing the ashes from the polymer using a large Amount of an organic solvent, becomes dispensable.

According to the invention, a propylene block copolymer by producing a crystalline propylene polymer be by first Polymerized propylene alone or propylene with a limited Amount of another α-olefin copolymerized, in each case in the presence of the above catalyst system, and then making a rubbery propylene copolymer by subsequently copolymerized propylene with an α-olefin other than propylene, without deactivating the above catalyst system after the first step.

The polymerization of the first step can be in a homopolymerization of propylene or in a copolymerization of propylene with an α-olefin other than propylene. Specific examples of α-olefins conclude acyclic monoolefins, such as ethylene, butene-1, 3-methylbutene-1, 3-methylpentene-1, 4-methylpentene-1, hexene-1, 4-methylhexene-1, octene-1, styrene-1, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, vinylcyclohexane, vinylcyclopentane, 2-vinylnaphthalene, 9-vinylanthracene and the like; cyclic monoolefins, such as cyclopentene, cyclohexene, norbornene and the like; and Diolefins such as dicyclopentadiene, 5-ethylidene norbornene-2,4-vinylcyclohexene, 1,5-hexadiene and the like.

The proportion of an α-olefin other than propylene, that produced in one by polymerizing the first step Crystalline polymer should be contained within such Range that maintain the properties of polypropylene remain, preferably for example 10% by weight or less. But when the content of an α-olefin other than propylene found in the crystalline Polymer is contained, exceeds 10 wt .-%, then increases Amount of by-products of low crystalline polymers.

In the second polymerization step a rubbery copolymer is made by using propylene an α-olefin other than propylene copolymerized. Specific examples of the α-olefins include acyclic ones Monoolefins, such as ethylene, butene-1, 3-methylbutene-1, 3-methylpentene-1, 4-methylpentene-1, hexene-1, 4-methylhexene, octene-1, styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, Vinylcyclohexane, vinylcyclopentane, 2-vinylnaphthalene, 9-vinylanthracene and the like; cyclic monoolefins, such as cyclopentene, cyclohexene, Norbornene and the like; and diolefins such as dicyclopentadiene, 5-ethylidene norbornene, 4-vinylcyclohexene, 1,5-hexadiene and the like on.

The salary of the second step The rubbery polymer obtained can be 3 to 40% by weight, preferably 5 make up to 30 wt .-% of the amount of the total block copolymer. The content of one other than propylene, in the rubbery one Copolymer contained α-olefin is preferably 10 to 40% by weight.

Regarding the type of polymerization in the first step and the copolymerization in the second step of The present invention can be used in an inert solvent executed Slurry polymerization, one using a liquid, as a solvent serving monomer Bulk polymerization, a gas phase polymerization by contacting a gaseous monomer used with a catalyst and a combination of these processes become. Among these methods is bulk polymerization preferred, in which in the first step a monomer in the liquid state polymerized and then carried out a gas phase polymerization by a gaseous monomer in the second step in contact with a catalyst.

Bulk polymerization is preferably carried out under temperature and pressure conditions which propylene or a monomer mixture of propylene and other α-olefins is kept in the liquid state. The polymerization temperature is generally 30 to 90 ° C, preferably 50 to 80 ° C, the polymerization time is generally 5 minutes to 5 hours.

Gas phase polymerization is used preferably carried out under temperature and pressure conditions, at which propylene or a monomer mixture of propylene and other α-olefins in the liquid Condition is maintained.

In gas phase polymerization the pressure is generally between atmospheric pressure and 3 MPa, preferably between atmospheric pressure and 2 MPa; the polymerization temperature is generally 30 to 120 ° C, preferred 40 to 100 ° C; the polymerization time is generally 30 minutes to 10 hours, preferably 1 to 7 hours.

A slurry polymerization will through introduction of propylene or a monomer mixture of propylene with one of Propylene various α-olefin in the presence of an inert solvent executed. Specific examples of the inert solvent include propane, Butane, pentane, hexane, heptane, octane and the like.

In the manufacture of a propylene block copolymer it is preferable to use one prepared by the above-mentioned methods prepolymer as a solid catalyst component (A).

With regard to the other conditions for copolymerization can the same as for homopolymerization can be used.

Since the catalyst system according to the invention high catalytic activity has a propylene block copolymer thus obtained high stereochemical regularity and a high melting point as well as a broad molecular weight distribution on. Its molecular weight distribution, expressed as the Mw / Mn ratio, is more more than 15, preferably more than 20, particularly preferably more than 30, obtained by calculation from the weight average molecular weight (Mw) and number average molecular weight (Mn), both using GPC measured using polystyrene as the standard substance were.

Since that obtained according to the invention Propylene block copolymer a great crystallizability and has a broad molecular weight distribution, have the shaped objects hence excellent stability, heat resistance and mechanical properties such as tensile strength and the like; about that in addition, there are no problems with the molded articles poor appearance, including the formation of flow points, because the polymer has a high strand expansion value at the shear rate when it is melted. The propylene block copolymer according to the invention can not only be used alone, but also as a starting material for compounding be used by mixing it with other plastics and / or Elastomers mixed. Furthermore, the block copolymer can be combined with inorganic fillers, such as glass fibers, talc or the like, and with organic ones fillers reinforcing Materials as well as used with nucleating agents. Thus points the α-olefin polymer excellent Properties as construction material for automobiles and electrical domestic appliances on; however, its use is not so limited.

The process of the present invention can be a propylene polymer having an Mw of 200,000 or less in terms of polystyrene measured by GPC, an Mw / Mn of 10 or more, a "mmmm-isopentad fraction" in ¹³ C-NMR of 96% or more, and provide a melting point of 162 ° C or higher if measured by the DSC method.

The propylene polymer according to the invention has the following properties; a weight average molecular weight (Mw) as polystyrene determined by GPC measurement, of 200,000 or less, preferably in the range from 50,000 to 200,000, it thus has a relatively low molecular weight.

The ratio of the weight average Molecular weight to number average molecular weight (Mw / Mn) is 10 or more, preferably 12 or more, particularly preferably 13 or more, very particularly preferably a value in the range from 13 to 30.

According to the ¹³ C-NMR measurement described in "Macromolecules", edition 8, p. 687 (1975), the configuration (dd or II is defined as m) of 5 types of methyl groups, the mmmm fraction of the continuous propylene monomer unit is 96% or more, preferably 97% or more, particularly preferably 97.5% to 99.5%.

The measured by the DSC method Melting point is preferably 162.5 to 166 ° C at a temperature gradient speed of 10 ° C per minute.

(worin R¹ für einen Kohlenwasserstoffrest mit 1 bis 8 Kohlenstoffatomen steht; und

für eine polycyclische Aminogruppe mit 7 bis 40 Kohlenstoffatomen steht, wobei die das cyclische Gerüst bildenden Kohlenstoffatome direkt an das Stickstoffatom gebunden sind).The present invention further relates to an aminosilane compound of the following general formula (1):

(wherein R ^{1 represents} a hydrocarbon radical having 1 to 8 carbon atoms; and

represents a polycyclic amino group having 7 to 40 carbon atoms, the carbon atoms forming the cyclic skeleton being bonded directly to the nitrogen atom).

In the case of polymerizing an α-olefin using the catalyst system according to the invention, the contains an aminosilane compound as one of the components with high polymerization activity an α-olefin polymer with high stereochemical regularity, a high melting point and a broad molecular weight distribution. About that In addition, in the case of copolymerization of an α-olefin with ethylene or other α-olefins using the catalyst system a copolymer with good statistical distribution and high melt viscoelasticity become.

Compared to a conventional one Titanium trichloride type catalyst used as the second catalyst Generation, the above catalyst system according to the invention high polymerization activity exhibit. About that Furthermore, an α-olefin polymer thus obtained has a molecular weight distribution that is almost that of the under Using the above conventional Polymer made of the titanium trichloride type catalyst is the same. Thus, using the catalyst according to the invention manufactured α-olefin polymer good shaping properties and there are no problems with regard to the external appearance the shaped objects, including Flow marks. Therefore, the catalyst system according to the invention as replacement for conventional Titanium trichloride type catalysts are used. The one polymerization also compared to that of a conventional titanium trichloride type catalyst significantly higher is the catalyst system according to the invention quite useful to simplify the polymerization process and the production costs to reduce by previously removing catalyst residue required from the polymers Steps are dispensable; d. H. the steps to remove the Ashes by using a large amount of an organic Solvent.

Examples

The present invention is accomplished by the following examples, preparation examples, synthesis examples and comparative examples explained. However, the scope of the present invention is not limited to these examples only limited.

In the following examples means the expression (co-) polymerization reaction rate a yield (kg) of (co) polymer obtained per 1 g of the solid catalyst.

The melt flow ratio (M.F.R.) is determined by weighing an amount (g) of one at a temperature of 230 ° C melted Polymers under a load of 2.16 kg 10 minutes corresponding to that procedures described in ASTM-D1238.

The melting point (Tm) is below Measured using DSC (Model: ASC-5200, manufactured by Seiko Denshi Kohgyo, Co.). The measurement conditions were set so that 10 mg of propylene polymer at a temperature of 23 ° C to 230 ° C with a Temperature gradients of 10 ° C were heated per minute, then the polymer in its 5 minutes Given condition was maintained and the temperature then from 230 ° C to 40 ° C with a Temperature gradients of 5 ° C was reduced per minute. The melting point is measured as the point in which the polymer thus treated by heating from 40 ° C to 230 ° C by a Temperature gradients of 10 ° C is melted again per minute.

The stereochemical regularity of the polymer is determined from the isopentad fraction (mmmm) (%) obtained by the microtacticity, which means that one of the characteristics of the stereochemical regularity of the polymer from the peak ratio of the ¹³ C-NMR spectrum corresponding to that in Macromolecules, Vol. 8, page 687 (1975). The ¹³ C-NMR spectrum is measured by a model EX-400 (manufactured by JEOL Ltd.), at a temperature of 130 ° C using TMS as a standard substance and o-dichlorobenzene as a solvent: the molecular weight distribution of a polymer is measured from the ratio (Mw / Mn) of the weight average molecular weight weight (Mw) and number average molecular weight (Mn) calculated using polystyrene as a standard substance, a GPC device (model: 150CV type, manufactured by Waters & Co.), o-dichlorobenzene as solvent, a SHODEX column , a temperature of 145 ° C and a concentration of 0.05 wt .-% can be determined.

The block copolymerization ratio is defined as the ratio (%) of the yield (parts by weight) of copolymer to the yield (parts by weight) of the entire polymer as shown by the following formula: [Yield (parts by weight) of copolymer] / [Yield (parts by weight) of total polymer] × 100

The heptane-insoluble parts (HI) are defined as the ratio (%) of the amount (parts by weight) of insoluble parts obtained by extraction (with a Soxhlet extractor) of a polymer sample with boiling n- heptane to the amount (parts by weight) the filled polymer sample as shown by the following formula: [Insoluble polymer (parts by weight)] / [Filled polymer (parts by weight) × 100

The contained in the copolymer formed The amount of ethylene is determined as shown below:

A sample of copolymer is placed on a hot plate and melted by heating. The sample is then cooled under pressure and quenched in a water bath, after which a film is formed with a thickness of approximately 30 μm. Using an infrared spectrophotometer, the absorption peaks of films produced in this way are measured at 974 cm ^-1 and 720 cm ^-1 , the ethylene content is calculated with reference to a previously recorded calibration curve.

The intrinsic viscosity [η] of a Rubber component is determined as shown below:

20 mg of a sample are weighed exactly and placed in a 25 ml volumetric flask, 20 ml decalin, 0.3% BHT contains are added. The sample is used one on one Temperature of 135 ° C preset thermostatted chamber completely dissolved at 135 ° C, then 20 ml of the above sample solution transferred to a viscometer; the Time to pass two calibration lines is measured so that the intrinsic viscosity [η] the Obtained rubber component using for the formula of viscosity becomes.

The weighing moment is accordingly the method ASTM-D-790 certainly. This means, 0.1% by weight Irganox-1010, 0.1% by weight Irganox-1076 and 0.1% by weight Calcium stearate is added as an additive to an α-olefin polymer powder. The resulting one Mixture is pelletized using an extruder, then several test pieces by means of injection molding (model: J100SAll, manufactured by The Japan Steel Works, Ltd.) under the conditions of 1.5 MPa back pressure and 60 ° C molding temperature manufactured.

The heat distortion temperature becomes corresponding ASTM-D-648 using one at the same time as determined above by injection molded test piece.

Denoted in the following examples the expression "%" unless otherwise indicated, "% by weight".

First, synthesis examples of aminosilane compounds according to the invention explained.

Synthesis example 1

Synthesis of bis (perhydroisoquinolino) dimethoxysilane

In a 200 ml flask equipped with a dropping funnel and a stirrer, after the atmosphere in the flask was replaced with nitrogen gas using a vacuum pump, 0.12 mol of perhydroisoquinoline and 60 ml of n- heptane were added. 75.0 ml (0.12 mol) of a hexane solution containing 1.6 mol / liter n- butyllithium were added to the dropping funnel. While cooling with ice, the n- butyllithium-hexane solution was slowly added dropwise to the flask, then the reaction mixture was stirred at room temperature for one hour to obtain lithium perhydroisoquinolide. The lithium perhydroisoquinolide thus obtained was transferred together with the solvent to the next reaction system without being isolated from the reaction system.

In the next reaction system, 0.06 mol of tetramethoxysilane and 60 ml of n- heptane were placed in a 500 ml flask equipped with a dropping funnel and a stirrer which was connected to a glass filter after the atmosphere in the flask was replaced with nitrogen gas by means of a vacuum pump given.

0.12 mol of previously synthesized lithium perhydroisoquinolide was added to the dropping funnel. With ice cooling, the lithium perhydroisoquinolide was slowly added dropwise to the flask, then the reaction mixture was stirred at room temperature for 12 hours. After making sure that the ge when the desired product was sufficiently formed, the precipitate was separated by filtration using the glass filter. The resulting filtrate was purified by distillation to give bis (perhydroisoquinolino) dimethoxysilane. The boiling point of the desired product was 180 ° C / 1 mmHg and the purity was 98.6%, determined using gas chromatography.

Furthermore, the assignment in ¹ H-NMR and ¹³ C-NMR was determined as follows. The NMR peaks were determined by the in “J. Chem. Soc. Perkin. Trans. ", Vol. 2, 510-511 (1979).
δ (ppm) = 0.80-1.90 (-CH ₂ -, CH-, 23.8H, m) 3.03-3.30 (-CH ₂ -N-CH ₂ -, 7.9H, m ) 3.45 (CH ₃ -O-Si, 6.0H, s)
¹³ C chemical shifts for bis (perhydroisoquinolino) dimethoxysilane in CDCl ₃

Synthesis example 2

Synthesis of bis (perhydroisoquinolino) dimethoxysilane

Performed by a procedure similar to that as used in Synthesis Example 1 above, except that Perhydroquinoline was used instead of perhydroisoquinoline. The boiling point of the desired Product was 180 ° C / 1 mmHg and the purity was 98.0% as determined by gas chromatography.

Furthermore, the assignment in ¹ H-NMR and ¹³ C-NMR was determined as follows. The NMR peaks were determined by the in “J. Chem. Soc. Perkin. Trans. ", Vol. 2, 615-621 (1972) and" J. Chem. Soc. Perkin. Trans. ", Vol. 2, 842 (1972).
δ (ppm) = 0.90-2.10 (-CH ₂ -, -CH-, 26.0H, m) 2.60-3.20 (-CH ₂ -N-CH ₂ -, 6.0H, m) 3.46 (CH ₃ -O-Si, 6.0H, s)
¹³ C chemical shifts for bis (perhydroquinolino) dimethoxysilane in CDCl ₃

Synthesis example 3

Synthesis of bis (1,2,3,4-tetrahydroisoquinolino) dimethoxysilane

Performed by a procedure similar to that as used in Synthesis Example 1 above, except that 1,2,3,4-tetrahydroisoquinoline was used instead of perhydroisoquinoline. The boiling point of the desired one Product was 168.5 ° C / 0.6 mmHg and the purity was 97.7%, determined by gas chromatography.

Furthermore, the assignment in ¹ H-NMR was determined as follows.
δ (ppm) = 2.79 (-CH ₂ -CH ₂ -N-Si, 4.2H, t) 3.33 (-CH ₂ -CH ₂ -N-Si, 4.3H, t) 3.54 (CH ₃ -O-Si, 6.0H, s) 4.24 (= C-CH ₂ -N-Si, 4.3H, s) 7.01-7.18 (-CH = CH-CH = CH -, 8.3H, m)

Synthesis example 4

Synthesis of bis (1,2,3,4-tetrahydroquinolino) dimethoxysilane

Performed by a procedure similar to that as used in Synthesis Example 1 above, except that 1,2,3,4-tetrahydroquinoline was used instead of perhydroisoquinoline. The boiling point of the desired one Product was 192 ° C / 0.7 mmHg and the purity was 98%, determined by gas chromatography.

Furthermore, the assignment in ¹ H-NMR was determined as follows.
δ (ppm) = 1.96 (-CH ₂ -CH ₂ -CH ₂ -, 4.3H, m) 2.88 (= CH ₂ -CH ₂ -, 4.3H, t) 3.57 (= CN -CH ₃ -, 4.3H t) 3.65 (CH ₃ -O-Si, 6.0H, s) 6.70-7.17 (-CH = CH-CH = CH-, 8.2H, m )

Synthesis example 5

Synthesis of bis (perhydroisoindolino) dimethoxysilane

Performed by a procedure similar to that as used in Synthesis Example 1 above, except that Perhydroisoindole was used instead of perhydroisoquinoline. The boiling point of the desired Product was 165.5 ° C / 0.9 mmHg and the purity was 96.2%, determined by gas chromatography.

Furthermore, the assignment in ¹ H-NMR and ¹³ C-NMR was determined as follows. The NMR peaks were determined according to the method described in Patterson, Soedigdo, J. Org. Chem., Vol. 32, 1081-1086 (1972).
δ (ppm) = 1.29-2.05 (-CH ₂ - + -CH-, 20.9H, m) 2.90-3.11 (-CH ₂ -N-CH ₂ -, 8.3H, m) 3.51 (CH ₃ -O-Si, 6.0H s)
¹³ C chemical shifts for bis (perhydroisoindolino) dimethoxysilane in CDCl ₃

Synthesis example 6

Synthesis of bis (perhydroindolino) dimethoxysilane

Performed by a procedure similar to that as used in Synthesis Example 1 above, except that Perhydroindole was used instead of perhydroisoquinoline. The boiling point of the desired Product was 150 ° C / 0.8 mmHg and the purity was 97.5%, determined by gas chromatography.

Furthermore, the assignment in ¹ H-NMR and ¹³ C-NMR was determined as follows. The NMR peaks were determined according to the method described in Patterson, Soedigdo, J. Org. Chem., Vol. 32, 1081-1086 (1972).
δ (ppm) = 1.00-2.15 (-CH ₂ - + -CH-, 23.4H, m) 3.05-3.25 (-CH ₂ -N-CH ₂ -, 6.1H, m) 3.45 (CH ₃ -O-Si, 6.0H s)
¹³ C chemical shifts for bis (perhydroindolino) dimethoxysilane in CDCl ₃

Synthesis example 7

Synthesis of n-propyl (perhydroisoquinolino) dimethoxysilane (not part of the invention)

In a 200 ml flask equipped with a dropping funnel and a stirrer, after to which the atmosphere in the flask was replaced with nitrogen gas using a vacuum pump, 0.06 mol of perhydroisoquinoline and 60 ml of n- heptane. 37.5 ml (0.06 mol) of a hexane solution containing 1.6 mol / liter n- butyllithium were added to the dropping funnel. While cooling with ice, the n- butyllithium-hexane solution was slowly added dropwise to the flask, then the reaction mixture was stirred at room temperature for one hour to obtain lithium perhydroisoquinolide. The lithium perhydroisoquinolide thus obtained was transferred together with the solvent to the next reaction system without being isolated from the reaction system.

In the next reaction system, in a 500 ml flask equipped with a dropping funnel and a stirrer and connected to a glass filter after the atmosphere in the flask had been replaced by nitrogen gas using a vacuum pump, 0.06 mol of tetramethoxysilane and 60 ml of n - Given heptane.

0.06 mol of previously synthesized lithium perhydroisoquinolide was added to the dropping funnel. With ice cooling, the lithium perhydroisoquinolide was slowly added dropwise to the flask, then the reaction mixture was stirred at room temperature for 12 hours. After ensuring that the desired product was sufficiently formed, the precipitate was separated by filtration using the glass filter. The resulting filtrate was purified by distillation, so that n- propyl (perhydroisoquinolino) dimethoxysilane was obtained. The boiling point of the desired product was 104.7 ° C / 1 mmHg and the purity was 99.8%, determined using gas chromatography.

Furthermore, the assignment in ¹ H-NMR was determined as follows.
δ (ppm) = 0.60 (-CH ₂ -Si-, 2.0H, t, J = 8.2 Hz) 0.94 (CH ₃ -CH ₂ -, 3.7H, t, J = 7, 1 Hz) 1.05-1.80 (CH ₃ -CH ₂ - + -CH ₂ - + -CH-, 13.6H, m) 2.50-3.30 (-CH ₂ -N-CH ₂ - , 4.0H, m) 3.47 (CH ₃ -O-Si, 6.0H, s)

Synthesis example 8

Synthesis of isopropyl (perhydroisoquinolino) dimethoxysilane (not part of the invention)

The desired compound was prepared by a method similar to that used in Synthesis Example 7, except that isopropyltrimethoxysilane was used instead of n- propyltrimethoxysilane. The boiling point of the desired product was 110.8 ° C / 2 mmHg and the purity was 99.9%, determined by gas chromatography.

Furthermore, the assignment in ¹ H-NMR was determined as follows.
δ (ppm) = 0.97 (CH ₃ -CH-CH ₃ , 7.9H, m) 1.01-1.83 (-CH ₂ - + -CH-, 11.6H, m) 2.55- 3.32 (-CH ₂ -N-CH ₂ -, 4.3H, m) 3.49 (CH ₃ -O-Si, 6.0H, s)

Synthesis example 9 (not Part of the invention)

Synthesis of isobutyl (perhydroisoquinolino) dimethoxysilane

The desired compound was prepared by a method similar to that used in Synthesis Example 7, except that isobutyltrimethoxysilane was used instead of n- propyltrimethoxysilane. The boiling point of the desired product was 108.5 ° C / 1 mmHg and the purity was 97.3%, determined by gas chromatography.

Furthermore, the assignment in ¹ H-NMR was determined as follows.
δ (ppm) = 0.58 (-CH ₂ -Si, 2.0H, d, J = 7.2 Hz) 0.94 (CH ₃ -CH-, 6.0H, d, J = 6.6 Hz ) 1.77-1.84 (CH ₃ -CN- + -CH ₂ - + -CH, 13.0H, m) 2.50-3.30 (-CH ₂ -N-CH ₂ -, 4.3H , m) 3.48 (CH ₃ -O-Si, 6.0H, s)

Synthesis example 10 (not Part of the invention)

Synthesis of diethylamino (perhydroisoquinolino) dimethoxysilane

The desired compound was prepared by a method similar to that used in Synthesis Example 7, except that dimethylaminotrimethoxysilane was used instead of n- propyltrimethoxysilane. The boiling point of the desired product was 123.0 ° C / 2 mmHg and the purity was 98.6%, determined by gas chromatography.

Furthermore, the assignment in ¹ H-NMR was determined as follows.
δ (ppm) = 0.99 (CH ₃ -CH ₂ -N-, 6.9H, t, J = 7.0 Hz) 1.07-1.74 (-CH ₂ - + -CH-, 12, 0H, m) 2.40-3.33 (-CH ₂ -N-CH ₂ -, 8.4H, m) 3.46 (CH ₃ -O-Si, 6.0H, s)

Synthesis example 11

Synthesis of (perhydroquinolino) (perhydroisoquinolino) dimethoxysilane

In a 200 ml flask equipped with a dropping funnel and a stirrer, after the atmosphere in the flask was replaced with nitrogen gas using a vacuum pump, 0.06 mol of perhydroquinoline and 60 ml of n- heptane were added. 37.5 ml (0.06 mol) of a hexane solution containing 1.6 mol / liter n- butyllithium were added to the dropping funnel. With ice cooling, the n -butyllithium hexane solution was slowly added dropwise to the flask, then the reaction mixture was stirred at room temperature for one hour to obtain lithium perhydroquinolide. The lithium perhydroquinolide thus obtained was transferred together with the solvent to the next reaction system without being isolated from the reaction mixture. Furthermore, lithium perhydroisoquinolide was prepared by a method similar to that used above, except that perhydroisoquinoline was used instead of perhydroquinoline. In the next reaction system, 0.06 mol of tetramethoxysilane and 60 ml of n- heptane were placed in a 500 ml flask equipped with a dropping funnel and a stirrer which was connected to a glass filter after the atmosphere in the flask was replaced with nitrogen gas by means of a vacuum pump given. 0.06 mol of previously synthesized lithium perhydroquinolide was added to the dropping funnel. While cooling with ice, the lithium perhydroquinolide was slowly added dropwise to the flask, then the reaction mixture was stirred at room temperature for 1 hour, and further stirred at 80 ° C for 3 hours. Then 0.06 mol of previously synthesized lithium perhydroisoquinolide was added to the empty dropping funnel. While cooling with ice, lithium perhydroisoquinolide was slowly added dropwise to the flask, then the reaction mixture was stirred at 80 ° C. for 3 hours, and stirring was continued for 12 hours at room temperature. After ensuring that the desired product was sufficiently formed, the precipitate was removed by filtration using the glass filter. The resulting filtrate was purified by distillation to give (perhydroquinolino) (perhydroisoquinolino) dimethoxysilane. The boiling point of the desired product was 181 ° C / 1 mmHg and the purity was 97.0%, determined by gas chromatography.

Furthermore, the assignment in ¹ H-NMR was determined as follows.
δ (ppm) = 0.85-2.00 (-CH ₂ - + -CH-, 26.1H, m.) 2.45-3.30 (-CH ₂ -N-CH ₂ - + -CH ₂ -N-CH-, 6.7H, m), 3.45 (CH ₃ -O-Si, 6.0H, s)

The following are manufacturing examples of α-olefin polymers described.

Preparation Examples 1-11

(1) Manufacture of solid Catalyst component (A)

15 millimoles of anhydrous aluminum chloride were added to 40 ml of toluene, then 15 mmol of methyltriethoxysilane was added dropwise with stirring. After the dropwise addition was complete, the mixture was reacted at 25 ° C for 1 hour. After the reaction product was cooled to -5 ° C, 18 ml of diisobutyl ether containing 30 mmol of butylmagnesium chloride was added dropwise to the reaction mixture with stirring, while maintaining the temperature of the reaction mixture in the range of -5 to 0 ° C. After the completion of the dropwise addition, the temperature of the reaction mixture was slowly raised, then the reaction was continued at 30 ° C for 1 hour. The sedimented solid was separated by filtration and washed with toluene and n- heptane. Then 4.9 g of the solid thus obtained were suspended in 30 ml of toluene, then 150 ml of titanium tetrachloride and 3.3 mmol of di-n-heptyl phthalate were added to this suspension and reacted with stirring at 90 ° C. for 1 hour. The solid was separated by filtration at the same temperature and washed with toluene and then with n- heptane. The resulting solid was again suspended in 30 ml of toluene and 150 mmol of titanium tetrachioride were added and then reacted with stirring at 90 ° C for 1 hour. The solid was separated by filtration at the same temperature and washed with toluene and then with n- heptane. The resulting solid catalyst component contains 3.55% by weight of titanium. This solid was suspended in 80 ml of heptane to make a heptane slurry of the solid catalyst component.

(2) Polymerization of propylene

A glass ampoule containing an n- heptane slurry (containing 7.9 mg of the solid catalyst component) of the solid catalyst component (A) was placed in a stainless steel autoclave with a filling volume of 2 liters equipped with a stirrer, then the atmosphere inside the autoclave was sufficiently replaced by nitrogen gas. Then, 2.1 ml of n- heptane solution containing 2.1 mmol of triethylaluminum as the organoaluminum compound of component (B) and 1.74 ml of n -Hep Tan solution containing 0.35 mmol of one of the organosilicon compounds shown in Table 1 as the organosilicon compound of the component (C) was added to the autoclave. After adding hydrogen gas at 0.2 MPa, 1.2 liters of liquefied propylene was added, then the autoclave was shaken. The autoclave was then cooled to 10 ° C. and the glass ampoule, which included the solid catalyst component, was destroyed by the onset of the stirring, and the prepolymerization was carried out for 10 minutes. The temperature inside the autoclave was continuously raised to 70 ° C, and the polymerization was continued at 70 ° C for 1 hour.

After polymerization was complete vented unreacted propylene gas, the resulting polymer was at 50 ° C Dried for 20 hours under reduced pressure so that white powdered polypropylene was obtained. Polymerization activity and test results Properties of the individual polymers are shown in Table 3.

Comparative Examples 1-2

Polymerizations of propylene were made through a process similar the one used in Synthesis Example 11 except that each of the organosilicon compounds shown in Table 2 as a catalyst component (C) was used. Test results regarding the polymerization and the properties of the individual polymers are shown in Table 3.

Table 1

Table 1 (continued)

Table 1 (continued)

Table 2

Table 3

Production Example 12 (not part of the extension)

A glass ampoule containing an n- heptane slurry (containing 7.9 mg of the solid catalyst component) of the solid catalyst component (A), which was used in the preparation example, was placed in a stainless steel autoclave with a filling volume of 2 liters and equipped with a stirrer 1 was prepared in the same way, then the atmosphere inside the autoclave was sufficiently replaced by nitrogen gas. Then, 2.1 ml of n- heptane solution containing 2.1 mmol of triethylaluminum as the organoaluminum compound of component (B) and 1.74 ml of n- heptane solution containing 0.35 mmol of (perhydroisoquinolino) ( tert - butoxy) dimethoxysilane as the organosilicon compound of the component (C) contained in the autoclave. After adding hydrogen gas at 0.2 MPa, 1.2 liters of liquefied propylene was added, then the autoclave was shaken. The autoclave was then cooled to 10 ° C. and the glass ampoule, which included the solid catalyst component, was destroyed by the onset of the stirring, and the prepolymerization was carried out for 10 minutes. The temperature inside the autoclave was continuously raised to 70 ° C, and the polymerization was continued at 70 ° C for 1 hour.

After polymerization was complete vented unreacted propylene gas, the resulting polymer was at 50 ° C Dried for 20 hours under reduced pressure so that white powdered polypropylene was obtained. The results of provisions regarding the Polymerization activity and the properties of the polymers are shown in Table 4.

Comparative Example 3

The polymerization of propylene became similar through a process the one used in Synthesis Example 12 except that methyl (perhydroisoquinolino) dimethoxysilane as Catalyst component (C) in place of (perhydroisoquinolino) (tert-butoxy) dimethoxysilane was used.

Table 4

The following are manufacturing examples for the Gas-phase polymerization explained.

Production Example 13

(1) Manufacture of Treated Prepolymerization catalyst

The atmosphere in a separable 500 ml flask with a glass filter was replaced with nitrogen gas, then 250 ml of distilled anhydrous n- heptane were introduced and 3.25 mmol of triethylaluminum as catalyst component (B) and 0.54 mmol (perhydroisoquinolino) dimethoxysilane as catalyst component ( C) added, the mixture was stirred at 10 ° C. for 5 minutes. Propylene gas was then added for 5 minutes at a flow rate of 0.3 Nl / min and continued for 5 minutes. Then, 1 g of the solid catalyst component (A), which was prepared in the same manner as in Production Example 1, was added to the flask, and the prepolymerization was carried out at 10 ° C. for 10 minutes. After prepolymerization was complete, the reaction mixture was subjected to filtration, and the resulting solid material was washed 3 times with 100 ml of distilled anhydrous n- butane and dried under reduced pressure to obtain prepolymerized treated solid. The prepolymerized treated solid obtained contains 5 g of polypropylene which has been polymerized on the basis of 1 g of the solid catalyst component.

(2) Polymerization of propylene

The atmosphere in a polymerization tank stainless steel with 2 liter filling volume, which was equipped with a sheathing was sufficiently through Nitrogen gas was replaced, then "Flowbeads" (CL12007) (manufactured by Sumitomo Seika Chemicals Co., Ltd.) was introduced as the bed powder. Then were 6 mmol of triethyl aluminum as catalyst component (B) and 1 mmol Bis (perhydroisoquinolino) dimethoxysilane as a catalyst component (C) added in this order and after the reaction mixture to 70 ° C had been heated, hydrogen gas became the chain transfer agent at a pressure of 0.03 MPa and propylene gas at a pressure of 0.45 MPa in the container given. Then was one previously in the container given glass ampoule which treated 65 mg of the above prepolymerized treated Solid included, destroyed by the start of polymerization, the Polymerization was at 70 ° C 1 hour. While the polymerization, the propylene pressure was kept at 0.45 MPa. After more complete Unreacted propylene gas was released from polymerization, the resulting polymer was reduced at 50 ° C for 20 hours Pressure dried so that further powdered polypropylene is obtained has been. The results of the determination of the polymerization activities and Properties of the polymers are shown in Tables 5 and 6.

Production Example 14

Propylene was made by processes similar to those as used in Preparation 13, polymerized with the Exception that the polymerization was carried out at 82 ° C. Results of the determination the polymerization activities and properties of the polymers are shown in Tables 5 and 6.

Production Example 15

Solid treated during manufacture for prepolymerization and polymerization of propylene were processes similar to those as used in Manufacturing Example 13, except that Bis (perhydroquinolino) dimethoxysilane instead of bis (perhydroisoquinolino) dimethoxysilane was used as the catalyst component (C). Results of the determination the polymerization activities and properties of the polymers are shown in Tables 5 and 6.

Production Example 16

Propylene was made by a procedure similar to that as used in Preparation 13, polymerized with the Exception that the polymerization was carried out at 82 ° C. Results of the determination the polymerization activities and properties of the polymers are shown in Tables 5 and 6.

Production Example 17

(1) Manufacture of solid Catalyst component (A)

In a flask equipped with a dropping funnel, glass filter and stirrer, 3 g of silicon oxide (produced by silicon oxide calcined under a stream of nitrogen gas at 200 ° C. for 2 hours under the trade name T6-20420 (manufactured by Fuji Davidson & Co.), which continued at 70 ° C. for 5 hours was calcined), 30 ml of diisopropyl ether, 16 mmol of tert-butyl magnesium chloride and 16 mmol of tert-butyl chloride, then the mixture was stirred at 23 ° C. for 2 hours. The liquid phase of the reaction mixture was removed and dried by heating at 60 ° C for 1 hour and continuously dried at 60 ° C for 1 hour under reduced pressure to give 4.3 g of a carrier.

Of the carrier, 40 ml of toluene, 136 mmol of titanium tetrachloride, 1.5 mmol di- were then placed in a similarly equipped as above flask, 3 g of n -Butylphthalat in this order, the resulting mixture was reacted for 1 hour at 90 ° C. After the reaction was complete, the reaction mixture was subjected to filtration, and the solid portions thus obtained were washed 5 times with 30 ml of toluene. Furthermore, 40 ml of toluene and 136 mmol of titanium tetrachloride were added and reacted again at 90 ° C. for 1 hour. The reaction mixture was then subjected to filtration, the resulting solid was washed 2 times with toluene and 5 times with n- heptane and dried at 23 ° C. under reduced pressure for 2 hours to obtain 3 g of the solid catalyst. The proportion of titanium in the solid catalyst was 3.88% by weight.

(2) Polymerization of propylene

The atmosphere in a polymerization tank stainless steel with 2 liter filling volume, which was equipped with a sheathing was sufficiently through Nitrogen gas was replaced, then "Flowbeads" (CL12007) (manufactured by Sumitomo Seika Chemicals Co., Ltd.) was introduced as the bed powder. Then were 6 mmol of triethylaluminum as catalyst component (B) and 1 mmol Bis (perhydroisoquinolino) dimethoxysilane as a catalyst component (C) added in this order and after the reaction mixture to 70 ° C had been heated, hydrogen gas became the chain transfer agent at a pressure of 0.03 MPa and propylene gas at a pressure of 0.45 MPa in the container given. Then was one previously in the container given glass ampoule, the 110 mg of the above catalyst solid included, destroyed by the onset of polymerization, the Polymerization was at 70 ° C 1 hour. While the polymerization, the propylene pressure was kept at 0.45 MPa. After more complete Unreacted propylene gas was released from polymerization, the resulting polymer was reduced at 50 ° C for 20 hours Pressure dried, so that further powdered polypropylene was obtained. The results of the determination of the polymerization activities and Properties of the polymers are shown in Tables 5 and 6.

Production Example 18

Propylene was made by processes similar to those as used in Preparation 17, polymerized with the Exception that the polymerization was carried out at 82 ° C. Results of the determination the polymerization activities and properties of the polymers are shown in Tables 5 and 6.

Comparative Example 4

Solid treated during manufacture for prepolymerization and polymerization of propylene were processes similar to those as used in Preparation Example 13 with the exception that cyclohexyldimethoxysilane instead of bis (perhydroisoquinolino) dimethoxysilane was used as the catalyst component (C). Results of the determination the polymerization temperature, polymerization activity and properties of the polymers are shown in Tables 5 and 6.

Comparative Example 5

Propylene was made by processes similar to those polymerized as used in Comparative Example 4, except that the polymerization at 82 ° C carried out has been. Results of the determination of the polymerization activity and properties of the polymers are shown in Tables 5 and 6.

Comparative Example 6

Propylene was made by processes similar to those as used in Preparation 16, polymerized with the Exception that cyclohexylmethyldimethoxysilane instead of bis (perhydroisoquinolino) dimethoxysilane was used. Results of the determination of the polymerization activity and properties of the Polymers are shown in Tables 5 and 6.

Comparative Example 7

Propylene was made by processes similar to those polymerized as used in Comparative Example 6, except that the polymerization at 82 ° C carried out has been. Results of the determination of the polymerization activity and properties of the polymer are shown in Tables 5 and 6.

Table 5

Table 6

The following are manufacturing examples represented by copolymers.

Production Example 19

(1) Manufacture of solid Catalyst component (A)

15 millimoles of anhydrous aluminum chloride were added to 40 ml of toluene, then 15 mmol of methyltriethoxysilane was added dropwise with stirring. After complete dropwise addition de the mixture reacted at 25 ° C for 1 hour. After the reaction product was cooled to -5 ° C, 18 ml of diisobutyl ether containing 30 mmol of butylmagnesium chloride was added dropwise to the reaction mixture with stirring, while maintaining the temperature of the reaction mixture in the range of -5 to 0 ° C. After the completion of the dropwise addition, the temperature of the reaction mixture was slowly raised, then the reaction was continued at 30 ° C for 1 hour. The sedimented solid was separated by filtration and washed with toluene and n- heptane. Furthermore, the solid was resuspended in 30 ml of toluene, then 150 ml of titanium tetrachloride were added and the mixture was reacted for 1 hour at 90 ° C. with stirring. The solid was separated by filtration at the same temperature and washed with toluene and then with n- heptane. The resulting solid catalyst component contains 3.55% by weight of titanium. This solid was suspended in 80 ml of heptane to make a heptane slurry of the solid catalyst component.

(2) prepolymerization

2.7 ml (2.7 mmol) of n- hexane solution of triethylaluminum as catalyst component (B) and 4.5 ml (0 ° C.) were placed in an autoclave made of stainless steel with a filling volume of 2 liters and equipped with a stirrer under a nitrogen gas atmosphere , 45 mmol) n- heptane solution containing bis (perhydroisoquinolino) dimethoxysilane and hydrogen gas at a valve pressure of 1 kg / cm ² , then 900 ml of liquefied propylene were added. The autoclave was then transferred to a water bath thermostatted at 10 ° C. and stirring was started. 10 minutes after the stirring, 9.1 mg of the solid catalyst component (A) (content of Ti = 3.55% by weight), which was prepared by (1) and was previously included, was added and the prepolymerization became 10 Minutes at 10 ° C.

(3) One-step bulk polymerization of propylene

After the prepolymerization was completed, the autoclave was immediately transferred to a thermostated vessel for main polymerization, after the temperature of the autoclave was raised to 60 ° C in 6 minutes, propylene was homopolymerized at the same temperature for 50 minutes. After the polymerization was complete, unreacted propylene gas was released from the reaction system. After the inside of the autoclave was sufficiently replaced with nitrogen gas, the internal pressure was kept at 0.2 kg / cm ² valve pressure, and 149.4 g of polymer was obtained. 31.4 g of the polymer was used as a sample for analysis.

(4) copolymerization of ethylene and propylene

(Gas phase polymerization)

A gas mixture of ethylene and propylene with a volume ratio of 1: 2 was continuously introduced (100 Ncc / min.) In an autoclave, in the interior of which a valve pressure of 0.2 kg / cm ^{2 was} maintained and the temperature was set at 40 ° C. or 200 Ncc / min), the pressure of the copolymerization was adjusted to 2 kg / cm ² valve pressure. To carry out the copolymerization at the same temperature and pressure for 4 hours, unreacted gases were released from the reaction system to keep the polymerization pressure at 2 kg / cm ² valve pressure, and the copolymerization was carried out at 40 ° C for 4 hours.

The copolymer obtained turned 20 Hours at 60 ° C dried under reduced pressure. By measuring the weight the yield of the copolymer was determined to be 10.1 g.

(Manufacture of rubber component)

five Grams of the ethylene-propylene copolymer obtained above became exact weighed out and into a container, containing 500 ml of p-xylene. Then was the copolymer dissolved by heating. Then was the solution overnight left at room temperature. By centrifugal separation solution obtained to remove the settled solid transferred into 1000 ml acetone and 1 hour with stirring left at room temperature. Deposited gummy solid was separated by a glass filter and 20 hours at 60 ° C under reduced Pressure dried so that a rubbery component was obtained. Polymerization conditions, results of the polymerization and properties of the copolymers are shown in Tables 7-11.

Examples 20-22

Copolymerizations were carried out by a method similar to that in Preparation Example 19 used, except that the polymerization conditions as shown in Table 7 were used.

Polymerization Results and Properties of the copolymers obtained are shown in Tables 8-11.

Comparative Examples 8-10

Copolymerizations were carried out by a procedure similar the one used in Preparation Example 1 except that diisopropyldimethoxysilane (DIPDMS) as a catalyst component (C) was used and polymerization conditions as in table 7 were used.

Polymerization Results and Properties of the copolymers obtained are shown in Tables 8-11.

Table 7

Table 8

Table 9 First Step Polymer (Product Before Ash Removal)

Table 10 Block copolymer (product before ash removal)

Table 11 Rubber component of the second step

Production Example 23

In a stainless steel autoclave with a filling volume of 2 liters, which was equipped with a stirrer, a glass ampoule containing an n- heptane slurry (containing 7.9 mg of the solid catalyst component) of the solid catalyst component (A), which was replaced by the im Production method 1 used was prepared, included, then the internal atmosphere of the autoclave was replaced with sufficient nitrogen gas. Then 2.1 ml of n-heptane solution containing 2.1 mmol of triethylaluminum as the organoaluminum compound of component (B) and 1.74 ml of n- heptane solution containing 0.35 mmol of bis (perhydro-indolino) dimethoxysilane contained as organosilicon compound of component (C), placed in the autoclave. After supplying hydrogen gas at a pressure of 0.2 MPa, 1.2 liters of liquefied propylene was added, then the autoclave was shaken. The autoclave was then cooled to 10 ° C. and the glass ampoule enclosing the solid catalyst component was destroyed by the start of stirring, the prepolymerization was carried out for 10 minutes. The temperature inside the autoclave was continuously raised to 70 ° C., and the polymerization was continued at 70 ° C. for 1 hour.

After polymerization was complete vented unreacted propylene gas from the autoclave, the resulting polymer was reduced at 20 ° C for 20 hours Print dried so that white powdery Polypropylene was obtained. Test results regarding polymerization activity and properties of the individual polymers are shown in Tables 12 and 13.

Example 24

Propylene was made by a process similar to that as used in Preparation Example 23, polymerized with the Exception that bis (perhydroquinolino) dimethoxysilane as a catalyst component (C) used in place of bis (perhydroindolino) dimethoxysilane has been. Results of the determination regarding the polymerization activity and properties of the polymers are shown in Tables 12 and 13.

Example 25

Propylene was made by a process similar to that as used in Preparation Example 23, polymerized with the Exception that the hydrogen gas at a pressure of 1 MPa in place of 0.7 MPa was and bis (perhydroisoindolino) dimethoxysilane as a catalyst component (C) used in place of bis (perhydroindolino) dimethoxysilane has been. Results of the determination regarding the polymerization activity and properties of the polymer are shown in Tables 12 and 13.

Example 26

Propylene was made by a process similar to that as used in Preparation Example 23, polymerized with the Exception that the hydrogen gas at a pressure of 1 MPa in place of 0.7 MPa was introduced and bis (perhydroisoquinolino) dimethoxysilane as a catalyst component (C) used in place of bis (perhydroindolino) dimethoxysilane has been. Results of the determination regarding the polymerization activity and properties of the polymer are shown in Tables 12 and 13.

Comparative Example 11

Propylene was made by a process similar to that as used in Preparation Example 23, polymerized with the Exception that cyclohexylmethyldimethoxysilane as a catalyst component (C) used in place of bis (perhydroindolino) dimethoxysilane has been.

Table 12

Table 13

Claims (12)

A process for producing an α-olefin polymer by polymerizing an α-olefin in the presence of a catalyst containing the following catalyst components (A), (B) and (C): (A) a solid catalyst component which is compulsorily magnesium, titanium, a halogen and contains an electron donor, (B) an organoaluminum compound and (C) an aminosilane compound according to the following general formula (1):

(wherein R ^{1 represents} a hydrocarbon radical having 1 to 8 carbon atoms; and

represents a polycyclic amino group with 7 to 40 carbon atoms, which form the polycyclic skeleton bonded to the nitrogen atom). The method of claim 1, wherein the α-olefin is Propylene, 1-butene, 1-hexene, 1 methylene or 1-octene. The method of claim 1, wherein the ratio of Amount of silicon atoms of the catalyst components (C) to the amount the aluminum atoms of the catalyst component (B) 0.01 to 1.0 in terms of the Si / Al atomic ratio, is. The process according to claim 1, wherein the catalyst component (C) is bis (perhydroisoquinolino) dimethoxysilane, bis (perhydroquinolino) dimethoxysilane), bis (perhydroisoindolino) dimethoxysilane, Bis (perhydroindolino) dimethoxysilane) or (perhydroquinolino) (perhydroisoquinolino) dimethoxysilane. The method of claim 1, wherein the polymerization an α-olefin in gaseous Condition. A process for producing a propylene block copolymer which comprises: (1) a step for producing a crystalline propylene polymer containing at most 10% by weight of an α-olefin by polymerizing propylene or propylene with an α-olefin other than propylene, and ( 2) a step for producing a rubbery propylene copolymer containing 10 to 40% by weight of an α-olefin by polymerizing propylene with an α-olefin other than propylene in the presence of a catalyst which contains the following catalyst components (A), (B) and (C) contains: (A) a solid catalyst component which contains magnesium, titanium, a halogen and an electron donor, (B) an organoaluminum compound and (C) an aminosilane compound according to the following general formula (1):

(wherein R ^{1 represents} a hydrocarbon radical having 1 to 8 carbon atoms; and

represents a polycyclic amino group with 7 to 40 carbon atoms, which form the polycyclic skeleton bonded to the nitrogen atom). The method of claim 6, wherein step (2) a gas phase copolymerization of propylene with one of propylene different α-olefin without deactivating the catalyst after the polymerization of propylene or propylene with an α-olefin other than propylene in the Step (1) is. The method of claim 6, wherein the content of the rubbery Propylene copolymer with an α-olefin other than propylene in the Propylene block copolymer is 3 to 40% by weight. The method of claim 6, wherein the α-olefin other than propylene around ethylene, butene-1, 3-methylbutene-1, 3-methylpentene-1, 4-methylpentene-1, hexene-1, 4-methylhexene-1, octene-1, styrene, 2-methylstyrene, 3-methylstyrene, Cyclopentene, cyclohexene or cyclopentadiene. Aminosilane compound of the following general formula (1):

(wherein R ^{1 represents} a hydrocarbon radical having 1 to 8 carbon atoms; and

represents a polycyclic amino group with 7 to 40 carbon atoms, which form the polycyclic skeleton bonded to the nitrogen atom). The silane compound according to claim 10, wherein R ^{1 represents} a methyl group; and

stands for a perhydroisoquinolino group, perhydroquinolino group, perhydroisoindolino group or perhydroindolino group. Aminosilane compound according to claim 10, wherein it the compound according to the general formula (1) um bis (perhydroisoquinolino) dimethoxysilane, bis (perhydroquinolino) dimethoxysilane, Bis (perhydroisoindolino) dimethoxysilane, bis (perhydroindolino) dimethoxysilane or (perhydroquinolino) (perhydroisoquinolino) dimethoxysilane.