JPH08198968A - Production of metallopolymeric silicon compound - Google Patents

Abstract

PURPOSE: To efficiently obtain under mild conditions a polymeric silicon compound having alternate recurring structure of metallocene and silylene by ring opening polymerization of a metallocyclic silicon compound in the presence of a Pt or Pd catalyst. CONSTITUTION: This metallopolymeric silicon compound of formula II is obtained by ring opening polymerization esp. pref. at 0-80 deg.C of a silylene-cross- linked metallocene compound of formula I (R<1> and R<2> are each a halogen, hydrocarbon, alkoxyl or aryloxyl; R<3> and R<10> are each H or an alkyl; M is Fe or Ru) in the presence of a Pt catalyst such as bis(1,5-cyclooctadiene)platinum or Pd catalyst such as bis(dibenzylideneacetone)palladium.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an improvement in a method for producing a metal-containing polymer silicon compound. More specifically, the present invention is a heat-resistant material, a material for engineering plastics, optical and electronic materials, a polymeric silicon compound having an alternating repeating structure of silylene and a silylene-bridged metallocene compound, which are useful as materials for ceramics and the like. By ring-opening polymerization under various conditions,
The present invention relates to an efficient manufacturing method.

[0002]

2. Description of the Related Art Conventionally, metal-containing polymeric silicon compounds have been known to be thermally stable and useful as heat-resistant materials and materials for engineering plastics, and also metallocene-based polymeric silicon compounds. In the case of a compound, it can be applied to an optical / electronic material utilizing the electrical oxidation / reduction of metallocene. Further, these polymers have been attracting attention as raw materials for new ceramic materials composed of silicon, carbon, metals, etc., when they are fired.

By the way, polymeric silicon compounds having an alternating repeating structure of metallocene and silylene have hitherto been produced mainly by thermal ring-opening polymerization of silylene-bridged metallocene compounds. However, in this method, in order to proceed the reaction smoothly, it is necessary to carry out the reaction at a high temperature [eg, "Journal of the American Chemical Society (J. Am. Ch.
em. Soc. ), 114, 6246 (1
1992)], and the reaction could not be efficiently performed under mild conditions such as 100 ° C. or lower.

[0004]

DISCLOSURE OF THE INVENTION The present invention overcomes the drawbacks of the prior art and provides a method for efficiently producing a polymeric silicon compound having an alternating repeating structure of metallocene and silylene under mild conditions. It was made for the purpose of providing.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies as to a method for producing a polymer silicon compound having a repeating unit of metallocene and silylene, and as a result, the silylene-bridged metallocene compound has been identified as a catalyst of a specific catalyst. Based on this finding, the present invention has been completed based on the finding that a ring-opening polymerization can be easily carried out under mild conditions under the presence of the polymer to efficiently give a polymer silicon compound having an alternating repeating structure of metallocene and silylene.

That is, the present invention has the general formula in the presence of a platinum or palladium catalyst.

Embedded image (In the formula, R ¹ and R ² are each a halogen atom, a hydrocarbon group, an alkoxy group or an aryloxy group, and they may be the same or different, and R ³ to R ¹⁰ Are each a hydrogen atom or an alkyl group, which may be the same or different from each other, and M is iron or ruthenium). General formula, characterized by

[Chemical 4] (Wherein R ¹ to R ¹⁰ and M have the same meanings as described above, and n is an integer of 2 or more).

In the method of the present invention, a metal-containing cyclic silicon compound represented by the above general formula (I), that is, a silylene-bridged metallocene compound is used as a raw material. In the compound represented by the general formula (I), R ¹ and R ²
Are each a halogen atom, a hydrocarbon group, an alkoxy group or an aryloxy group, and examples of the halogen atom include a fluorine atom and a chlorine atom.
Further, the hydrocarbon group is an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or the like, and the alkyl group or the alkenyl group may be linear or branched. Specific examples of such a hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n
Examples include -butyl group, isobutyl group, sec-butyl group, t-butyl group, hexyl group, phenyl group, tolyl group, naphthyl group, benzyl group, phenethyl group and styryl group. Furthermore, specific examples of the alkoxy group and aryloxy group include a methoxy group, an ethoxy group, a phenoxy group,
Examples thereof include a benzyloxy group. The R ¹ and R ² may be the same or different. On the other hand, R ³ to R ¹⁰ are each a hydrogen atom or an alkyl group, and the alkyl group is preferably a lower alkyl group such as a methyl group, an ethyl group, an n-propyl group or an isopropyl group. it can. The R ³
To R ¹⁰ may be the same or different.

Examples of the compound represented by the general formula (I) include (1,1'-ferrocenediyl) dimethylsilane, (1,1'-ferrocenediyl) diethylsilane, and (1,1'-ferrocenediyl). Dipropylsilane, (1,1'-ferrocenediyl) diisobutylsilane, (1,1'-ferrocenediyl) hexylmethylsilane, (1,1'-ferrocenediyl) methylphenylsilane, (1,1'-ferrocenediyl) ) Methyl (1-
Or 2-naphthyl) silane, (1,1′-ferrocenediyl) benzylmethylsilane, (1,1′-ferrocenediyl) methylphenethylsilane, (1,1′-ferrocenediyl) methylstyrylsilane, (1,1 '-Ferrocenediyl) dimethoxysilane, (1,1'-ferrocenediyl) diethoxysilane, (1,1'-ferrocenediyl) diphenoxysilane, (1,1'-ferrocenediyl) difluorosilane, (1,1 ′ -Ferrocenediyl) dichlorosilane, (2,2 ′-, 2,3′-,
2,4'-, 2,5'-, 3,3'- or 3,4'-dimethylferrocene-1,1'-diyl) dimethylsilane, (1,1'-ruthenocenediyl) dimethylsilane,
(1,1'-ruthenocenediyl) diphenylsilane and the like can be mentioned.

In the method of the present invention, a platinum or palladium catalyst is used as a catalyst. As the platinum or palladium catalyst, various ones including conventionally known ones such as platinum or palladium metal complex, metal salt, metal or supported metal catalyst can be used. Specific examples of this catalyst include bis (1,5-cyclooctadiene) platinum, dichloro (1,5-cyclooctadiene) platinum, bis (benzonitrile) dichloroplatinum, tris (dibenzylideneacetone) diplatinum, dichloro (1,5-Cyclooctadiene) palladium, bis (dibenzylideneacetone) palladium, dichlorobis (benzonitrile) palladium, di-μ-chlorobis (π-allyl) dipalladium, dichloro (1,5-cyclooctadiene) palladium , Dichlorobis (pyridine) palladium, tetrakis (triphenylphosphine) palladium, dichlorobis (triethylphosphine) palladium, diiodobis (diethylphenylphosphine) palladium, dibromo [1,2-bis (diphenylphosphino) butane] palladium, Chlorobis (triphenylphosphine) palladium, chloroplatinic acid, platinum chloride, palladium acetate, palladium chloride, palladium iodide, activated carbon-supported platinum, etc. palladium on charcoal and the like.

These catalysts may be used alone or in combination of two or more kinds, and the same ligands as those contained in the metal compounds exemplified above should be used together. You can also

In the present invention, the amount of these platinum or palladium catalysts to be used is not particularly limited, but it is a ratio such that the molar ratio is 0.0001 to 0.5 with respect to the silylene-bridged metallocene compound which is usually the starting material. Used in.
Furthermore, in the present invention, the ring-opening polymerization reaction is usually -1.
It is carried out at a temperature of 00 ° C or higher, preferably -80 to 100 ° C, more preferably 0 to 80 ° C. The ring-opening polymerization reaction is carried out in the absence or presence of a solvent. When a solvent is used, the solvent is a solvent inert to the reaction, such as benzene, toluene, xylene, hexane, decalin, etc. The hydrocarbon-based solvent, the ether-based solvent such as dibutyl ether, and the like can be used.

There is no particular limitation on the method for separating and purifying the desired metal-containing polymer silicon compound from the reaction-completed liquid, and there are known commonly used methods such as reprecipitation method and chromatography method. It can be purified.

In this way, the general formula

Embedded image A metal-containing polymeric silicon compound represented by the formula (R ¹ to R ¹⁰ and M in the formula have the same meanings as described above and n is an integer of 2 or more) is obtained. This metal-containing polymer silicon compound usually has a weight average molecular weight of 500 or more.

Specific examples of the metal-containing polymer silicon compound represented by the general formula (II) include poly [(1,1 '
-Ferrocenediyl) (dimethylsilylene)], poly [(1,1'-ferrocenediyl) (diethylsilylene)], poly [(1,1'-ferrocenediyl) (dipropylsilylene)], poly [(1, 1'-ferrocenediyl) (diisobutylsilylene)], poly [(1,1 '
-Ferrocenediyl) (hexylmethylsilylene)],
Poly [(1,1'-ferrocenediyl) (diphenylsilylene)], poly [(1,1'-ferrocenediyl)
(Methylphenylsilylene)], poly {(1,1′-ferrocenediyl) [methyl (1- or 2-naphthyl) silylene]}, poly [(1,1′-ferrocenediyl)
(Benzylmethylsilylene)], poly [(1,1′-ferrocenediyl) (methylphenethylsilylene)], poly [(1,1′-ferrocenediyl) (methylstyrylsilylene)], poly [(1,1 ′ -Ferrocenediyl)
(Dimethoxysilylene)], poly [(1,1′-ferrocenediyl) (diethoxysilylene)], poly [(1,
1'-ferrocenediyl) (diphenoxysilylene)], poly [(1,1'-ferrocenediyl) (difluorosilylene)], poly [(1,1'-ferrocenediyl) (dichlorosilylene)], poly [( 2,2'-,
2,3'-, 2,4'-, 2,5'-, 3,3'-, or 3,4'-dimethylferrocene-1,1'-diyl)
(Dimethylsilylene)], poly [(1,1′-ruthenocenediyl) (dimethylsilylene)], poly [(1,1 ′
-Ruthenocenediyl) (diphenylsilylene)] and the like.

[0015]

According to the present invention, a silylene-bridged metallocene compound is subjected to ring-opening polymerization under a mild condition using a platinum or palladium catalyst to efficiently produce a polymer silicon compound having an alternating repeating structure of metallocene and silylene. It can be manufactured, and its separation and purification are easy.

The metal-containing polymer silicon compound obtained by the method of the present invention is useful as, for example, a heat resistant material, a material for engineering plastics, an optical / electronic material, a material for ceramics and the like.

[0017]

EXAMPLES The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 Bis (1,5-cyclooctadiene) platinum 0.004 m
mol, 0.20 mmol of (1,1′-ferrocenediyl) dimethylsilane and 0.5 ml of benzene were heated under nitrogen in a sealed tube at 70 ° C. for 12 hours. Next, benzene was added to the red-orange reaction solution and the mixture was filtered, and the filtrate was concentrated under reduced pressure. When the concentrate was reprecipitated from benzene-hexane, 44 mg of poly [(1,1'-ferrocenediyl) (dimethylsilylene)], a yellow solid polymer silicon compound (0.18 mmo per repeating unit) was obtained.
1, yield 91%) was obtained.

This product had a weight average molecular weight Mw (based on standard polystyrene) of 8.0 × 10 ⁵ and a polydispersity (weight average molecular weight / number average molecular weight Mw / Mn) of 6.2.

Examples 2 to 10 were carried out in the same manner as in Example 1 under the reaction conditions shown in Table 1,
Poly [(1,1'-ferrocenediyl) (dimethylsilylene)] was prepared. The results are shown in Table 1.

[0021]

[Table 1] [Note] 1) cod: 1,5-cyclooctadiene dba: dibenzylideneacetone py: pyridine 2) Purified poly [(1,1′-ferrocenediyl)
(Dimethylsilylene)] 3) Purified poly [(1,1'-ferrocenediyl)]
(Dimethylsilylene)] molecular weight (based on standard polystyrene), Mw: weight average molecular weight, Mw / Mn: polydispersity (weight average molecular weight / number average molecular weight) 4) Bimodal molecular weight distribution (high molecular component / low molecular component) = 3
4/66), polymer component: Mw = 1.0 × 10 ⁶ (Mw
/Mn=1.5), low molecular weight component: Mw = 6.9 × 10 ^4.
(Mw / Mn = 3.1) 5) Unpurified, insoluble solid Common polymerization conditions: (1,1′-ferrocenediyl) dimethylsilane 0.20 mmol, catalyst 0.004 mmol
(Per Pt or Pd), benzene 0.5 ml

Claims (2)

[Claims] 1. A compound of the general formula: ## STR1 ## in the presence of a platinum or palladium catalyst. (In the formula, R ¹ and R ² are each a halogen atom, a hydrocarbon group, an alkoxy group or an aryloxy group, and they may be the same or different, and R ³ to R ¹⁰ Are each a hydrogen atom or an alkyl group, which may be the same or different from each other, and M is iron or ruthenium). And a general formula: (R ¹ to R ¹⁰ and M in the formula have the same meanings as described above, and n is an integer of 2 or more). 2. The production method according to claim 1, wherein the reaction temperature is 0 to 80 ° C.