JPH0673182A - Dehydrogenation condensation catalyst of organosilicon monomer - Google Patents

Abstract

PURPOSE:To obtain the subject catalyst providing an organosilicon polymer from an organosilicon monomer in a short time efficiently because of high activity, being readily synthesized, having easy handleability, comprising a specific metallocene compound and an organometallic compound. CONSTITUTION:The objective catalyst comprises (A) a metallocene dihalide of the formula CP2MX2 [Cp is (substituted) eta<5>-cyclopentadienyl; M is Ti, Zr or Hf; X is F, Cl, Br or I] compound and (B) an organometallic compound of a metal of group 12 or group 13. The component A is preferably synthesized from a cyclopentadienyl Grignard reagent and a corresponding metal halide. An organometallic compound of boron, aluminum or zinc such as [(CH3)C]3Al, triethylboron or Zn(CH=CH2)2 is preferable as the component B. In the case of dehydration condensation of an organosilicon by using the catalyst, the amount of the component A used is preferably 1X10<-4>-10mol% based on the organosilicon monomer and that of the component B is preferably 1X10<-7>-10<4>mol% based on the component A.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a catalyst used for producing an organosilicon polymer, and more particularly to a catalyst used for producing an organosilicon polymer by dehydrogenative condensation of an organosilicon monomer.

[0002]

Organosilicon polymers are used as electronic material devices, photoresist materials and photoinitiators, as well as carbonized silicon carbide fibers, silicon carbide binders, silicon carbide sheets, silicon carbide coatings and silicon carbide sintered bodies. It is a polymer useful as a precursor of silicon materials.

Organosilicon polymers have hitherto been synthesized by the Wurtz reaction of dihalosilane, the dehydrogenative condensation of hydrosilane, or the like.

However, the method for preparing the organosilicon polymer by the Wurtz reaction of dihalosilane is known as dihalosilane 1
More than 2 mol of alkali metal is needed per mol, and there is a risk of ignition of alkali metal, etc .; reaction conditions are extreme, types of side chains that can be produced are limited; molecular weight and molecular weight distribution Poor controllability; a large amount of salt is by-produced, and the yield of organosilicon polymer is 10 ~
It is as low as 50%; and a small amount of chlorine, which is a by-product, remains in the organosilicon polymer (it is difficult to remove it) and the electrical properties of the organosilicon polymer deteriorate. Have.

On the other hand, in recent years, a dehydrogenative condensation reaction of hydrosilane using a transition metal complex catalyst has become known. For example, E. Hengge et al. Have used Cp ₂ TiMe ₂ , Cp ₂ ZrMe ₂ , Cp ₂ Ti (n- as catalysts.
Bu) ₂ , Cp ₂ Zr (n-Bu) ₂ (where Cp represents a cyclopentadienyl group, Me represents a methyl group, and Bu represents a butyl group. Hereinafter, similarly, an ethyl group is Et and propyl group. Group is Pr, normal hexyl group is n-Hex, cyclohexyl group is c-Hex, toluyl group is tol, and phenyl group is sometimes abbreviated as Ph.), Dimethyldisilane is converted into oligosilane or polysilane. (J. Organomet. Che
m., 410, C1 to C4,1991). As described above, a metallocene catalyst is mainly used as a catalyst used in the dehydrogenative condensation reaction, and in addition, for example, Harrod et al. Use Cp ₂ TiMe ₂ , Cp ₂ ZrMe ₂ , Cp ₂ as a catalyst.
A linear organosilicon polymer is synthesized from organotrihydrosilane using Ti (CH ₂ Ph) ₂ or the like (J.Organomet.Chem., 279, C11-C13,1985, CAN.J.CHEM. V
OL.65,1804-1809,1987). Further, in JP-A-2-67288, a linear organosilicon polymer is synthesized by using Cp ₂ TiAr ₂ (where Ar is a substituted or unsubstituted phenyl group or naphthyl group) as a catalyst. . Compared with the method using the Wurtz reaction, these methods have the advantages that they proceed under relatively mild conditions, that the only by-product is hydrogen, which is easy to separate, and that the yield is as high as 80%. .

[0006]

In the method using the above-mentioned dehydrogenative condensation reaction, a transition metal complex catalyst is used, but those complexes require several steps of chemical reaction for synthesis.

Therefore, an object of the present invention is to provide a dehydrogenative condensation catalyst for organosilicon monomers which is easy to synthesize and highly active.

[0008]

The present invention provides, as a first component, a compound of the formula Cp ₂ MX ₂ (wherein each Cp independently represents a substituted or unsubstituted η ⁵ -cyclopentadienyl group, Cyclopentadienyl groups may be covalently bonded to each other via one or more atoms, M is Ti, Zr,
Hf and X represents F, Cl, Br and I. ) Metallocene dihalide, and the first component as the second component
A catalyst for dehydrogenative condensation of an organosilicon monomer, which comprises an organometallic compound of a Group 2 or Group 13 metal.

The metallocene dihalide used as the first component is, for example, Cp ₂ TiCl ₂ , Cp ₂ ZrCl.
_{2, Cp 2 HfCl 2, Cp} 2 TiBr 2, Cp 2 Zr
Br ₂ , Cp ₂ HfBr ₂ , Cp ₂ TiI ₂ , Cp ₂ Z
rI ₂ , Cp ₂ HfI ₂ , Cp ^* ₂ TiCl ₂ , Cp ^*
₂ ZrCl ₂ , Cp ^* ₂ HfCl ₂ , Cp ^* ₂ TiB
r ₂ , Cp ^* ₂ ZrBr ₂ , Cp ^* ₂ HfBr ₂ , Cp
^* ₂ TiI ₂ , Cp ^* ₂ ZrI ₂ , Cp ^* ₂ HfI ₂ ,
Cp ^* CpTiCl ₂ , Cp ^* CpZrCl ₂ , C
p ^* CpHfCl ₂ , Cp ^* CpTiBr ₂ , Cp ^* C
pZrBr ₂ , Cp ^* CpHfBr ₂ , Cp ^* CpTi
I ₂ , Cp ^* CpZrI ₂ , Cp ^* CpHfI
₂ (where Cp ^* is

[0010]

[Chemical 1] Indicates. ), And the following formula:

[0011]

[Chemical 2]

[0012]

[Chemical 3] Etc. Here, as the atom that bonds the two cyclopentadienyl groups of the metallocene dihalide used as the first component by a covalent bond, for example, C, S
Examples thereof include i, O, N, Ge and the like. It is desirable to use the first component separately synthesized and purified, but it is also possible to add the raw materials for producing these components to the reaction system and prepare it in the system. Further, these components may be supported on a carrier before use.

The first component used in the present invention is G.I. It has been synthesized by Wilkinson et al. From a cyclopentadienyl Grignard reagent and the corresponding metal halide (J. Am. Chem. S.
oc. , 76, 4281-4284, 1954). Moreover, a commercial item can also be utilized.

As the second component, an organometallic compound of Group 12 or Group 13 metal is used.

Here, the Group 12 metal represents zinc, cadmium and mercury, and the Group 13 metal represents boron, aluminum, gallium, indium and thallium. Particularly, boron, aluminum and zinc are preferably used.

Examples of the organic group bonded to these metals include
Examples thereof include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and an aralkyl group. Some of them may be substituted with an alkoxyl group, a halogen atom, or the like, or may be substituted.

The alkyl group preferably has 1 to 20 carbon atoms, and particularly preferably 1 to 5 carbon atoms. The alkenyl group preferably has 1 to 20 carbon atoms, and particularly preferably 1 to 8 carbon atoms. The alkyl group and alkenyl group may be linear or branched. The aryl group and aralkyl group preferably have 6 to 20 carbon atoms, and particularly 6 to 1 carbon atoms.
Two is preferable.

Examples of the organometallic compound of Group 12 or Group 13 metal include Et ₂ Zn, Et ₃ B, Me ₃ A
1, Et ₃ Al, i-Bu ₃ Al, Me ₂ AlCH ₂ A
1Me ₂ , H ₂ C = C (CH ₃ ) CH ₂ AlMe ₂ , A
l (CH ₂ CH ₂ CH = CH ₂ ) ₃ , [(CH ₃ )
₃ C] ₃ Al, ZnMe ₂ ,

[0019]

[Chemical 4] Et ₂ AlCH = CHCH ₂ CH ₃ , PhAlEt ₂ ,
Ph ₃ Al, ZnPh ₂ , Zn (HC = CH ₂ ) ₂ ,

[0020]

[Chemical 5] Et ₂ AlOAc, EtAl (OEt) ₂ , Me ₂ Al
OPh, PhCOOAlEt ₂ , EtZnOAc, Et
ZnOEt, EtZnOCPh ₃ , Et ₂ AlOEt,

[0021]

[Chemical 6] Cl ₂ AlCH ₂ AlCl ₂ , EtAlCl ₂ , EtA
_{lI 2, (CH 3) 3} CAlCl 2, PhCH 2 AlC
l ₂ , MeZnCl, Zn (CH ₂ I) ₂ , EtZn
I, (CH ₃ ) ₃ CZnCl, PhZnBr, PhZn
Cl, EtZnCl, Me ₂ AlCl, Et ₂ AlC
1, Et ₂ AlCN, Et ₂ AlNHMe, Me ₂ Al
_{SC (CH 3) 3, (} Me 3 SiCH 2) 3 Al,

[0022]

[Chemical 7] Etc. (where:

[0023]

[Chemical 8] Represents a cyclopropyl group. Hereinafter, a cyclobutyl group and the like may be referred to in the same manner. ).

The catalyst of the present invention is one of organosilicon monomers having at least one hydrosilyl group, such as hydrosilane, dihydrosilane, trihydrosilane, or an organosilicon compound monomer having a hydrosilyl group, dihydrosilyl group, or trihydrosilyl group. The above is used for dehydrogenative condensation to produce an organosilicon polymer.

As the above-mentioned organosilicon compound monomer,
For example, the following compounds may be mentioned. MeSiH ₃ , Et
_{SiH 3, PhSiH 3, Me 3} SiSiH 3,

[0026]

[Chemical 9] ,as well as

[0027]

[Chemical 10] ,as well as

[0028]

[Chemical 11], And H₃Si-CH₂-SiH₃, H₃Si-CH
(SiMe₃) -SiH₃, H₃Si-CH (Me)-
SiH₃, H₃Si-CH (Et) -SiH₃, H₃S
i-CH (n-Pr) -SiH₃, H₃Si-C (M
e)₂-SiH₃, H₃Si-CH (i-Pr) -Si
H₃, H₃Si-C (Me) (Et) -SiH ₃, H₃
Si-C (Me) (SiMe₃) -SiH₃, H₃Si
-C (Et) (SiMe₃) -SiH₃, H₃Si-C
(SiMe₃)₂-SiH₃, H₃Si-CH₂CH
(Me) -SiH₃, H₃Si-CH₂CH (Et)-
SiH₃, H₃Si-CH₂C (Me)₂-SiH₃,
H₃Si-CH (Me) CH (Me) -SiH₃, H₃
Si-CH₂CH (SiMe₃) -SiH₃, H₃Si
-CH₂C (Me) (SiMe₃) -SiH₃, H₃S
i-CH₂C (SiMe₃)₂-SiH₃, H₃Si-
CH (Me) CH (SiMe₃) -SiH₃, H₃Si
-CH (SiMe₃) CH (SiMe₃) -SiH₃,
H₃Si- (CH₂)₃-SiH₃, H₃Si- (CH
₂)₂CH (Me) -SiH₃, H₃Si-CH (Si
Me₃) CH₂CH₂-SiH₃, H₃Si-CH₂C
H (SiMe₃) CH₂-SiH₃, H₃Si-CH =
CHCH₂-SiH₃, H₃Si- (CH₂)_Four-Si
H₃, H₃Si-CH = CHCH = CH-SiH₃, H
₃Si-CH₂CH = CHCH₂-SiH₃,

[0029]

[Chemical 12] And

[0030]

[Chemical 13] The dehydrogenative condensation reaction carried out using the catalyst of the present invention may be carried out in an open system or a closed system. The reaction may be carried out in a liquid phase or without a solvent, but is preferably a hydrocarbon solvent such as hexane, benzene or toluene, and / or tetrahydrofuran (TH
F), in the presence of a solvent such as ether. As an example of preferable reaction conditions, preferably 1.0 × 10 ^{−7 to} 100 mol%, particularly preferably 1.0 × 10 ⁻⁴ to 10 mol% of the formula Cp ₂ M of the first component with respect to the organosilicon monomer.
The metallocene dihalide represented by X ₂ , and preferably 1.0 × 10 ⁻¹⁰ to 10 ⁵ mol% relative to the first component,
Particularly preferably, the reaction system is placed under a non-oxidizing gas atmosphere of hydrogen, nitrogen, argon, helium, etc., using the above-mentioned catalyst consisting of 1.0 × 10 ⁻⁷ to 10 ⁴ mol% of the second component organometallic compound. , The reaction temperature is about −60 to 300 ° C., more preferably about 20 to 180 ° C., and the reaction time is about 5 minutes to 10 days,
More preferably, it is about 10 minutes to 48 hours. The repeating unit, molecular weight, dehydrogenation rate, and degree of crosslinking of the polymer can be changed by changing the temperature, reaction time, catalyst, etc. during the reaction. For example, when the reaction temperature is low and the reaction time is short, the molecular weight is low, and conversely, when the reaction temperature is high and the reaction time is long, the molecular weight is high.

Although the present invention is not limited by a particular theory, the reason why the catalyst of the present invention exerts its effect is that the metallocene dihalide as the first component, the organometallic compound as the second component, and the reacting organic compound. It is considered that the three silicon monomers participate in each other to proceed the reaction, and at this time, the organometallic compound as the second component acts as a reducing agent to reduce the metallocene dihalide and generate a reactive species.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

[0033]

【Example】

[0034]

Example 1 5.0 g of phenylsilane as a monomer
(46 mmol), toluene 5 ml, Cp ₂ TiCl ₂
87 mg (0.33 mmol, 0.7 for monomer)
2 mol%), 0.70 mmol of trimethylaluminum (7 ml of 0.1 M hexane solution) were added to a pressure resistant reactor of 100 ml capacity equipped with a needle valve and a magnetic stirrer,
After freezing and deaeration twice, the tube was sealed under a nitrogen atmosphere. This was heated in an oil bath at 50 ° C. for 5 hours, passed through a Florisil column (toluene solvent) to remove the catalyst, and then the solvent was distilled off under reduced pressure. 4.5 g of organosilicon polymer was obtained (yield 90
%). The molecular weight by GPC analysis is M in terms of polystyrene.
_n (number average molecular weight) 690, M _w (weight average molecular weight) 9
It was 20. ¹ H-NMR of this organosilicon polymer
When the spectrum was measured (the spectrum is shown in FIG. 1), the peak due to hydrogen bonded to the silicon atom at 4.2 to 4.8 ppm was due to the proton of the phenyl group at 6.6 to 7.8 ppm. Each peak was observed (the peak of the methyl group of the residual solvent toluene at 2.1 ppm and the peak of the internal standard reagent tetramethylsilane at 0 ppm). Further, the IR spectrum of this organosilicon polymer was measured (the spectrum is shown in FIG. 2), and Si—H and Si—H were found around 2107 cm ⁻¹ .
_A peak based on ₂ and a peak based on Si—H ₂ were observed near 911 cm ⁻¹ .

[0035]

Example 2 n-hexylsilane as a monomer 5.
3 g (46 mmol), hexane 3 ml, Cp ₂ ZrC
96 mg (0.33 mmol, 0.72 mol% with respect to the monomer) of 1 _{2 and} 0.70 mmol of triethylborane (7 ml of 0.1 M hexane solution) were treated in the same manner as in Example 1, and then treated with an oil bath at 150 ° C. The mixture was heated at 10 ° C. for 10 hours, passed through a Florisil column (toluene solvent) to remove the catalyst, and then the solvent was distilled off under reduced pressure. 4.4 g of organosilicon polymer was obtained (yield 83%). The molecular weight by GPC analysis was M _n 610 and M _w 810 in terms of polystyrene.

[0036]

Example 3 4.8 g (46 mmol) of 1,1,1-trimethyldisilane as a monomer, 5 ml of benzene,
Cp ₂ HfCl ₂ 125 mg (0.33 mmol, 0.72 mol% relative to monomer), dimethylaluminum chloride 0.70 mmol (0.1 M hexane solution 7 ml)
Was treated in the same manner as in Example 1, then heated in an oil bath at 70 ° C. for 6 hours, passed through a Florisil column (toluene solvent) to remove the catalyst, and then the solvent was distilled off under reduced pressure. 4.1 g of organosilicon polymer was obtained (yield 85%). The molecular weight by GPC analysis is polystyrene conversion M _n 4320, M _w 125
It was 00.

[0037]

Example 4 p-Tolylsilane as a monomer 5.6
g (46 mmol), hexane 5 ml, Cp ₂ ZrBr
₂ 126 mg (0.33 mmol, 0.72 mol% with respect to the monomer) and 0.70 mmol triethylaluminum (0.1 ml hexane solution 7 ml) were treated in the same manner as in Example 1, and then treated in an oil bath at 50 ° C. After heating for 10 hours and passing through a Florisil column (toluene solvent) to remove the catalyst, the solvent was distilled off under reduced pressure. 5.0 g of organosilicon polymer was obtained (yield 89%). The molecular weights by GPC analysis were M _n 760 and M _w 1010 in terms of polystyrene.

[0038]

Example 5 5.2 g (46 mmol) of cyclohexylsilane as a monomer, 5 ml of THF, Cp ₂ Zr
I ₂ 157 mg (0.33 mmol, 0.72 mol% based on monomer), diethylaluminum chloride 0.70
After treating millimoles (0.1 M hexane solution 7 ml) in the same manner as in Example 1, the mixture was heated in an oil bath at 110 ° C. for 8 hours, passed through a Florisil column (toluene solvent) to remove the catalyst, and then the solvent was distilled off under reduced pressure. did. 4.6 g of organosilicon polymer was obtained (88% yield). The molecular weight by GPC analysis was M _n 310 and M _w 490 in terms of polystyrene.

[0039]

Example 6 2-silylbutane 4.0 as a monomer
g (46 mmol), diethyl ether 5 ml, CpC
119 mg of p ^* ZrCl ₂ (0.33 mmol, 0.72 mol% based on monomer), 0.70 mmol of diethylaluminum ethoxide (7 m of 0.1 M hexane solution)
After treating 1) in the same manner as in Example 1, the mixture was heated in an oil bath at 130 ° C. for 7 hours, passed through a Florisil column (toluene solvent) to remove the catalyst, and then the solvent was distilled off under reduced pressure. 3.7 g of organosilicon polymer was obtained (yield 93%). The molecular weight by GPC analysis is polystyrene converted into M _n 630 and M _w 7
It was 70.

[0040]

Example 7 5.6 g (46 mmol) of phenylmethylsilane as a monomer, 5 ml of toluene, Cp ₂ Z
rCl ₂ 96 mg (0.33 mmol, 0.72 mol% based on monomer), ethyl aluminum dichloride 0.7
0 mmol (7 ml of 0.1 M hexane solution) was used in Example 1
After the same treatment as above, the mixture was heated in an oil bath at 150 ° C. for 15 hours, passed through a Florisil column (toluene solvent) to remove the catalyst, and then the solvent was distilled off under reduced pressure. 4.9 g of organosilicon polymer was obtained (yield 88%). The molecular weights by GPC analysis were _Mn 290 and _Mw 460 in terms of polystyrene.

[0041]

Example 8 6.1 g (46 mmol) of 2-trimethylsilylethylsilane as a monomer and 5 m of toluene
1, Cp ₂ ZrCl ₂ 96 mg (0.33 mmol, 0.72 mol% relative to the monomer), triisobutylaluminum 0.70 mmol (0.1 M hexane solution 7 m
l) was treated as in Example 1 and then treated in an oil bath at 80 ° C. for 5 hours.
After heating for a while and passing through a Florisil column (toluene solvent) to remove the catalyst, the solvent was distilled off under reduced pressure. 5.3 g of organosilicon polymer was obtained (yield 87%). The molecular weight by GPC analysis is _Mn 890, M _w 12 in terms of polystyrene.
It was 10.

[0042]

Example 9 5.5 g (46 mmol) of 2,2-dimethyltrisilane as a monomer, 5 ml of toluene, Cp
₂ ZrCl ₂ 96 mg (0.33 mmol, 0.72 mol% with respect to the monomer) and diethyl zinc 0.70 mmol (0.1 M hexane solution 7 ml) were treated in the same manner as in Example 1, and then oil at 80 ° C. The mixture was heated in a bath for 6 hours, passed through a Florisil column (toluene solvent) to remove the catalyst, and then the solvent was distilled off under reduced pressure. 4.9 g of organosilicon polymer was obtained (yield 89%). The molecular weights by GPC analysis were M _n 4550 and M _w 23300 in terms of polystyrene.

[0043]

Example 10: Disilylethane 4.1 as a monomer
g (46 mmol), ether 5 ml, Cp ₂ ZrCl
₂ 96 mg (0.33 mmol, 0.
72 mol%) and 0.72 mmol of C ₂ H ₅ ZnCl (7 ml of 0.1 M ether solution) were treated in the same manner as in Example 1, and then heated in an oil bath at 60 ° C. for 5 hours to remove the solvent. 6 g of organosilicon polymer was obtained (yield 88
%). The molecular weight by GPC analysis is M in terms of polystyrene.
_n 3900 and _Mw 19200.

[0044]

Comparative Example 1 5.0 g of phenylsilane as a monomer
(46 mmol), benzene 5 ml, Cp ₂ ZrCl ₂
96 mg (0.33 mmol, 0.7 for monomer)
(2 mol%) was added to a pressure resistant reactor having a capacity of 100 ml equipped with a needle valve and a magnetic stirrer, freeze-deaerated twice, and then sealed under a nitrogen atmosphere. 1 in an oil bath at 150 ° C
Heated for 5 hours. No polymer was obtained and the monomer phenylsilane was recovered.

[0045]

[Comparative Example 2] 5.0 g of phenylsilane as a monomer
(46 mmol), benzene 5 ml, trimethylaluminum 0.70 mmol (0.1 M hexane solution 7 m
l) is a needle valve and a volume 100 equipped with a magnetic stirrer.
The mixture was added to a pressure resistant reactor of ml, freeze-deaerated twice, and then sealed under a nitrogen atmosphere. This was heated in a 150 ° C. oil bath for 15 hours. No polymer was obtained and the monomer phenylsilane was recovered.

[0046]

INDUSTRIAL APPLICABILITY As described above, the present invention can provide a highly active dehydrogenative condensation catalyst which is easy to synthesize and easy to handle. Further, the organosilicon polymer can be efficiently produced from the organosilicon monomer in a short time.

[Brief description of drawings]

¹ H of the organosilicon polymer obtained in Example 1
-NMR spectrum chart.

FIG. 2 IR of the organosilicon polymer obtained in Example 1.
Spectrum chart.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yasushi Nomura 1-3-1 Nishitsurugaoka, Oi-cho, Iruma-gun, Saitama Inside Tonen Research Institute

Claims (1)

[Claims] 1. The first component has the formula Cp ₂ MX ₂ (wherein Cp is independently substituted or unsubstituted η ^5-
A cyclopentadienyl group is shown, and two cyclopentadienyl groups may be covalently bonded to each other via one or more atoms. M is Ti, Zr, Hf, X is F, C
l, Br and I are shown. ), And a catalyst for dehydrogenative condensation of an organosilicon monomer, comprising a metallocene dihalide represented by the formula (4) and an organometallic compound of a Group 12 or Group 13 metal as a second component.