JPH11236388A - Silicon-containing compound and post-treatment in production of silicon-containing polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To permit a metal catalyst to be simply and readily removed by allowing a silyl compound to react with an ethynyl compound in the presence of the metal catalyst, then treating the reaction mixture with an aqueous solution. SOLUTION: A silyl compound of the formula: R4-m -SiHm (m is a positive integer of <=4; R is a 1-30C alkyl, an alkenyl or the like), for example, methylsilane and an ethynyl compound of the formula: R<1> -C≡CH (R<1> is H, a 1-30C alkyl or the like) as acetylene are allowed to react with each other in the presence of a metal hydride, a metal compound or a typical element metal to prepare a silylacetylene of the formula (I is a positive integer of <=m). After completion of this reaction, the reaction mixture is treated with an aqueous solution to remove the catalyst. In a preferred embodiment, the reaction mixture is poured in the water whose pH is adjusted to 0-5 with an acid to decompose and separate the catalyst, the remaining is washed with neutral water or aqueous solution to remove the acidic components.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing an industrially useful silicon-containing compound and polymer using a metal hydride, a metal compound or a typical element metal as a catalyst from a silyl compound and an ethynyl compound. And a post-treatment method for removing a catalyst by treating the catalyst with an aqueous solution.

[0002]

2. Description of the Related Art Conventionally, as a method for synthesizing a silicon-containing compound or a silicon-containing polymer having an acetylene bond from a silyl compound and an acetylene compound, cuprous chloride described in a paper by JF Harrod et al. With cocatalyst (Hua Qin Liu and John F. Harr
od, Canadian Journal of Chemistry, Vol. 68, 1100-1
105 (1990)), a method using a basic metal oxide catalyst proposed by the present inventors (for example, see JP-A-5-345825,
Japanese Patent Laid-Open No. 194541/1993 is known. The present inventors have further conducted a method using a metal hydride catalyst (Japanese Unexamined Patent Publication No.
-120689) and metal compounds, but since these catalysts become basic hydroxides having a hydrolytic action of Si—C≡C bond or Si—H bond in the presence of water,
After the completion of the reaction, it was necessary to remove the catalyst from the reaction solution.

[0003]

DISCLOSURE OF THE INVENTION The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that metal hydrides,
In the production of a silicon-containing compound or polymer having an acetylene bond using a metal compound or a typical element metal as a catalyst, it has been found that the catalyst can be easily removed by treating the reaction solution with an aqueous solution.

[0004]

SUMMARY OF THE INVENTION The present invention relates to R _4-m -SiH.
_m (where m is a positive integer of 4 or less, and R is 1 carbon atom)
To 30 alkyl groups, alkenyl groups, alkynyl groups,
It is an aromatic group and may contain a halogen atom, a hydroxyl group, an amino group, a carboxyl group, or an ether group. When m is 1 or 2, each R may be the same or different. Silyl compound with R ¹ -C≡CH (wherein represented by), R ¹ represents an alkyl group having 1 to 30 number of hydrogen atoms or carbon atoms, an alkenyl group, an alkynyl group, an aromatic group, a halogen atom, a hydroxyl group, An ethynyl compound represented by the formula (1) (which may contain an amino group, a carboxyl group or an ether group) is reacted in the presence of a metal hydride, a metal compound or a typical elemental metal. )

[0005]

Embedded image (In the formula, m is a positive integer of 4 or less, and R is an alkyl group, alkenyl group, alkynyl group, or aromatic group having 1 to 30 carbon atoms, and is a halogen atom, a hydroxyl group, an amino group, a carboxyl group, an ether group. And when m is 1 or 2, each R may be the same or different, and R ¹ is a hydrogen atom or an alkyl, alkenyl, alkynyl, or aromatic group having 1 to 30 carbon atoms. In the method for producing a silylacetylene compound represented by the formula (1), the reaction may be terminated by a halogen atom, a hydroxyl group, an amino group, a carboxyl group, or an ether group, and i is a positive integer of m or less. An object of the present invention is to provide a post-treatment method characterized by removing a catalyst by treating a post-reaction liquid with an aqueous solution.

In the present invention, R ² —SiH ₂ —R ³ (wherein R ² and R ³ independently represent a hydrogen atom or an alkyl, alkenyl, alkynyl or aromatic group having 1 to 30 carbon atoms) These groups may include a halogen atom, a hydroxyl group, an amino group, a carboxyl group, and an ether group.) And a hydrosilyl compound represented by the general formula (2):

[0007]

Embedded image (Wherein, R ⁴ represents an alkylene group having 1 to 30 carbon atoms, an alkenylene group, an alkynylene group, a divalent aromatic group, an alkylene group having 1 to 30 carbon atoms, directly or via a bridge member, alkenylene A group linked to a group, an alkynylene group or an aromatic group, which may include a halogen atom, a hydroxyl group, an amino group, a carboxyl group, or an ether group, and n is a positive integer of 0 or 4 or less. Is reacted in the presence of a metal hydride, a metal compound or a typical elemental metal to obtain a compound represented by the general formula (3):

[0008]

Embedded image (Wherein, R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, an alkenyl group, an alkynyl group, or an aromatic group; R ⁴ is an alkylene group having 1 to 30 carbon atoms; Alkenylene group, alkynylene group, divalent aromatic group, a group in which an aromatic group is linked to an alkylene group having 1 to 30 carbon atoms, alkenylene group, alkynylene group, or aromatic group directly or via a crosslinking member; May have a halogen atom, a hydroxyl group, an amino group, a carboxyl group, or an ether group. N is 0 or a positive integer of 4 or less.) It is an object of the present invention to provide a post-treatment method for producing a silicon polymer, wherein the catalyst is removed by treating the reaction solution with an aqueous solution after the completion of the reaction.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The characteristics of the post-treatment method of the present invention can be summarized as follows: a silyl compound represented by R _4-m -SiH _m and an ethynyl compound represented by R ¹ -C≡CH are metal hydrides. A method of producing a silylacetylene compound represented by the general formula (1) by reacting in the presence of a metal compound or a typical elemental metal, wherein the reaction solution is treated with an acidic or neutral aqueous solution to form a catalyst. It can be easily removed.

The method further comprises reacting a hydrosilyl compound represented by R ² —SiH ₂ —R ³ with a diethynyl compound represented by the general formula (2) in the presence of a metal hydride, a metal compound or a typical element metal. In the method for producing a silicon-containing polymer having an acetylene bond containing a repeating unit represented by the general formula (3), the catalyst can be easily removed by treating the reaction solution with an acidic or neutral aqueous solution.

In the method for producing the silylacetylene compound represented by the general formula (1), a method for removing the catalyst by treating the reaction solution with an acidic or neutral aqueous solution will be described. The reaction solution was prepared using R _4-m -S to produce the silylacetylene compound represented by the general formula (1).
A silyl compound represented by iH _m and an ethynyl compound represented by R ¹ -C≡CH are mixed with or without a solvent in the presence of a metal hydride, a metal compound or a typical elemental metal at a predetermined temperature for a predetermined time. It is obtained by reacting (JP-A-10-120689).

The reactor comprises a part for supplying raw materials, a stirring device inside the reactor, a part for controlling the temperature of the reactor, and the like. This reaction can be carried out without a solvent or in a solvent. In a container, a raw material silyl compound represented by R _4-m -SiH _m and an ethynyl compound represented by R ¹ -C≡CH, and a metal hydride, a metal compound or a typical element metal as a catalyst, Charge the solvent accordingly.
The metal hydride can be charged as it is without being dissolved in a solution, suspension or solvent. The order of charging these containers is not particularly limited. The reaction solution is allowed to react for a predetermined time while being stirred while being controlled at a predetermined temperature.

The silyl compound represented by the raw material R _4-m -SiH _m is, specifically, methylsilane, dimethylsilane, trimethylsilane, ethylsilane, diethylsilane, triethylsilane, phenylsilane, diphenylsilane, triphenylsilane. , Hexylsilane, vinylsilane, allylsilane, ethynylsilane, 2-propynylsilane, benzoylsilane, trifluoromethylsilane, (3,3,3-trifluoropropyl) silane, 4
-Silyltoluene, 4-silylstyrene, 4-silyl-
α, α, α-trifluorotoluene, methoxysilane,
Examples include dimethoxysilane, trimethoxysilane, ethoxysilane, diethoxysilane, triethoxysilane and the like.

Examples of the ethynyl compound represented by R ¹ -C≡CH as a raw material include acetylene, propyne, 1-butyne, 1-hexyne, vinyl acetylene,
Examples include diacetylene, phenylacetylene, ethynylcyclohexane, 4-ethynyltoluene, 4-ethynylaniline, and 3-ethynylaniline.

[0015] Catalysts which can be used are metal hydrides, metal compounds.
Object or typical elemental metal. As metal hydride
Metal hydrides, composite metal hydrides and their water
Part of the alkyl is an alkyl group, an allyl group, an alkoxy group,
And a compound replaced with a phenyl group. metal
Examples of hydrogen compounds include Group 1 compounds such as LiH, NaH, and KH.
Typical element hydride, CaH_TwoGroup 2 typical element hydrogenation
Compound, BH_Three, AlH_ThreeGroup 13 typical element hydrogenation
Things. Also, as a composite metal hydride
Is LiBH_Four, NaBH_Four, KBH_Four, Mg (BH_Four)
_Two, Ca (BH_Four)_Two, Ba (BH_Four)_Two, Sr (BH
_Four)_Two, Zn (BH_Four)_Two, Al (BH_Four)_Three, LiA
1H_Four, NaAlH_Four, (CH_Three)_FourNBH_Four, (N-
C_FourH₉)_FourNBH_FourAnd the like. Also, hydrogen
Compounds partially substituted by other substituents include Li
BH (C_TwoH_Five)_Three, LiBH (s-C_FourH₉)_Three, K
BH (C₆H_Five)_Three, NaBH (OCH_Three)_Three, NaB
H (OC₆H_Five)_Three, NaBH (OCOCH_Three)_Three, N
aBH_ThreeCN, (i-C_ThreeH₇)_TwoAlH, (i-C_Four
H₉)_TwoAlH, LiAlH_Two(OC_TwoH_Five)_Two, Li
AlH (OC_TwoH_Five)_Three, LiAlH (OC (C
_TwoH_Five)_Three)_Three, LiAlH (OC (CH_Three) _Three)_Three,
NaAlH_Two(OCH_TwoCH_TwoCH_Three)_Two, NaAlH
_Two(C_TwoH_Five) _Two, SnH (n-C_FourH₉)_Three, SnH
(C₆H_Five)_ThreeAnd the like. Hydrogenation of these metals
Products may be used alone or as a mixture of two or more.
it can.

Metal compounds are hydrocarbon groups on the metal atom,
A compound to which an alkoxy group, an amino group, etc. are bonded,
In addition to these substituents, a hydrogen atom or a halogen atom may be bonded to the metal. These metal compounds can be roughly classified into organometallic compounds, metal alkoxides and metal amides.

Examples of the organometallic compounds include an organic metal in which a hydrocarbon group such as an alkyl group, an alkynyl group, an alkenyl group, and an aryl group is bonded to one metal, and a composite organic metal in which two or more metals are bonded. Can be

As the metal element, lithium, sodium,
Group 1 typical elements such as potassium, rubidium and cesium,
Examples include Group 2 typical elements such as beryllium, magnesium, calcium, strontium, and barium; Group 13 typical elements such as boron and aluminum; and Group 12 transition metal elements such as cadmium and zinc.

An alkyl group bonded to these metal elements,
Alkynyl, alkenyl, hydrocarbon groups such as aryl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, cyclopentadienyl, hexyl, Cyclohexyl group, octyl group, vinyl group, allyl group, 1-
Propenyl, ethynyl, hexynyl, phenylethynyl, phenyl, naphthyl, benzyl, methylbenzyl, tolyl, mesityl, diphenylmethyl, triphenylmethyl, styryl, α-methylbenzyl, etc. Is mentioned. However, the valence of the metal is 2
In the above case or in the composite organic metal, in addition to these organic groups, a halogen group such as a fluoro group, a chloro group, a bromo group, an iodo group, a hydrogen atom, an alkoxy group such as a methoxy group or an ethoxy group, or an amino group is bonded. It may be.

Examples of the organometallic compounds in which a hydrocarbon group such as an alkyl group, an alkynyl, an alkenyl, and an aryl group is bonded to a metal include, specifically, methyl lithium, ethyl lithium, propyl lithium, isopropyl lithium,
n-butyllithium, isobutyllithium, t-butyllithium, pentyllithium, hexyllithium, cyclohexyllithium, octyllithium, vinyllithium, allyllithium, 1-propenyllithium, ethynyllithium, 1-hexynyllithium, phenyllithium, naphthyllithium , Benzyllithium, methylbenzyllithium, tolyllithium, mesityllithium, diphenylmethyllithium, triphenylmethyllithium, styryllithium, α-methylbenzyllithium,
Phenylethynyl lithium, methyl sodium, ethyl sodium, propyl sodium, isopropyl sodium, n-butyl sodium, pentyl sodium, cyclopentadienyl sodium, hexyl sodium,
Ethynyl sodium, 1-hexynyl sodium, phenyl sodium, naphthyl sodium, phenylethynyl sodium, methyl potassium, ethyl potassium, propyl potassium, isopropyl potassium, n-butyl potassium, isobutyl potassium, t-butyl potassium, phenyl potassium, naphthyl potassium, Phenylethynyl potassium, ethyl rubidium, n-butyl rubidium, phenyl rubidium, ethyl cesium, n-butyl cesium, t-butyl cesium, phenyl cesium, diethyl beryllium, dipropyl beryllium, di-n-butyl beryllium, diphenyl beryllium, ethyl beryllium chloride , N-butyl beryllium chloride, phenyl beryllium chloride, ethyl beryllium bromide, butyl beryllium chloride Mide, phenyl beryllium bromide, ethyl beryllium iodide, n-butyl beryllium iodide, phenyl beryllium iodide, diethyl magnesium, di-n-butyl magnesium, di-t-butyl magnesium, dihexyl magnesium, diphenyl magnesium, ethyl magnesium fluoride, n -Butyl magnesium fluoride, hexyl magnesium fluoride, phenyl magnesium fluoride, ethyl magnesium chloride, butyl magnesium chloride, t-butyl magnesium chloride, hexyl magnesium chloride, phenyl magnesium chloride, ethyl magnesium bromide, butyl magnesium bromide, hexyl magnesium bromide, Phenyl magnesium Amide, ethylmagnesium iodide, n- butylmagnesium iodide, hexyl magnesium iodide,
Phenyl magnesium iodide, ethyl magnesium hydride, ethyl magnesium ethoxide, diethyl calcium, di-n-butyl calcium, dihexyl calcium, diphenyl calcium, ethyl calcium chloride, n-butyl calcium chloride, phenyl calcium chloride, ethyl calcium bromide, n-butyl Calcium bromide, phenyl calcium bromide, ethyl calcium iodide, n-
Butyl calcium iodide, phenyl calcium iodide, diethyl strontium, dibutyl strontium, dihexyl strontium, diphenyl strontium dimethyl barium, diethyl barium, dipropyl barium, di-n-butyl barium, di-t-n-
Butyl barium, dipentyl barium, dihexyl barium, diphenyl barium, diethynyl barium, di (1-hexynyl) barium, di (phenyl) barium, dinaphthyl barium, dibenzyl barium, ditolyl barium, dimesityl barium, bis (diphenyl Methyl) barium, bis (triphenylmethyl) barium, styryl) barium, di (α-methylbenzyl) barium, di (phenylethynyl) barium, di (3-ethynylphenylethynyl) barium, di (4-ethynylphenylethynyl) Barium, ethyl barium chloride, ethyl barium bromide, ethyl barium iodide, ethynyl barium hydride, phenyl ethynyl barium hydride, ethyl barium ethoxide, propyl barium pro Oxide, butyl barium butoxide, ethynyl barium ethoxide, phenyl ethynyl barium propoxide, phenyl ethynyl barium butoxide, ethyl barium amide, phenyl barium amide, triethyl borane, tripropyl borane, tri n-butyl borane, tri-n-butyl borane, tri Hexyl borane, triphenyl borane, triethyl aluminum, tripropyl aluminum, tri n-butyl aluminum, trihexyl aluminum, triphenyl aluminum, chlorodiethyl aluminum, chlorodipropyl aluminum, chlorodi n-butyl aluminum, chlorodiphenyl aluminum, bromodiethyl aluminum , Diethyl zinc, dipropyl zinc, dihexyl zinc, diphenyl zinc, diethyl cadmium , Dipropyl cadmium, dihexyl cadmium, diphenyl cadmium and the like.

Among the organometallic compounds, the composite organic metal includes lithium tetraethylaluminum, lithium tetrahexynylaluminum, lithium tetra (phenylethynyl) aluminum, lithium tri (phenylethynyl) aluminum ethoxide, and lithium di (phenylethynyl). ) Aluminum diethoxide, sodium tetraethylaluminum, sodium tetrahexynylaluminum, sodium tetra (phenylethynyl) aluminum, lithium triethylzinc, lithium tri (phenylethynyl) zinc, sodium triethylzinc, sodium tri (phenylethynyl) zinc,
Examples include calcium tetraethyl zinc, calcium tetrapropyl zinc, strontium tetraethyl zinc, strontium tetrapropyl zinc, and the like.

The alkoxides are classified into metal alkoxide compounds in which the metal bonded to the alkoxy group is one kind and heterometal alkoxide compounds in which the metal is two kinds. Examples of the metal element to which the alkoxy group is bonded include group 1 typical elements such as lithium, sodium, potassium, rubidium and cesium, group 2 typical elements such as beryllium, magnesium, calcium, strontium and barium, and boron, aluminum, gallium and indium. 13
Group III transition metal elements such as Group III transition metal elements such as titanium and zirconium; Group V transition metal elements such as niobium; Group 6 transition metal elements such as chromium; and Group 7 transition metal elements such as manganese And a Group 8 transition metal element such as iron, a Group 9 transition metal element such as cobalt, a Group 10 transition metal element such as nickel, a Group 11 transition metal element such as copper, and a Group 12 transition metal element such as zinc.

The alkoxy groups bonded to these metal elements include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, t-
Butoxy, pentyloxy, hexyloxy, octyloxy, allyloxy, benzyloxy,
Phenoxy, naphthyloxy, methoxyethoxy, methoxyethoxyethoxy, methoxypropoxy and the like. However, when the valence of the metal is 2 or more or in a heterometal alkoxide compound, in addition to these alkoxy groups, alkyl groups, alkynyl groups, alkenyl groups, hydrocarbon groups such as aryl groups, fluoro groups,
A halogen group such as a chloro group, a bromo group and an iodo group, a hydrogen atom or an amino group may be bonded.

Specific examples of the metal alkoxide compound in which an alkoxy group is bonded to a group 1 typical metal element include lithium methoxide, lithium ethoxide, lithium propoxide, lithium isopropoxide, lithium n-butoxide, and lithium isobutoxide. , Lithium t-butoxide, lithium pentyl oxide, lithium hexyl oxide, lithium octyl oxide, lithium allyl oxide, lithium benzyl oxide, lithium phenoxide, lithium naphthyl oxide, lithium methoxy ethoxide, lithium methoxy ethoxy ethoxide, lithium methoxy propoxide, sodium Methoxide, sodium ethoxide, sodium propoxide, sodium isopropoxide, sodium n-butoxide, sodium isobutoxide Sid, sodium t- butoxide,
Sodium hexyl oxide, sodium octyl oxide, sodium phenoxide, sodium methoxy ethoxide, sodium methoxy ethoxy ethoxide, sodium methoxy propoxide, potassium ethoxide,
Examples include potassium propoxide, potassium t-butoxide, potassium phenoxide, potassium naphthyl oxide, rubidium ethoxide, rubidium t-butoxide, rubidium benzyl oxide, rubidium phenoxide, cesium ethoxide, cesium propoxide, cesium t-butoxide, and the like.

Specific examples of the metal alkoxide compound in which an alkoxy group is bonded to a group 2 typical metal element include beryllium di (ethoxide), beryllium di (n-butoxide), beryllium di (isobutoxide), and beryllium di (t). -Butoxide), beryllium di (hexyl oxide), beryllium di (phenoxide), magnesium di (ethoxide), magnesium di (propoxide), magnesium di (isopropoxide), magnesium di (n-butoxide), magnesium di (t) -Butoxide), magnesium di (hexyl oxide), magnesium di (phenoxide), magnesium di (methoxyethoxide), calcium di (ethoxide), calcium di (propoxide), calcium di (isopropoxide), calcium di (n − Toxide), calcium di (isobutoxide), calcium di (t-butoxide), calcium di (hexyl oxide), calcium di (octyl oxide), calcium di (phenoxide), calcium di (methoxy ethoxide), calcium di (methoxy ethoxy) (Propoxide), strontium di (ethoxide), strontium di (propoxide), strontium di (isopropoxide), strontium di (n-butoxide), strontium di (t-butoxide), strontium di (hexyl oxide), strontium di (Phenoxide), strontium di (methoxy ethoxide), barium di (methoxide), barium di (ethoxide), barium di (propoxide), barium di (isopropoxide), barium di (n- Tokishido), barium di (isobutoxides), barium di (s- butoxide), barium di (t- butoxide),
Barium di (pentyl oxide), barium di (hexyl oxide), barium di (octyl oxide), barium di (benzyl oxide), barium di (phenoxide), barium di (methoxy ethoxide), barium di (methoxy ethoxy ethoxide), barium di (methoxy propoxide) And the like.

Specific examples of metal alkoxide compounds in which an alkoxy group is bonded to a group 13 typical metal element include boron tri (ethoxide), boron tri (propoxide), boron tri (isopropoxide), boron tri (n-butoxide), Boron tri (isobutoxide),
Boron tri (t-butoxide), boron tri (phenoxide), aluminum tri (ethoxide), aluminum tri (propoxide), aluminum tri (isopropoxide), aluminum tri (n-butoxide), aluminum tri (t-butoxide), gallium Tri (ethoxide), gallium tri (propoxide), gallium tri (isopropoxide), gallium tri (n-butoxide), gallium tri (isobutoxide), gallium tri (t-butoxide), gallium tri (hexyl oxide), Gallium tri (phenoxide), indium tri (ethoxide), indium tri (propoxide),
Indium tri (isopropoxide) and the like can be mentioned.

Specific examples of the metal alkoxide compound in which an alkoxy group is bonded to a Group 3 transition metal element include yttrium tri (ethoxide), yttrium tri (isopropoxide side), and yttrium tri (methoxyethoxide side). No.

Specific examples of the metal alkoxide compound in which an alkoxy group is bonded to a Group 4 transition metal element include titanium tetra (ethoxide), titanium tetra (propoxide), titanium tetra (isopropoxide), and titanium tetra (methoxy). (Ethoxide), zirconium tetra (ethoxide), zirconium tetra (propoxide), zirconium tetra (isopropoxide), zirconium tetra (methoxyethoxide) and the like.

Specific examples of the metal alkoxide compound in which an alkoxy group is bonded to a group V transition metal element include niobium penta (ethoxide). Specific examples of the metal alkoxide compound in which an alkoxy group is bonded to a Group 6 transition metal element include chromium tri (ethoxide),
Chromium tri (isopropoxide) and the like. Specific examples of the metal alkoxide compound in which an alkoxy group is bonded to a Group 7 transition metal element include manganese di (methoxide) and manganese di (ethoxide).

Specific examples of the metal alkoxide compound in which an alkoxy group is bonded to a Group VIII transition metal element include iron tri (ethoxide). 9 alkoxy groups
Specific examples of the metal alkoxide compound bonded to the group III transition metal element include cobalt di (methoxide) and cobalt di (ethoxide). Specific examples of the metal alkoxide compound in which an alkoxy group is bonded to a Group 10 transition metal element include nickel di (ethoxide) and nickel di (methoxide).

Specific examples of the metal alkoxide compound in which an alkoxy group is bonded to a Group 11 transition metal element include copper di (methoxide), copper di (ethoxide), copper di (propoxide), and copper di (isopropoxide). ), Copper di (n-butoxide), copper di (t-butoxide), copper di (methoxy ethoxide) and the like. Specific examples of the metal alkoxide compound in which an alkoxy group is bonded to a Group 12 transition metal element include zinc diethoxide and zinc di (methoxy ethoxide).

As the hetero metal alkoxide compound,
Specifically, lithium aluminum tetramethoxide,
Lithium aluminum tetraethoxide, lithium aluminum tetrapropoxide, sodium aluminum tetrabutoxide, sodium aluminum tetramethoxide, sodium aluminum tetraethoxide, sodium aluminum tetrapropoxide, sodium aluminum tetrabutoxide, potassium aluminum tetramethoxide, potassium aluminum tetraethoxy And potassium aluminum tetrapropoxide, potassium aluminum tetrabutoxide and the like.

In the present invention, a metal amide is a metal amide compound in which one hydrogen atom of ammonia or a primary or secondary amine is substituted with a metal atom; and two hydrogen atoms of ammonia or a primary amine are metal atoms. A substituted metal imide compound; and a metal nitride compound in which three hydrogen atoms of ammonia have been replaced by metal atoms.

The primary or secondary amine may be methylamine, dimethylamine, ethylamine, ethylamine, propylamine, dipropylamine, isopropylamine, diisopropylamine, butylamine, dibutylamine, isobutylamine, diisobutylamine, t-butylamine, t-butylamine, pentylamine, dipentylamine, hexylamine, dihexylamine,
Octylamine, allylamine, diallylamine, trimethylsilylamine, bis (trimethylsilyl) amine, aniline, diphenylamine and the like can be mentioned.

The metal elements to be substituted include group 1 typical elements such as lithium, sodium, potassium, rubidium and cesium and group 2 typical elements such as beryllium, magnesium, calcium, strontium and barium. However, when the valence of the metal is 2 or more, these metal atoms may be a hydrogen atom or a halogen group such as a fluoro group, a chloro group, a bromo group, an iodo group, an alkyl group, an alkynyl group, an alkenyl group, an aryl group, or the like. Hydrocarbon groups,
An alkoxy group such as a methoxy group or an ethoxy group may be bonded.

As the metal amide compound in which the metal atom replacing the hydrogen atom is a group 1 typical metal element, specifically,
Lithium amide, lithium methylamide, lithium dimethylamide, lithium ethylamide, lithium diethylamide, lithium propylamide, lithium dipropylamide, lithium isopropylamide, lithium diisopropylamide, lithium butylamide, lithium dibutylamide, lithium isobutylamide, lithium diisobutylamide , Lithium t-butylamide, lithium di-t-butylamide, lithium pentylamide, lithium dipentylamide, lithium hexylamide, lithium dihexylamide, lithium octylamide, lithium allylamide, lithium diallylamide, lithium trimethylsilylamide, lithium bis (trimethylsilyl) amide, Lithium phenylamide, lithium diphenylamide, nato Sodium amide, sodium dimethylamide, sodium diethylamide, sodium dipropylamide, sodium diisopropylamide, sodium dibutylamide, sodium diisobutylamide, sodium di-t-butylamide, sodium dipentylamide, sodium hexylamide, sodium dihexylamide, sodium diallylamide, sodium trimethylsilyl Amide, sodium bis (trimethylsilyl) amide, sodium diphenylamide, potassium amide, potassium dimethylamide, potassium diethylamide, potassium dipropylamide, potassium isopropylamide, potassium diisopropylamide, potassium dibutylamide, potassium isobutylamide, potassium diisobutylamide, potassium bis (G Methylsilyl) amide, potassium diphenyl amide, rubidium amide,
Examples include rubidium diethylamide, rubidium diisopropylamide, rubidium dibutylamide, rubidium bis (trimethylsilyl) amide, cesium amide, cesium dimethylamide, cesium diethylamide, cesium diisopropylamide, cesium dibutylamide, and cesium bis (trimethylsilyl) amide.

As the metal amide compound in which the metal atom replacing the hydrogen atom is a Group 2 typical metal element, specifically,
Beryllium diamide, beryllium bis (dimethylamide), beryllium bis (diethylamide), beryllium bis (dipropylamide), beryllium bis (dibutylamide), beryllium bis (bis (trimethylsilyl))
Amide), beryllium bis (diphenylamide), magnesium diamide, magnesium bis (dimethylamide), magnesium bis (diethylamide), magnesium bis (dipropylamide), magnesium bis (isopropylamide), magnesium bis (diisopropylamide), magnesium bis (Dibutylamide), magnesium bis (diisobutylamide), magnesium bis (t-butylamide), magnesium bis (di-t-
Butylamide), magnesium bis (dihexylamide), magnesium bis (diallylamide), magnesium bis (trimethylsilylamide), magnesium bis (bis (trimethylsilyl) amide), magnesium bis (phenylamide), magnesium bis (diphenylamide), calcium diamide , Calcium bis (methylamide), calcium bis (dimethylamide), calcium bis (ethylamide), calcium bis (diethylamide), calcium bis (propylamide), calcium bis (dipropylamide), calcium bis (isopropylamide), calcium bis (Diisopropylamide), calcium bis (dibutylamide), calcium bis (di-t-butylamide), calcium bis (dihexylamide) Calcium bis (diallylamide), calcium bis (bis (trimethylsilyl) amide), calcium bis (diphenylamide), strontium diamide, strontium bis (dimethylamide), strontium bis (diethylamide), strontium bis (dipropylamide), strontium bis (Diisopropylamide), strontium bis (dibutylamide), strontium bis (di-t-butylamide), strontium bis (dihexylamide), strontium bis (bis (trimethylsilyl) amide), strontium bis (diphenylamide), barium diamide, barium bis (Methylamide), barium bis (dimethylamide), barium bis (ethylamide), barium bis (diethylamide), barium Mbis (propylamide), barium bis (dipropylamide), barium bis (isopropylamide), barium bis (diisopropylamide), barium bis (butylamide), barium bis (dibutylamide), barium bis (isobutylamide), barium bis (Diisobutylamide), barium bis (t-butylamide), barium bis (di-t-butylamide), barium bis (pentylamide), barium bis (dipentylamide), barium bis (hexylamide), barium bis (dihexylamide), Barium bis (octylamide), barium bis (allylamide), barium bis (diallylamide), barium bis (trimethylsilylamide), barium bis (bis (trimethylsilyl) amide), barium bis (f Enylamide), barium bis (diphenylamide), barium (hydro) amide, barium (hydro) dimethylamide, and the like.

Examples of the metal imide compound in which the metal atom replacing the hydrogen atom is a group 1 typical metal element include:
Lithium imide, lithium methyl imide, lithium ethyl imide, lithium propyl imide, lithium isopropyl imide, lithium butyl imide, lithium isobutyl imide, lithium t-butyl imide, lithium pentyl imide, lithium hexyl imide, lithium octyl imide, lithium allyl imide, lithium trimethyl silyl Imide, lithium phenylimide, sodium imide, sodium methyl imide, sodium ethyl imide, sodium propyl imide, sodium isopropyl imide, sodium butyl imide, sodium isobutyl imide, sodium t-butyl imide, sodium pentyl imide, sodium hexyl imide, sodium octyl imide, Sodium allyl imide, sodium trimethylsilyl Imide, sodium phenylimide, potassium imide, potassium ethyl imide, potassium propyl imide, potassium butyl imide, potassium hexyl imide, potassium phenyl imide, rubidium imide, rubidium ethyl imide, rubidium butyl imide, rubidium isobutyl imide, rubidium t-butyl imide, cesium Ethyl imide, cesium butyl imide and the like can be mentioned.

As the metal imide compound in which the metal atom replacing the hydrogen atom is a Group 2 typical metal element, specifically,
Beryllium imide, beryllium ethyl imide, beryllium butyl imide, beryllium t-butyl imide, lylium hexyl imide, beryllium trimethylsilyl imide, beryllium phenyl imide, magnesium imide,
Magnesium ethyl imide, magnesium propyl imide, magnesium isopropyl imide, magnesium butyl imide, magnesium t-butyl imide, magnesium pentyl imide, magnesium hexyl imide, magnesium trimethylsilyl imide, magnesium phenyl imide, calcium imide, calcium methyl imide, calcium ethyl imide, calcium propyl Imide, calcium isopropyl imide, calcium butyl imide, calcium isobutyl imide, calcium t-
Butyl imide, calcium hexyl imide, calcium allylmimide, calcium trimethylsilyl imide, calcium phenyl imide, strontium imide, strontium ethyl imide, strontium propyl imide, strontium isopropyl imide, strontium butyl imide, strontium t-butyl imide, strontium hexyl imide, strontium octyl imide, Strontium allyl imide, strontium trimethylsilyl imide, strontium phenyl imide, barium imide, barium methyl imide, barium ethyl imide, barium propyl imide, barium isopropyl imide, barium butyl imide, barium isobutyl imide, barium t-butyl imide, barium pentyl imide, barium Arm hexyl imide, barium octyl imide, barium allyl imide, barium trimethylsilyl imide, barium phenyl imide.

Examples of the metal nitride compound include lithium nitride, sodium nitride, potassium nitride, rubidium nitride, cesium nitride, beryllium nitride, magnesium nitride, calcium nitride, strontium nitride, barium nitride and the like. Can be These metal compounds can be used alone or in combination of two or more.

The typical element metals include Group 1 typical element metals such as lithium, sodium, potassium, rubidium and cesium, and Group 2 typical element metals such as beryllium, magnesium, calcium, strontium and barium. These metals can be used as they are,
In particular, the Group 2 element metal is desirably used in the form of activated fine particles. As a method of obtaining activated metal fine particles, a method of reducing a metal halide with a lithium / aromatic complex (H. Xiong, and RD Rieke, Journal of
Organic Chemistry, Vol. 54, 3247-3249 (1989)., T.
Wu, H. Xiong, and RD Rieke, Journal of Organic
Chemistry, Vol. 55, 5045-5051 (1990)., A. Yanagisa
wa, S. Habaue, K. Yasue, and H. Yamamoto, Journal
of American Chemical Society, Vol. 116, 6130-6141
(1994).) And methods for reducing metal halides with potassium (TP Burns, and RD Rieke, Journal of Org
anic Chemistry, Vol. 52, 3674-3680 (1987)), a method of simultaneously condensing a metal vapor and a solvent (KJ Klabunde,
HF Efner, L. Satek, and W. Donley, Journal of O
rganometallic Chemistry, Vol. 71 309-313 (1974))
And the like.

The ratio of the raw materials of the silyl compound represented by R _4-m -SiH _m and the ethynyl compound represented by R ¹ -C≡CH is not particularly limited, but is preferably 100 mmol of the ethynyl compound. On the other hand, from lmmol to l
0000 mmol. The metal hydride, metal compound or typical element metal as a catalyst can be used alone or in combination of two or more. The amount of catalyst used is R ¹
0.0001 mmol to 200 mmol for 100 mmol of the ethynyl compound represented by -C≡CH.

Examples of the solvent include saturated aliphatic hydrocarbon solvents such as pentane, hexane, heptane, and octane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and mesitylene; diethyl ether; Ether solvents such as butyl ether, anisole, diphenyl ether, tetrahydrofuran, dioxane, bis (2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, and halogen-containing solvents such as dichloromethane and chloroform; N-
Organic polar solvents such as methylpyrrolidone, dimethylformamide, dimethylacetamide, and mixed solvents thereof can be used. The amount of the solvent is 0.1 to 40 m per 1 mmol of the raw material ethynyl compound represented by R ¹ -C の CH.
l is preferred.

The reaction temperature is from 0 to 300 ° C, more preferably from 20 to 150 ° C. The reaction pressure may be normal pressure or pressurization. Although the reaction time varies depending on the reaction temperature and the like, 0.1 to 200 hours is appropriate.

The purification of the product may be carried out without any treatment of the reaction solution, but is preferably carried out after dispersing the reaction solution in water to decompose and separate the catalyst. The water for decomposing and separating the catalyst may be acidic or neutral, but may be HF, HCl, HBr, HI, H ₂ SO
₄ , HNO ₃ , H ₂ CO ₃ , H ₃ PO ₄ , HClO ₂ ,
It is preferable to use an inorganic acid such as H ₂ S, H ₂ SO ₃ , H ₂ S ₂ O ₃ or an acid such as HCOOH, CH ₃ COOH, C ₆ H ₅ COOH, oxalic acid or the like to make it acidic to pH 0 to pH ₅ . The amount of water is 0.4 m per 1 mmol of the catalyst.
1 to 400 ml. When no solvent or a reaction solvent having a solubility in water of 5% by weight or more is used, an aromatic hydrocarbon solvent such as benzene, toluene, or xylene that has been dehydrated and dried before dispersion is represented by R ¹ -C≡CH as a raw material. 0.1 ml to 40 m per 1 mmol of ethynyl compound
It is preferable to add l.

The method of decomposing and separating the catalyst will be described in more detail. The method of dispersing the reaction solution in water includes a method of pouring and stirring the reaction solution in an aqueous solution, a method of pouring and stirring the aqueous solution in the reaction solution, Any method may be employed in which the aqueous solution and the reaction solution are simultaneously poured into one container and stirred, but a method in which the reaction solution is poured into the aqueous solution and stirred is preferable. The reaction liquid is dispersed in water by mixing and stirring to move the catalyst to the aqueous layer side, and then the organic layer is separated. The organic layer is preferably further washed once to ten times with an aqueous solution.
The amount of the aqueous solution varies depending on the product concentration in the reaction solution, the type and concentration of the catalyst.
ml to 400 ml. When an acidic aqueous solution is used as the aqueous solution, the concentration of the acid varies depending on the type of the acid, but the concentration is such that the pH of the aqueous solution is in the range of 0 to 5. The neutral aqueous solution is pure water or an aqueous solution of an inorganic salt or an organic salt having a pH in the range of 6 to 9.

No solvent or solubility in water is 5 wt%
When the above reaction solvent is used, an aromatic hydrocarbon solvent such as benzene, toluene, xylene or the like having a solubility in water of less than 5 wt% before dispersing is represented by R ¹ -C≡CH as a raw material. 1m charge of ethynyl compound
It is preferable to add to the reaction solution in a ratio of 0.1 ml to 40 ml based on mol. These solvents may be added to the aqueous solution side without performing dehydration drying. In addition, as a solvent having a solubility in water of less than 5 wt%, in addition to an aromatic solvent, a halogen-containing solvent such as chloroform, and a saturated aliphatic hydrocarbon such as pentane, hexane, heptane, and octane can be used. These solvents can be used alone or in combination of two or more.

When the catalyst is removed with an acidic aqueous solution,
The reaction solution may be used as it is, but it is preferable to remove the acid component by washing with neutral water or an aqueous solution. The number of washings for removing the acid component varies depending on the type and amount of the acid used, but is until the pH of the washed water becomes 6 or more, and is usually about 1 to 30 times. Reaction liquid (oil layer)
If the separation of the aqueous layer from the water is poor, use LiCl, NaCl, Na ₂
SO ₄ , NaNO ₃ , KCl, MgCl ₂ , CaCl ₂
It is preferable to use an aqueous solution of an inorganic salt such as The amount of water used is 0.01 to 100 ml per 1 ml of the reaction solution.

After the above-described catalyst removal operation, the product is separated and purified from the reaction solution by a method such as distillation, column separation, extraction, or recrystallization, and the reaction solution is dried with a desiccant before separation and purification. It is preferable to keep it. The desiccant is P
Acidic desiccant such as ₂ O ₅ , H ₂ SO ₄ , molecular sieve, silica gel, alumina, Na ₂ SO ₄ , Na ₂ C
O ₃ , MgSO ₄ , Mg (ClO ₄ ) ₂ , CaSO ₄ ,
Neutral drying agents such as CaCl ₂ and CuSO ₄ can be used, but it is preferable to use neutral drying agents. The amount of the desiccant varies depending on the type of the desiccant and the type of the solvent.
It is 0.01 g to 50 g per ml. The drying time varies depending on the type and amount of the desiccant and the type of the solvent, but is from 5 minutes to 100 minutes.
Days, preferably 12 hours to 10 days.

Next, a method for removing the catalyst by treating the reaction solution with an acidic or neutral aqueous solution in the production of a silicon-containing polymer having an acetylene bond containing a repeating unit represented by the general formula (3) will be described. . The reaction solution contains a silyl compound represented by R ² —SiH ₂ —R ³ and a silyl compound represented by the general formula (2) in order to produce a silicon-containing polymer having an acetylene bond containing a repeating unit represented by the general formula (3). Is obtained by reacting the diethynyl compound represented by the formula (1) with or without a solvent in the presence of a metal hydride, a metal compound or a typical element metal at a predetermined temperature at a predetermined temperature for a predetermined time (JP-A-10-12068).
9).

The reactor comprises a part for supplying raw materials, a stirring device inside the reactor, a part for controlling the temperature of the reactor, and the like. This reaction can be carried out without a solvent or in a solvent. In a container, a raw material hydrosilyl compound represented by R ² —SiH ₂ —R ³ , a diethynyl compound represented by the general formula (2) and a metal hydride, a metal compound or a typical element metal as a catalyst, Charge the solvent accordingly. The metal hydride, metal compound or typical elemental metal can be charged in a solution state, a suspension state, or as it is without being dissolved in a solvent. The reaction solution is allowed to react for a predetermined time while being stirred while being controlled at a predetermined temperature.

Hydrosilyl compounds represented by R ² —SiH ₂ —R ^{3 as} raw materials include methylsilane, dimethylsilane, ethylsilane, diethylsilane, phenylsilane, and the like.
Diphenylsilane, hexylsilane, vinylsilane, allylsilane, ethynylsilane, 1-silyl-2-propyne, benzoylsilane, trifluoromethylsilane, 1
-Silyl-3,3,3-trifluoropropane, 4-silyltoluene, 4-silylstyrene, 4-silylethynyltoluene, 4-silyl-α, α, α-trifluorotoluene, methoxysilane, dimethoxysilanesilane, Ethoxysilane, diethoxysilane and the like can be mentioned.

The diethynyl compound represented by the general formula (2) as a raw material is specifically, diacetylene, m-
Diethynylbenzene, p-diethynylbenzene, o-diethynylbenzene, 3,5-diethynyltoluene, 2,
7-diethynylnaphthalene, 5,10-diethynylanthracene, 4,4′-diethynylbiphenyl, bis (4
-Ethynylphenyl) methane, 2,2-bis (p-ethynylphenyl) propane, 2,2-bis (p-ethynylphenyl) trifluoropropane, bis (4-ethynylphenyl) ether, 2,2-bis (p -Ethynylphenyl) sulfone, 2,6-diethynylpyridine, 2,
5-diethynylthiophene, chemical formula (4)

[0054]

Embedded image , Chemical formula (5)

[0055]

Embedded image , Chemical formula (6)

[0056]

Embedded image , Chemical formula (7)

[0057]

Embedded image , Chemical formula (8)

[0058]

Embedded image It is.

As the metal hydride, metal compound or typical elemental metal of the catalyst, the same ones that can be used for producing the silylacetylene compound represented by the general formula (1) can be used. The ratio of the raw material, the hydrosilyl compound represented by R ² —SiH ₂ —R ³ , to the diethynyl compound represented by the general formula (2) is not particularly limited, but is preferably 10 mmol per 100 mmol of the diethynyl compound.
1 to 1000 mmol. The metal hydride, metal compound or typical element metal as a catalyst can be used alone or in combination of two or more. The amount of the catalyst used is 0.0001 per 100 mmol of the diethynyl compound.
It is from 200 mmol to 200 mmol.

Examples of the solvent include aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene and mesitylene, diethyl ether, n-butyl ether, anisole, diphenyl ether, tetrahydrofuran, dioxane, bis (2-methoxyethyl) ether Solvents such as 1,2-bis (2-methoxyethoxy) ethane, halogen-containing solvents such as dichloromethane and chloroform, and organic polar solvents such as N-methylpyrrolidone, dimethylformamide, and dimethylacetamide; Can be used. The amount of the solvent is 0.1 to 1 mmol of the starting diethynyl compound.
~ 40 ml is preferred. Further, since water contained in the solvent may reduce the activity of the catalyst, it is preferable to use a solvent which has been previously dehydrated and dried. Reaction temperature is 0-3
00 ° C, more preferably 20 to 150 ° C. The reaction pressure may be normal pressure or pressurization. Although the reaction time varies depending on the reaction temperature and the like, 0.1 to 200 hours is appropriate.

The purification of the product may be carried out without any treatment of the reaction solution, but is preferably carried out after dispersing the reaction solution in water to decompose and separate the catalyst. The water for decomposing and separating the catalyst may be acidic or neutral, but may be HF, HCl, HBr, HI, H ₂ SO
₄ , HNO ₃ , H ₂ CO ₃ , H ₃ PO ₄ , HClO ₂ ,
It is preferable to use an inorganic acid such as H ₂ S, H ₂ SO ₃ , H ₂ S ₂ O ₃ or an acid such as HCOOH, CH ₃ COOH, C ₆ H ₅ COOH, oxalic acid or the like to make it acidic to pH 0 to pH ₅ . The amount of water is 0.4 m per 1 mmol of the catalyst.
1 to 400 ml. In the case of using no solvent or a reaction solvent having a solubility in water of 5% by weight or more, an aromatic hydrocarbon solvent such as benzene, toluene, or xylene which has been dehydrated and dried before dispersing is represented by the general formula (2) as a raw material. 0.1 ml to 40 m per 1 mmol of diethynyl compound
It is preferable to add l.

The method of decomposing and separating the catalyst will be described in more detail. As a method of dispersing the reaction solution in water, a method of pouring and stirring the reaction solution in an aqueous solution, a method of pouring and stirring the aqueous solution in the reaction solution, Any method may be employed in which the aqueous solution and the reaction solution are simultaneously poured into one container and stirred, but a method in which the reaction solution is poured into the aqueous solution and stirred is preferable. The reaction liquid is dispersed in water by mixing and stirring to move the catalyst to the aqueous layer side, and then the organic layer is separated. The organic layer is preferably further washed once to ten times with an aqueous solution.
The amount of the aqueous solution varies depending on the product concentration in the reaction solution, the type and concentration of the catalyst.
ml to 400 ml. When an acidic aqueous solution is used as the aqueous solution, the concentration of the acid varies depending on the type of the acid, but the concentration is such that the pH of the aqueous solution is in the range of 0 to 5. The neutral aqueous solution is pure water or an aqueous solution of an inorganic salt or an organic salt having a pH in the range of 6 to 9.

No solvent or solubility in water is 5 wt%
In the case where the above reaction solvent is used, before dispersing, a dehydrogenated aromatic hydrocarbon solvent such as benzene, toluene, xylene or the like having a solubility in water of less than 5% by weight is used as a starting material for diethynyl represented by the general formula (2). Compound preparation 1m
It is preferable to add to the reaction solution in a ratio of 0.1 ml to 40 ml based on mol. These solvents may be added to the aqueous solution side without performing dehydration drying. In addition, as a solvent having a solubility in water of less than 5 wt%, in addition to an aromatic solvent, a halogen-containing solvent such as chloroform, and a saturated aliphatic hydrocarbon such as pentane, hexane, heptane, and octane can be used. These solvents can be used alone or in combination of two or more.

When the catalyst is removed with an acidic aqueous solution,
The reaction solution may be used as it is, but it is preferable to remove the acid component by washing with neutral water or an aqueous solution. The number of washings for removing the acid component varies depending on the type and amount of the acid used, but is until the pH of the washed water becomes 6 or more, and is usually about 1 to 30 times. Reaction liquid (oil layer)
If the separation of the aqueous layer from the water is poor, use LiCl, NaCl, Na ₂
SO ₄ , NaNO ₃ , KCl, MgCl ₂ , CaCl ₂
It is preferable to use an aqueous solution of an inorganic salt such as The amount of water used is 0.01 to 100 ml per 1 ml of the reaction solution.

After the above-described catalyst removal operation, the product is separated and purified from the reaction solution by a method such as column separation or precipitation. It is preferable that the reaction solution be dried with a desiccant before separation and purification. . The desiccant is an acidic desiccant such as P ₂ O ₅ , H ₂ SO ₄ , molecular sieve, silica gel, alumina, Na ₂ SO ₄ , Na ₂ CO ₃ , MgSO ₄ , M
g (ClO ₄ ) ₂ , CaSO ₄ , CaCl ₂ , CuSO
_Although a neutral desiccant such as ₄ can be used, it is preferable to use a neutral desiccant. The amount of the desiccant varies depending on the type of the desiccant and the type of the solvent, but 0.01 g per 1 ml of the reaction solution.
５０50 g. The drying time varies depending on the type and amount of the desiccant and the type of the solvent, but is 5 minutes to 100 days, preferably 12 hours to 10 days.

Examples of the poor solvent which can be used for separating and separating the polymer include aliphatic hydrocarbons such as pentane, hexane, heptane and octane, and aliphatic alcohols such as methanol, ethanol and propanol. The amount of the poor solvent used is 0.01 to 200 ml, more preferably 0.1 to 50 m, per 1 mmol of the raw material diethynyl compound.
l.

[0067]

The present invention will be described below with reference to examples and comparative examples.
I will tell. Example 1 A magnetic stirrer was installed inside a 100 ml glass container.
Then, the inside of the container was replaced with high-purity nitrogen gas. Then in the container
5.7 g (53 mmol) of phenylsilane as a raw material
5.4 g (53 mmol) of phenylacetylene, solvent
(2-methoxyethyl) ether 10 ml, catalyst L
iAlH_Four0.103 g (2.7 mmol) was charged,
Stirring was performed at 120 ° C. for 20 hours. After the reaction, the reaction solution is G
The analysis was performed by C (gas chromatography). As a product
Phenylethynyl (phenyl) silane (yield 42%)
And bis (phenylethynyl) (phenyl) silane
(Yield 9%) was obtained. The reaction rate is phenylsila
53% and phenylacetylene 56%. This result
From the results, the silyl acetylene is more easily
It was shown that the compound could be prepared. Dehydrate the reaction solution
Add 20 ml of Ruen and add to 20 ml of 1N aqueous hydrochloric acid.
Dispersed. Wash the organic phase with 5 ml of 1N aqueous hydrochloric acid
Thereafter, the pH of the aqueous phase is adjusted to 6 with 5 ml of ion-exchanged water.
And washed with CaSO _FourDrying overnight with 10 g.
The reaction solution was concentrated to 9.2 g with an evaporator. Anti
When the residual amount of lithium in the reaction solution was measured, it was 1 μg / g.
Was less than.

Example 2 Phenylsilane was placed in a 70 ml pressure-resistant stainless steel container.
8 g (53 mmol), m-diethynylbenzene 6.7
g (53 mmol), tetrahydrofuran 1 as a solvent
0 ml, LiAlH ₄ 0.100 g as catalyst (2.
6 mmol) was sealed and stirred at 120 ° C. for 20 hours. The reaction mixture was analyzed by GC to find that the conversion of phenylsilane was 76% and that of m-diethynylbenzene was 92%.
%Met. 20 ml of dehydrated toluene was added to the reaction solution, and 1
It was dispersed in 20 ml of a normal aqueous hydrochloric acid solution. The organic phase was washed with 5 ml of a 1 N aqueous hydrochloric acid solution and then with 5 ml of pure water until the pH of the aqueous phase reached 6. After dehydrating overnight with 10 g of CaSO _4, vacuum drying was performed at 0.7 kPa for 52 hours to obtain 8.4 g of a polymer (yield 67%).
The weight average molecular weight in terms of styrene measured by GPC (gel permeation chromatography) was 2,400.
When the residual amount of lithium in the polymer was measured, it was 1 μg.
/ G.

Comparative Example 1 A polymer reaction solution having a weight average molecular weight in terms of styrene of 2200 was obtained by the same reaction procedure as in Example 2. Without performing the catalyst removal operation with an aqueous hydrochloric acid solution, the reaction solution was concentrated as it was,
The solvent and monomer were removed by vacuum drying to obtain 8.9 g of a polymer. The residual amount of lithium in the polymer is 20
It was 00 μg / g.

Example 3 As a silyl compound, 5.8 g (54 mm) of phenylsilane was used.
ol) and phenylacetylene as an ethynyl compound.
3 g (52 mmol), 10 ml of bis (2-methoxyethyl) ether as a solvent, and 0.103 g of n-butyllithium hexane solution as a catalyst (0.3 ml of n-butyllithium)
The reaction was carried out in the same manner as in Example 1 except for using 2 mmol). After the reaction, the reaction solution was analyzed by GC (gas chromatography). Phenylethynyl (phenyl) silane (44% yield) and bis (phenylethynyl) (phenyl) silane (9% yield) were obtained as products. The reaction rates were phenylsilane 62% and phenylacetylene 77%. After performing the same post-treatment as in Example 1, the reaction solution was concentrated to 10.6 g with an evaporator. When the amount of lithium remaining in the reaction solution was measured, it was less than 1 μg / g.

Example 4 6.7 g (53 mmol) of m-diethynylbenzene was used in place of phenylacetylene, and stirring was carried out at 80 ° C. for 20 hours under the same conditions as in Example 3. The reaction solution was analyzed by GC. As a result, the conversion of phenylsilane was 64%, and the conversion of m-diethynylbenzene was 76%. After the same post-processing as in Example 2, 0.7 kP
Vacuum drying was performed at 50a for 50 hours to obtain 8.4 g of a polymer (yield 67%). The weight average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography) was about 2,200. When the residual amount of lithium in the polymer was measured, it was less than 1 μg / g.

Example 5 0.30 ml (0.34 ml) of a 1.04 mol / l hexane solution of lithium bis (trimethylsilyl) amide was used as a catalyst.
1 mmol), and the mixture was stirred at 80 ° C. for 8 hours under the other conditions as in Example 4. The reaction mixture was analyzed by GC. As a result, the conversion of phenylsilane was 65%, and the conversion of m-diethynylbenzene was 78%. 20 ml of dehydrated toluene was added to the reaction solution and dispersed in 20 ml of a 1N aqueous hydrochloric acid solution. The organic phase was washed with 5 ml of a 1 N aqueous hydrochloric acid solution, and then washed with 5 ml of a 13 wt% aqueous sodium chloride solution until the pH of the aqueous phase reached 6. After dehydration with CaSO _4, vacuum drying was performed at 0.7 kPa for 50 hours to obtain 7.9 g of a polymer (yield: 68%). When the residual amount of lithium in the polymer was measured, it was less than 1 μg / g.

Example 6 Barium diisopropoxide 0.26 mmol as catalyst
l, 6.2 g (49 mmol) of m-diethynylbenzene was used as a diethynyl compound, and stirring was performed at 80 ° C. for 3.75 hours under the other conditions in the same manner as in Example 23. When the reaction solution was analyzed by GC, the conversion of phenylsilane was 90%, and the conversion of m-diethynylbenzene was 98%.
%Met. After the same post-processing as in Example 5,
Vacuum drying was performed at 7 kPa for 12 hours to obtain 9.8 g of a yellow polymer (83% yield). The weight average molecular weight in terms of styrene measured by GPC (gel permeation chromatography) was about 530,000. When the residual amount of barium in the polymer was measured, it was less than 2 μg / g.

Comparative Example 2 A polymer reaction solution having a weight average molecular weight in terms of styrene of 480,000 was obtained by the same reaction procedure as in Example 6. The reaction solution was concentrated without removing the catalyst with an aqueous hydrochloric acid solution, and the solvent and the monomer were removed by vacuum drying.
0.1 g was obtained. The residual amount of barium in the polymer is 34
It was 00 μg / g.

Synthesis Example 1 Literature (A. Yanagisawa, S. Habaue, K. Yasue, and H. Y
amamoto, Journal of American Chemical Society, Vol.
116, 6130-6141 (1994))
An HF (tetrahydrofuran) suspension was prepared. 0.482 g (1.13 mmol) of barium iodide dihydrate was heated at 150 ° C. and 0.4 kPa for 3 hours to obtain 0.443 g of anhydrous barium iodide. Biphenyl 0.389
g (2.52 mmol) and lithium 0.017 g
(2.45 mmol) in 5.6 ml of THF to form a lithium / biphenyl complex, and react with 0.443 g of anhydrous barium iodide in 5 ml of THF to react with 10.11 g of an active barium THF suspension.
I got

Example 7 5.5 g (51 mmol) of phenylsilane as a raw material,
Using 5.4 g (53 mmol) of phenylacetylene and 2.49 g (corresponding to 0.28 mmol of barium) of the barium suspension prepared in Synthesis Example 1 as a catalyst, the other conditions were the same as those in Example 1 at 80 ° C. Stirring was performed for hours.
After the reaction, the reaction solution was analyzed by GC (gas chromatography). Phenylethynyl (phenyl) silane (28% yield) and bis (phenylethynyl) as products
(Phenyl) silane (5% yield) was obtained. The reaction rate was 44% for phenylsilane and 41% for phenylacetylene.
%Met. After performing the same post-treatment as in Example 1, the reaction solution was concentrated to 7.9 g with an evaporator. When the residual amount of barium in the reaction solution was measured, it was less than 2 μg / g.

Example 8 Instead of phenylacetylene, 6.7 g (53 mmol) of m-diethynylbenzene was used, and 4.78 g of barium suspension (equivalent to 0.53 mmol of barium) was used. The mixture was stirred at 80 ° C. for 8 hours in the same manner as described above. When the reaction solution was analyzed by GC, the conversion of phenylsilane was 68%, and the conversion of m-diethynylbenzene was 78%. After the same post-treatment as in Example 2, vacuum drying was performed at 0.7 kPa for 50 hours, and 7.6 was obtained.
g polymer was obtained (62% yield). The weight average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography) was about 1900. When the residual amount of barium in the polymer was measured, it was less than 2 μg / g. From the above results, it is clear that the catalyst can be easily removed by the catalyst removing operation.

[0078]

According to the method for producing a silylacetylene compound from a silyl compound and an ethynyl compound and a silicon-containing polymer from a hydrosilyl compound and a diethynyl compound using a metal hydride, a metal compound or a typical element metal as a catalyst, the reaction after the reaction is completed. The catalyst could be removed by treating the liquor with an acidic or neutral aqueous solution.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Masayoshi Ito 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Inside (72) Inventor Shiro Fujikake 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Chemical Co., Ltd.

Claims (2)

[Claims] 1. R _4-m —SiH _m (where m is a positive integer of 4 or less, R is an alkyl group having 1 to 30 carbon atoms,
It is an alkenyl group, an alkynyl group, or an aromatic group, and may contain a halogen atom, a hydroxyl group, an amino group, a carboxyl group, or an ether group. When m is 1 or 2, each R may be the same or different. Silyl compound with R ¹ -C≡CH (wherein represented by), R ¹ represents an alkyl group having 1 to 30 number of hydrogen atoms or carbon atoms, an alkenyl group, an alkynyl group, an aromatic group, a halogen atom, a hydroxyl group, An ethynyl compound represented by the formula (1) (which may contain an amino group, a carboxyl group, or an ether group) is reacted in the presence of a metal hydride, a metal compound or a typical elemental metal. ) (In the formula, m is a positive integer of 4 or less, and R is an alkyl group, alkenyl group, alkynyl group, or aromatic group having 1 to 30 carbon atoms, and is a halogen atom, a hydroxyl group, an amino group, a carboxyl group, an ether group. And when m is 1 or 2, each R may be the same or different, and R ¹ is a hydrogen atom or an alkyl, alkenyl, alkynyl, or aromatic group having 1 to 30 carbon atoms. In the method for producing a silylacetylene compound represented by the formula (1), the reaction may be terminated by a halogen atom, a hydroxyl group, an amino group, a carboxyl group, or an ether group, and i is a positive integer of m or less. A post-treatment method comprising removing the catalyst by treating the post-reaction solution with an aqueous solution. 2. R ² —SiH ₂ —R ³ (wherein R ² and R ³ are each independently a hydrogen atom or a carbon atom having 1 to 30 carbon atoms.
Alkyl group, alkenyl group, alkynyl group, and aromatic group, and these groups may include a halogen atom, a hydroxyl group, an amino group, a carboxyl group, and an ether group. ) And a general formula (2)
(Chemical formula 2) (Wherein, R ⁴ represents an alkylene group having 1 to 30 carbon atoms, an alkenylene group, an alkynylene group, a divalent aromatic group, an alkylene group having 1 to 30 carbon atoms, directly or via a bridge member, alkenylene A group linked to a group, an alkynylene group or an aromatic group, which may include a halogen atom, a hydroxyl group, an amino group, a carboxyl group, or an ether group, and n is a positive integer of 0 or 4 or less. Is reacted in the presence of a metal hydride, a metal compound or a typical elemental metal to give a general formula (3). (Wherein, R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, an alkenyl group, an alkynyl group, or an aromatic group; R ⁴ is an alkylene group having 1 to 30 carbon atoms; Alkenylene group, alkynylene group, divalent aromatic group, a group in which an aromatic group is linked to an alkylene group having 1 to 30 carbon atoms, alkenylene group, alkynylene group, or aromatic group directly or via a crosslinking member; May have a halogen atom, a hydroxyl group, an amino group, a carboxyl group, or an ether group. N is 0 or a positive integer of 4 or less.) In a method for producing a silicon polymer, a post-treatment method comprising removing a catalyst by treating a reaction solution with an aqueous solution after completion of the reaction.