JPH05125177A - Method for producing silicon-containing polyoxyalkylene compound - Google Patents

Abstract

PURPOSE:To obtain the subject compound useful as a raw material for elastic sealant by one process and efficiently by reacting a polyether polyol with a hydrogenated silicon group-containing compound in the presence of a catalyst of transition metal of the group VIII. CONSTITUTION:(A) A polyether polyol (having preferably 500-6,000 average molecular weight) is reacted with (B) a compound (e.g. ethylsilane) containing preferably two hydrogenated silicon groups in the presence of preferably 0.01-5wt.% (based on the component B) catalyst (e.g. Raney-nickel catalyst) of transition metal of the group VIII at 40-150 deg.C to give the objective compound. The reaction is preferably carried out in a weight ratio of hydrogenated silicon group/hydroxyl group of 0.5-2.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a polyoxyalkylene compound containing silicon.

[0002]

2. Description of the Related Art Conventionally, a method for producing a polyoxyalkylene compound containing silicon has been to prepare a polyoxyalkylene compound having an ether type allyl olefin group at the end of the polyoxyalkylene compound and then hydrogenate it in the presence of a Group VIII transition metal. A production method of reacting with a compound having a silicon group (for example, JP-B-58-41291 and JP-B-59-2).
5808) is known.

[0003]

However, in this production method, the first step is to make the end of the polyoxyalkylene compound a polyoxyalkylene compound having an ether type allyl olefin group, and the second step is to react it with a compound having a silicon hydride group.
It was composed of two steps, which was disadvantageous in terms of process.

[0004]

As a result of intensive studies to solve the above problems, the present inventors have found a one-step production method using a specific catalyst and arrived at the present invention. That is, the present invention is the following production methods [I], [II] and [III].
[I]: The polyether polyol (i) and the compound (ii) having a silicon hydride group are combined with a Group VIII transition metal catalyst (iii)
A process for producing a silicon-containing polyoxyalkylene compound, which comprises reacting in the presence of [II]: Polyether polyol (i) and compound (iia) having two silicon hydride groups
And a silicon hydride group / hydroxyl group equivalent ratio of 1 to 2 are used in the reaction in the presence of the Group VIII transition metal catalyst (iii) to obtain an aliphatic group having 1 to 4 carbon atoms. A process for producing a silicon-containing polyoxyalkylene compound, which comprises reacting alcohol (iv) in the presence of (iii). [II
I]: Polyether polyol (i), compound (iia) having two silicon hydride groups, and aliphatic alcohol (iv) having 1 to 4 carbon atoms, [silicon hydride group of (iia)] /
The equivalent ratio of [(i) hydroxyl group] is 1-2, and
The equivalent ratio of [(i) hydroxyl group] / [(iv) hydroxyl group] is 0.
When used in a ratio of 1 to 1, a Group VIII transition metal catalyst (ii
A process for producing a silicon-containing polyoxyalkylene compound, which comprises reacting in the presence of i).

Examples of (i) include compounds having a structure in which alkylene oxide is added to an active hydrogen-containing compound such as polyhydric alcohol, polyhydric phenol, amines and polycarboxylic acid. Examples of the polyhydric alcohol include dihydric alcohols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol and neopentyl glycol; glycerin, trimethylolpropane, trimethylolethane and hexanetriol. Trihydric alcohols such as triethanolamine; pentahydric alcohols such as pentaerythritol, methylglycoside and diglycerin; pentahydric alcohols such as adonitol, arabitol and xylitol; hexahydric alcohols such as sorbitol and mannitol; glucose, mannose and fructose. Monosaccharides; polysaccharides such as sucrose, crehalose, lactose and raffinose; polyols (ethylene glycol,
Glycols such as propylene glycol, glycerin,
Glucosides such as trimethylolpropane and alkane polyols such as hexanetriol; polyglycerins such as triglycerin and tetraglycerin; polypentaerythritol such as dipentaerythritol and tripentaerythritol; and cycloalkanes such as tetrakis (hydroxymethyl) cyclohexanol Examples include polyols. Examples of polyhydric phenols include
Monocyclic polyhydric phenols such as pyrogallol, hydroquinone and phloroglucin; bisphenols such as bisphenol A and bisphenol sulfone; condensates of phenol and formaldehyde (Novolak) US Patent No. 32
The polyphenol described in the specification of 65641 is mentioned. Examples of amines include ammonia; alkanolamines such as mono-, di-, and tri-ethanolamine, isopropanolamine, aminoethylethanolamine; C ₁ -C ₂₀ alkylamines; C ₂ -C _6.
Aliphatic amines such as alkylenediamine (ethylenediamine, propylenediamine, hexamethylenediamine, etc.), polyalkylenepolyamine (diethylenetriamine, triethylenetetramine, etc.); aniline, phenylenediamine, diaminotoluene, xylylenediamine, methylenedianiline, diphenyletherdiamine And aromatic amines such as; alicyclic amines such as isophoronediamine, cyclohexylenediamine, and dicyclohexylmethanediamine; and heterocyclic amines such as aminoethylpiperazine described in JP-B-55-21044. As the polycarboxylic acid, for example,
Aliphatic polycarboxylic acids such as succinic acid, adipic acid, sebacic acid, maleic acid, dimer acid; and phthalic acid,
Aromatic polycarboxylic acids such as trimellitic acid may be mentioned. Two or more kinds of these active hydrogen atom-containing compounds may be used in combination. Of these, preferred are polyhydric alcohols and amines having a valence of 2 or more, and more preferred are polyhydric alcohols and amines having a valence of 2 to 3. Examples of the alkylene oxide to be added to the active hydrogen atom-containing compound include ethylene oxide, propylene oxide, 1,2- or 1,4-butylene oxide, styrene oxide, and a combination of two or more thereof (block addition or random addition). But it may be). The silicon-containing polyoxyalkylene compound produced by the production method of the present invention has Si-O- in the molecule.
It has a C bond, and this bond is generally susceptible to hydrolysis, but the hydrolyzability can be controlled by the type of alkylene oxide to be added. That is, if a large amount of ethylene oxide is used as the alkylene oxide to be added to the active hydrogen atom-containing compound, the hydrophilicity of the produced silicon-containing polyoxyalkylene compound is increased, and the hydrolyzability can be increased, and propylene oxide,
If a large amount of 1,2- or 1,4-butylene oxide or styrene oxide is used, the hydrophobicity of the produced silicon-containing polyoxyalkylene compound is increased and the hydrolyzability can be suppressed. In (i), two or more compounds having a structure in which an alkylene oxide is added to the above active hydrogen-containing compound can be used in combination, and the average molecular weight thereof is usually 200 to 12,000, preferably 500 to
It is 6,000.

As (ii), compounds having one or more silicon hydride groups (Si-H) in the molecule can be used. Examples of the compound having one silicon hydride group in the molecule include trichlorosilane, dimethylchlorosilane, diethylchlorosilane, dimethoxychlorosilane, methyldichlorosilane, ethyldichlorosilane, methoxydichlorosilane, methyldimethoxysilane, methyldiethoxysilane and phenyl. Examples thereof include dimethylsilane and triethylsilane. Examples of the compound having two silicon hydride groups in the molecule include diethylsilane, diethoxysilane, methylphenylsilane, diphenylsilane, 1,
1,3,3-tetramethyldisiloxane, 1,1,3
3-tetramethyldisilazane, 1,4-bis (dimethylsilyl) benzene, 1,1,3,3,5,5-hexamethyltrisiloxane, 1,1,1,3,5,7,7,7
-Octamethyltetrasiloxane and the like. Further, examples of the compound having three or more silicon hydride groups in the molecule include 1,3,5,7-tetramethylcyclotetrasiloxane, phenylsilane, 1,3,5,7,9-pentamethylcyclopentasiloxane. Etc. Two or more of these silicon hydride group-containing compounds can be used in combination. Of these, preferred are compounds having one or two silicon hydride groups in the molecule.

As (iia), among the compounds listed as (ii), those exemplified as the compounds having two silicon hydride groups in the molecule can be used alone or in combination of two or more kinds. Of these, preferred are 1,1,3,3-
Tetramethyldisiloxane, 1,4-bis (dimethylsilyl) benzene, 1,1,3,3,5,5-hexamethyltrisiloxane, 1,1,1,3,5,7,7,7-
Octamethyltetrasiloxane.

As (iii), cobalt, nickel,
At least one group VIII transition metal complex compound selected from the group consisting of rubidium, rhodium, palladium, and platinum can be used. Among these, preferred are Raney nickel catalyst, rubidium-carbon catalyst in which rubidium metal is supported on activated carbon, rhodium-carbon catalyst in which rhodium metal is supported on activated carbon, and palladium-carbon on which palladium metal is supported on activated carbon. It is at least one compound selected from the group consisting of a catalyst, palladium chloride and chloroplatinic acid, and more preferably a palladium-carbon catalyst in which palladium metal is supported on activated carbon and / or palladium chloride. The amount of (iii) used is usually 0.001 relative to the silicon hydride group-containing compound (ii).
10 to 10% by weight, preferably 0.01 to 5% by weight.
If it is less than 0.001% by weight, the time required for production becomes extremely long, and if it exceeds 10% by weight, the catalytic effect is not improved.

In the production processes [I], [II] and [III], the reaction temperature is usually 20 to 200 ° C., preferably 40 to 150.
℃. If it is lower than 40 ° C, the reaction is slow, and if it exceeds 150 ° C, the reaction solution may be colored. The reaction pressure is usually atmospheric pressure, but it may be carried out under pressure.

In the production method [I], the use ratio of the polyether polyol (i) and the silicon hydride group-containing compound (ii) can be arbitrarily selected according to the purpose. When a compound having one silicon hydride group in the molecule is used as (ii), the terminal of (i) is partially substituted depending on the equivalent ratio of silicon hydride group / hydroxyl group of (i) and (ii). From a silicon-containing polyoxyalkylene compound having a structure in which (ii) is dehydrogenatively condensed,
A silicon-containing polyoxyalkylene compound having a structure in which the terminal of (i) is completely dehydrogenated and condensed in (ii) can be quantitatively produced. When the compound (iia) having two silicon hydride groups in the molecule is used as (ii), by reacting the silicon hydride group / hydroxyl group at an equivalent ratio of 1 to 2, A silicon-containing polyoxyalkylene polymer having a silicon hydride group can be produced, and the silicon hydride group / hydroxyl group equivalent is reacted at a ratio of 0.5 to 1 to give silicon having a hydroxyl group at the terminal. A polyoxyalkylene polymer containing can be produced.

The polyether polyol (i) and the compound (iia) having two silicon hydride groups used in the production method [II] have a silicon hydride group / hydroxyl group equivalent ratio of 1 to 2
It is preferable to use it in a ratio such that When the equivalent ratio of silicon hydride group / hydroxyl group is less than 1, a silicon-containing polyoxyalkylene compound having a hydroxyl group at the terminal is obtained, and a silicon-containing polyoxyalkylene compound having an alkoxysilicon group cannot be produced. When the equivalent ratio of silicon hydride group / hydroxyl group exceeds 2, a by-product having a structure in which both ends of (iia) used are alkoxylated is generated.

The polyether polyol (i) used in the production method [III], the compound (iia) having two silicon hydride groups, and the aliphatic alcohol (iv) having 1 to 4 carbon atoms.
Has an equivalence ratio of [silicon hydride group of (iia)] / [hydroxyl group of (i)] of 1 to 2 and an equivalence ratio of [hydroxyl group of (i) / [hydroxyl group of (iv)] , 0.1 to 1 is preferably used. When the equivalent ratio of [silicon hydride group of (iia)] / [hydroxyl group of (i)] is less than 1, a silicon-containing polyoxyalkylene compound having a hydroxyl group at the terminal is the main component, and when it exceeds 2, it is used. Since the by-product having a structure in which both ends of (iia) are alkoxylated becomes the main component, it is not suitable for producing a silicon-containing polyoxyalkylene compound having an alkoxy silicon group. If the equivalent ratio of [(i) hydroxyl group] / [(iv) hydroxyl group] exceeds 1, the by-product of the structure in which both ends of (iia) used are alkoxylated becomes the main component, When the equivalent ratio of the hydroxyl groups of (i) and (iv) is less than 0.1, the silicon-containing polyoxyalkylene compound having a hydroxyl group at the terminal becomes the main component, and for producing a silicon-containing polyoxyalkylene compound having an alkoxy silicon group, Not suitable.

In the production processes [I], [II] and [III], a solvent can be used if necessary. Suitable solvents are those having no active hydrogen such as ethers, aliphatic hydrocarbons, aromatic hydrocarbons and halogenated hydrocarbons.

(Iii) used in the production processes [I], [II] and [III] is usually in a heterogeneous suspension state, and can be easily removed from the system by filtration after the reaction is completed. .. The filtered (iii) can be reused as it is, and the present invention is also advantageous in the process from the viewpoint of the process in this respect.

[0015]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited to these examples. Parts in the examples are parts by weight.

Example 1 300 parts (about 0.1 mol) of polyoxypropylene glycol having a number average molecular weight of about 3,000 and 10% palladium-
1.65 parts of carbon was placed in a glass reaction vessel, and 23 parts (about 0.2 mol) of methyldichlorosilane was added dropwise over 2 hours while stirring at 40 ° C. After continuing the reaction at 40 ° C. for 3 hours, the catalyst was removed by filtration to obtain a transparent liquid product. As a result of quantifying the amount of methyldichlorosilane remaining in the product by gas chromatography, the reaction rate was 99.7%. The infrared absorption spectrum of the product shows that SiH derived from methyldichlorosilane (2120 cm-
Since the absorption of 1) did not exist at all, it was found that polyoxypropylene having a methyldichlorosilyl group at the terminal was quantitatively produced. Product viscosity is 25 ° C
Was 350 cps.

Example 2 300 parts (about 0.1 mol) of polyoxypropylene glycol having a number average molecular weight of about 3,000 and 10% palladium-
0.68 parts of carbon was placed in a glass reaction vessel, and 6.75 parts (about 0.05 mol) of tetramethyldisiloxane was added dropwise over 2 hours while stirring at 50 ° C. Continued at 50 ℃
The reaction was carried out for 1 hour at 70 ° C. for 2 hours. The reaction liquid was filtered to remove palladium-carbon, and a transparent liquid product was obtained. Tetramethyldisiloxane remaining in the product,
Tetramethyldisiloxane was below the detection limit as determined by gas chromatography, and the reaction rate was 100.
%Met. The number average molecular weight of the product was measured and found to be 5,600. The infrared absorption spectrum of the product shows that SiH derived from tetramethyldisiloxane (2120 cm-
Since there was no absorption of 1), it was found that polyoxypropylene glycol dimerized with tetramethyldisiloxane was produced in high yield. The viscosity of the product was 5,800 cps at 25 ° C.

Example 3 300 parts (about 0.1 mol) of polyoxypropylene glycol having a number average molecular weight of about 3,000 and 2.02 parts of 10% palladium-carbon were placed in a glass reaction vessel and stirred at 50 ° C. Meanwhile, 20.15 parts (about 0.15 mol) of tetramethyldisiloxane was added dropwise over 3 hours. Continued 5
When tetramethyldisiloxane remaining in the product after reacting at 0 ° C. for 1 hour and at 90 ° C. for 4 hours was quantified by gas chromatography, tetramethyldisiloxane was below the detection limit, and the reaction rate was 100. %Met. 6
It was cooled to 0 ° C and 16.0 parts of methyl alcohol (about 0.5
Mol) was added. After stirring at 60 ℃ for 2 hours, 100 ℃
After heating, the excess methyl alcohol was distilled off under reduced pressure.
The reaction liquid was filtered to remove palladium-carbon, and a transparent liquid product was obtained. The number average molecular weight of the product was measured to be 5,900, and the infrared absorption spectrum of the product showed that SiH (2120
There is no absorption of cm-1) and SiOCH3 (850
cm-1) was detected, polyoxypropylene glycol was dimerized with tetramethyldisiloxane, and methoxysilylated polyoxypropylene glycol having a methoxysilyl group at the terminal was produced in high yield. I understood it. The product viscosity was 4,200 cps at 25 ° C.

Example 4 300 parts (about 0.1 mol) of polyoxypropylene glycol having a number average molecular weight of about 3,000, 3.2 parts (about 0.1 mol) of methyl alcohol and 10% palladium-carbon 2 0.02 part was placed in a glass reaction vessel, and 20.15 parts of tetramethyldisiloxane (about 0.
15 mol) was added dropwise over 2.5 hours. Continued at 50 ℃
When tetramethyldisiloxane remaining in the product after reacting for 1 hour at 100 ° C. for 6 hours was quantified by gas chromatography, tetramethyldisiloxane was below the detection limit, and the reaction rate was 100%. there were. The reaction liquid was filtered to remove palladium-carbon, and a transparent liquid product was obtained. The number average molecular weight of the product was measured to be 5,300, and the infrared absorption spectrum of the product showed that the product had a SiH (2120c
There is no absorption of m-1), and SiOCH3 (850c
Since m-1) absorption was detected, polyoxypropylene glycol was dimerized with tetramethyldisiloxane, and methoxysilylated polyoxypropylene glycol having a methoxysilyl group at the terminal was produced in high yield. I understood it. The product viscosity was 3,900 cps at 25 ° C.

[0020]

INDUSTRIAL APPLICABILITY According to the production method of the present invention, not only the silicon-containing polyoxyalkylene compound can be produced in a very process-wise manner as compared with the conventional production method, but also the production of the silicon-containing polyoxyalkylene compound is difficult with the conventional technique. It is also possible to synthesize a high molecular weight polyoxyalkylene having the above structure. From such effects, the silicon-containing polyoxyalkylene compound production technology of the present invention is used as a raw material for elastic sealants such as construction, ships, automobiles and roads, and as a base material for cosmetics, pharmaceuticals, lubricating oils, etc. Or resin,
It can be applied to a wide range of fields as a modifier for surfactants.

Claims (6)

[Claims] 1. A silicon-containing polyoxyalkylene compound characterized in that a polyether polyol (i) and a compound (ii) having a silicon hydride group are reacted in the presence of a Group VIII transition metal catalyst (iii). Manufacturing method. 2. The method according to claim 1, wherein (ii) is a compound (iia) having two silicon hydride groups. 3. The method according to claim 2, wherein (i) and (iia) are reacted at a ratio such that the equivalent ratio of silicon hydride group / hydroxyl group is 0.5 to 2. 4. The polyether polyol (i) and the compound (iia) having two silicon hydride groups are used at a ratio of the silicon hydride group / hydroxyl group equivalent ratio of 1 to VI.
The reaction was conducted in the presence of a Group II transition metal catalyst (iii), and the aliphatic alcohol (iv) having 1 to 4 carbon atoms was added to (iii)
A process for producing a silicon-containing polyoxyalkylene compound, which comprises reacting in the presence of 5. A polyether polyol (i), a compound (iia) having two silicon hydride groups, and 1 to 4 carbon atoms.
Of the aliphatic alcohol (iv) of [(iia) silicon hydride group] / [hydroxy group of (i)] is 1 to 2, and
The equivalent ratio of [(i) hydroxyl group] / [(iv) hydroxyl group] is 0.
When used in a ratio of 1 to 1, a Group VIII transition metal catalyst (ii
A process for producing a silicon-containing polyoxyalkylene compound, which comprises reacting in the presence of i). 6. The method according to claim 1, wherein (iii) is palladium metal and / or palladium chloride.