CN112759607A - Method for producing imino group-containing organooxysilane compound - Google Patents
Method for producing imino group-containing organooxysilane compound Download PDFInfo
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- CN112759607A CN112759607A CN202011127979.0A CN202011127979A CN112759607A CN 112759607 A CN112759607 A CN 112759607A CN 202011127979 A CN202011127979 A CN 202011127979A CN 112759607 A CN112759607 A CN 112759607A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/188—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-O linkages
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
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Abstract
Provided is a method for efficiently producing an organooxysilane compound containing an imino group with high yield. The method for producing an imino-containing organooxysilane compound represented by general formula (3) by reacting a carbonyl-containing compound represented by general formula (1) with an aminoorganooxysilane compound represented by general formula (2), wherein the reaction is carried out in the presence of water as a by-product using a compound mixed with water at 25 ℃ in a mass ratio of 1: 1 as a solvent.
(R1Represents a hydrogen atom or a C1-20 m-valent hydrocarbon group which may contain a hetero atom, R2Represents a hydrogen atom or a C1-20 hydrocarbon group, and m represents 1 to EAn integer of 10. ) H2N‑R3‑SiR4 n(OR5)3‑n(2)(R3R is a C1-20 2-valent hydrocarbon group4And R5Represents a C1-20 1-valent hydrocarbon group, and n represents 0, 1 or 2. )
(in the formula, R1～R5M and n represent the same meanings as described above).
Description
Technical Field
The present invention relates to a method for producing an imino group-containing organoxysilane compound.
Background
The nitrogen-containing organoxysilane compound is useful as a coating additive, an adhesive, a silane coupling agent, a fiber treating agent, a surface treating agent, and the like.
In particular, since the imino group-containing organooxysilane compound has a structure in which the amino group is protected, it can be mixed with an epoxy resin raw material to prepare a one-pack type composition, and can be used as a curable composition having an effect of adding an amino silane coupling agent (improvement in adhesiveness and reinforcement). That is, the composition containing the organooxysilane compound having an imino group is stable because it shows no reactivity if it is a system blocking moisture, but it shows the same effect as that when the amino silane coupling agent is added, because deprotection by hydrolysis of the imino group and regeneration of the amino group occur by contact with moisture.
Examples of the method for producing the imino group-containing organoxysilane compound include a method in which 3-aminopropyltrimethoxysilane and cinnamaldehyde are reacted while azeotropic dehydration is carried out using an organic solvent (patent document 1); a method in which 3-aminopropyltrimethoxysilane is dropped under reflux of methyl isobutyl ketone and reacted while azeotropic dehydration is performed (patent document 2); as a method of reacting benzaldehyde with 3-aminopropyltrimethoxysilane while azeotropically dehydrating it under toluene reflux (patent document 3), a method of quickly distilling out water produced as a reaction by-product of a carbonyl group-containing compound and an aminoorganoxysilane compound to the outside of a reactor by azeotropic dehydration using a nonpolar solvent such as toluene is generally widely used.
In addition, as in a method of reacting methyl isobutyl ketone with butylamine using hexamethyldisilazane as a dehydrating agent to prepare methyl isobutylidene butylamine, and then reacting the methyl isobutylidene butylamine with aminopropyltrimethoxysilane (patent document 4), a method of distilling water from the inside of a reactor by adding a dehydrating agent is also generally used.
Documents of the prior art
Patent document
Patent document 1: specification of U.S. Pat. No. 2942019
Patent document 2: japanese laid-open patent publication No. 7-247294
Patent document 3: japanese patent laid-open publication No. 2017-66335
Patent document 4: japanese patent laid-open publication No. 2019-151598
Disclosure of Invention
Problems to be solved by the invention
The reason why the water produced as a reaction by-product is quickly distilled off from the reactor by azeotropic dehydration during the reaction in the methods described in the above patent documents 1 to 3 is that (1) the reaction is carried out in a state in which the equilibrium of the reaction is inclined toward the imino group producing reaction side, and (2) the hydrolytic condensation reaction of the produced imino group-containing organooxysilane due to the water produced as a by-product is prevented. The reason why a nonpolar solvent such as toluene is used is that the use of a nonpolar solvent reduces the polarity in the system, and water separation can suppress the hydrolytic condensation reaction.
However, the methods of patent documents 1 to 3 have a problem that, particularly when the number of organic oxy groups bonded to silicon atoms in the target compound is 4 or more, the separated water generates organic substances and water-insoluble solids that are highly hydrolyzed and condensed, and the organic substances and the water-insoluble solids adhere to the reactor wall and cannot be removed after the reaction, and thus the industrial production is difficult.
On the other hand, in the method of patent document 4, the formation of a water-insoluble solid by high hydrolytic condensation does not occur as in the case of azeotropic dehydration, but the reaction step is two steps, and further, the reaction rate with aminopropyltrimethoxysilane in the second step is slow, so that it is not industrially advantageous.
In view of the above circumstances, an object of the present invention is to provide a method for efficiently producing an organoxysilane compound containing an imino group with high yield.
Means for solving the problems
The present inventors have made extensive studies to achieve the above object, and as a result, have found that: by using a mixture of 1: 1 as a solvent, and the by-produced water is uniformly present in the system without forming water droplets, and no organic matter or water-insoluble solid is produced, thereby completing the present invention.
Namely, the present invention provides:
1. a method for producing an imino-containing organooxysilane compound represented by the following general formula (3) by reacting a carbonyl-containing compound represented by the following general formula (1) with an aminoorganooxysilane compound represented by the following general formula (2), wherein the reaction is carried out at 25 ℃ in a mass ratio of 1: 1 reacting in the presence of water as a by-product, using a compound mixed with water as a solvent,
[ CHEM 1]
(in the formula, R1Represents a hydrogen atom or a C1-20 m-valent hydrocarbon group which may contain a hetero atom, R2Represents a hydrogen atom or a C1-valent hydrocarbon group having 1 to 20 carbon atoms, and m represents an integer of 1 to 10. )
[ CHEM 2]
H2N-R3-SiR4 n(OR5)3_n (2)
(in the formula, R3R is a C1-20 2-valent hydrocarbon group4And R5Each independently represents a C1-20 1-valent hydrocarbon group, and n represents 0, 1 or 2. )
[ CHEM 3]
(in the formula, R1～R5M and n are as defined above. )
2.1A process for producing an imino-containing organoxysilane compound, wherein the compound to be mixed with water is 1 or 2 or more selected from the group consisting of an alcohol compound having 1 to 3 carbon atoms, an ether compound, a ketone compound, a nitrile compound, an amide compound, a sulfoxide compound and a phosphoric triamide compound,
3.1 or 2, wherein the product of m and (3-n) in the general formula (3) is an integer of 4 or more,
4.1 to 3 of the process for producing an imino-containing organoxysilane compound, wherein R is2Is a hydrogen atom.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the production method of the present invention, the water produced as a by-product does not exist uniformly in the system as water droplets, and therefore, the nitrogen-containing organoxysilane compound useful as a paint additive, an adhesive, a silane coupling agent, a fiber treatment agent, a surface treatment agent, and the like can be produced efficiently and in high yield without locally highly hydrolyzing the water droplets produced as a by-product to produce an organic substance and a water-insoluble solid as in the conventional technique.
Detailed Description
The present invention will be specifically described below.
The method for producing an imino-containing organooxysilane compound represented by the following general formula (3) of the present invention comprises reacting a carbonyl-containing compound represented by the following general formula (1) with an aminoorganooxysilane compound represented by the following general formula (2) at 25 ℃ in a mass ratio of 1: 1 as solvent, a compound mixed with water.
[ CHEM 4]
In the general formulae (1) and (3), R1Represents a hydrogen atom or an m-valent hydrocarbon group having 1 to 20 carbon atoms and which may contain a hetero atom, R2Represents a hydrogen atom or a C1-valent hydrocarbon group having 1 to 20 carbon atoms, and m represents an integer of 1 to 10.
In the general formulae (2) and (3), R3R is a C1-20 2-valent hydrocarbon group4And R5Each independently represents a C1-20 1-valent hydrocarbon group, and n represents 0, 1 or 2.
R is as defined above1The m-valent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, which may contain a hetero atom, may be any of linear, branched and cyclic, and specific examples thereof includeA linear alkyl group such as an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, and an eicosyl group; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-hexyl and 2-ethylhexyl; cyclic alkyl groups such as cyclopentyl and cyclohexyl; alkenyl groups such as vinyl, allyl (2-propenyl), and 1-propenyl; aryl groups such as phenyl and tolyl; aralkyl groups such as benzyl; aryl groups containing hetero atoms such as pyridyl and pyrazinyl; alkylene groups such as methylene, ethylene, methylethylene (propylene), trimethylene, 1-methyltrimethylene, 2-methyltrimethylene (isobutylene), tetramethylene, hexamethylene, octamethylene, and decamethylene; arylene groups such as phenylene; aralkylene groups such as methylenephenylene and methylenephenylenemethylene; and heteroatom-containing alkylene groups such as 1-oxamethylene (1-oxamethylene) and 1-azamethylene.
Among these, R is particularly preferred from the viewpoints of availability of raw materials and usefulness of products1Preferably an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, etc.; aryl groups having 6 to 7 carbon atoms such as phenyl and tolyl; a phenylene group.
R is as defined above2、R4And R5The 1-valent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, may be any of a straight chain, a branched chain, and a cyclic, and specific examples thereof include straight chain alkyl groups such as a methyl group, an ethyl group, a n-propyl group, a n-butyl group, a n-pentyl group, a n-hexyl group, a n-heptyl group, a n-octyl group, a n-decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, and an eicosyl group; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-hexyl and 2-ethylhexyl; cyclic alkyl groups such as cyclopentyl and cyclohexyl; alkenyl groups such as vinyl, allyl, butenyl, pentenyl and the like; aryl groups such as phenyl and tolyl; aralkyl groups such as benzyl group, etc.
Among these, R is particularly preferred from the viewpoints of availability of raw materials and usefulness of products2Preferably an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, etc.; allyl, butenyl, pentenThe alkenyl group having 1 to 5 carbon atoms such as a radical is more preferably a hydrogen atom from the viewpoint of greatly exhibiting an effect of suppressing the formation of an organic substance or a water-insoluble solid, which is one of the effects of the present invention.
In another aspect, R4And R5Particularly, from the viewpoint of availability of raw materials and usefulness of products, alkyl groups having 1 to 3 carbon atoms such as methyl, ethyl, propyl and the like are preferable.
R is as defined above3The 2-valent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms may be any of a straight chain, a branched chain, and a cyclic, and specific examples thereof include an alkylene group such as a methylene group, an ethylene group, a methylethylene group (propylene group), a trimethylene group, a 1-methyltrimethylene group, a 2-methyltrimethylene group (isobutylene group), a tetramethylene group, a hexamethylene group, an octamethylene group, and a decamethylene group; arylene groups such as phenylene; and aralkylene groups such as ethylene phenylene and ethylene phenylenemethylene.
Among these, R is particularly preferred from the viewpoints of availability of raw materials and usefulness of products3Preferably an alkylene group having 1 to 3 carbon atoms such as a methylene group, an ethylene group, a methylethylene group (propylene group), a trimethylene group, etc.; a phenylene group.
In the general formula (1), m represents an integer of 1 to 10, preferably an integer of 1 to 5, and in the general formula (2), n is 0, 1 or 2, and from the viewpoint of significantly exhibiting the effects of the present invention, it is preferable that the product of m and (3-n) in the general formula (3) is an integer of 4 or more.
Specific examples of the carbonyl group-containing compound represented by the general formula (1) include aliphatic aldehyde compounds such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, and cyclohexanecarboxaldehyde; aromatic aldehyde compounds such as benzaldehyde and tolualdehyde; cinnamaldehyde compounds such as cinnamaldehyde, α -methylcinnamaldehyde, and α -pentylcinnamaldehyde; pyridine-containing aldehyde compounds such as pyridylaldehyde; dialdehyde compounds such as malondialdehyde, succinaldehyde, o-phthalaldehyde, m-phthalaldehyde and p-phthalaldehyde; trialdehyde compounds such as 1, 2, 4-benzenetricarboxylic acid and 1, 3, 5-benzenetricarboxylic acid; aliphatic ketone compounds such as acetone, methyl ethyl ketone, methyl isobutyl ketone and acetylacetone; aromatic ketone compounds such as acetophenone, benzophenone, and diacetylbenzene.
Specific examples of the aminoorganoxysilane compound represented by the general formula (2) include an aminomethylorganoxysilane compound such as aminomethyltrimethoxysilane, aminomethyldimethoxymethylsilane, aminomethylmethoxydimethylsilane, aminomethyltriethoxysilane, aminomethyldiethoxymethylsilane, and aminomethylethoxydimethylsilane; aminopropyl organoxysilane compounds such as 3-aminopropyl trimethoxysilane, 3-aminopropyl dimethoxymethylsilane, 3-aminopropyl methoxydimethylsilane, 3-aminopropyl triethoxysilane, 3-aminopropyl diethoxymethylsilane and 3-aminopropyl ethoxydimethylsilane, and the like.
As a specific example of the imino group-containing organoxysilane compound represented by the general formula (3) obtained by the above reaction, examples thereof include methyleneamino group-containing organooxysilane compounds such as methyleneaminomethyl trimethoxysilane, methyleneaminomethyl dimethoxymethylsilane, methyleneaminomethyl methoxydimethylsilane, methyleneaminomethyl triethoxysilane, methyleneaminomethyl diethoxymethylsilane, methyleneaminomethyl ethoxydimethylsilane, 3- (methyleneamino) propyltrimethoxysilane, 3- (methyleneamino) propyldimethoxymethylsilane, 3- (methyleneamino) propylmethoxydimethylsilane, 3- (methyleneamino) propyltriethoxysilane, 3- (methyleneamino) propyldiethoxymethylsilane, and 3- (methyleneamino) propylethoxydimethylsilane; benzylamino-containing organoxysilane compounds such as benzylamino-methyltrimethoxysilane, benzylamino-methyldimethoxysilane, benzylamino-methylmethoxydimethylsilane, benzylamino-methyltriethoxysilane, benzylamino-methyldiethoxymethylsilane, benzylamino-methylethoxydimethylsilane, 3- (benzylamino) -propyltrimethoxysilane, 3- (benzylamino) -propyldimethoxymethylsilane, 3- (benzylamino) -propylmethoxydimethylsilane, 3- (benzylamino) -propyltriethoxysilane, 3- (benzylamino) -propyldiethoxymethylsilane, and 3- (benzylamino) -propylethoxydimethylsilane; pyridylmethyleneaminomethyltrimethoxysilane, pyridylmethyleneaminomethyldimethoxymethylsilane, pyridylmethyleneaminomethylmethoxydimethylsilane, pyridylmethyleneaminomethyltriethoxysilane, pyridylmethyleneaminomethyldiethoxymethylsilane, pyridylmethyleneaminomethylethoxydimethylsilane, pyridylmethyleneamino-containing organooxysilane compounds such as 3- (pyridylmethyleneamino) propyltrimethoxysilane, 3- (pyridylmethyleneamino) propyldimethoxymethylsilane, 3- (pyridylmethyleneamino) propylmethoxydimethylsilane, 3- (pyridylmethyleneamino) propyltriethoxysilane, 3- (pyridylmethyleneamino) propyldiethoxymethylsilane, and 3- (pyridylmethyleneamino) propylethoxydimethylsilane; n, N-bis (trimethoxysilylmethyl) -1, 4-xylene- α, α ' -diimine, N-bis (dimethoxymethylsilylmethyl) -1, 4-xylene- α, α ' -diimine, N-bis (methoxydimethylsilylmethyl) -1, 4-xylene- α, α ' -diimine, N-bis (triethoxysilylmethyl) -1, 4-xylene- α, α ' -diimine, N-bis (diethoxymethylsilylmethyl) -1, 4-xylene- α, α ' -diimine, N-bis (methoxydimethylsilylmethyl) -1, 4-xylene- α, α ' -diimine, N-bis [3- (trimethoxysilyl) propyl ] -1, 4-xylene- α, α ' -diimine, N-bis [3- (dimethoxymethylsilyl) propyl ] -1, 4-xylene- α, α ' -diimine, N-bis [3- (methoxydimethylsilyl) propyl ] -1, 4-xylene- α, α ' -diimine, N-bis [3- (triethoxysilyl) propyl ] -1, 4-xylene- α, α ' -diimine, N-bis [3- (diethoxymethylsilyl) propyl ] -1, 1, 4-xylene- α, α ' -diimine compounds containing a diorganooxysilyl group such as 4-xylene- α, α ' -diimine and N, N-bis [3- (ethoxydimethylsilyl) propyl ] -1, 4-xylene- α, α ' -diimine.
In the production method of the present invention, the amount of the aminoorganoxysilane compound represented by the general formula (2) to be used is not particularly limited, but is preferably 0.5 to 2.0 mol, more preferably 0.8 to 1.5 mol, based on 1 mol of the carbonyl group-containing compound represented by the general formula (1), from the viewpoints of reactivity and productivity.
As described above, in order to suppress the by-produced organic substances and the water-insoluble solids subjected to the high hydrolysis condensation, the by-produced water should be uniformly present in the system without being separated as the reaction proceeds. However, the solubility of the reaction product itself in water is very small, and in order to completely dissolve the water by-produced in the reaction together with the reaction product, the solvent used needs to have a ratio of 1: 1 degree of mixing, i.e. the degree of solubility in water to which it can be mixed with water in the smallest amount.
Therefore, in the production method of the present invention, a resin composition comprising, at 25 ℃ in a mass ratio of 1: 1 as solvent, a compound mixed with water. The solvent is selected based on the minimum amount of water to be mixed as a by-product at 25 ℃ which is an arbitrary reaction temperature.
Specific examples of such compounds include alcohol compounds having 1 to 3 carbon atoms such as methanol, ethanol, 1-propanol, 2-propanol, ethylene glycol, and glycerol; ether compounds such as tetrahydrofuran and 1, 4-dioxane, preferably cyclic ether compounds having 4 to 5 carbon atoms; ketone compounds such as acetone, preferably ketone compounds having 2 to 3 carbon atoms; nitrile compounds such as acetonitrile; amide compounds such as N-methylformamide, N-dimethylformamide, N-diethylformamide, N-dimethylacetamide, and N-methylpyrrolidone; sulfoxide compounds such as dimethyl sulfoxide; phosphoric triamide compounds such as hexamethylphosphoric triamide are preferably alcohol compounds from the viewpoint of suppressing the hydrolysis reaction. Further, these compounds may be used alone in 1 kind, or 2 or more kinds may be mixed and used.
At 25 ℃, the weight ratio of 1: the amount of the compound to be mixed with water 1 is not particularly limited as long as the water by-produced as the reaction proceeds is uniformly present in the system without being separated, but the amount is preferably 1 to 40 times, more preferably 2 to 20 times, the mass of the water produced in the reaction.
Further, the amount of the organic solvent may be adjusted to a value within a mass ratio of 1: 1 solvent other than the compound mixed with water.
Specific examples of such solvents include hydrocarbon solvents such as pentane, hexane, cyclohexane, heptane, isooctane, benzene, toluene, and xylene; ether solvents such as ether; ester solvents such as ethyl acetate and butyl acetate; chlorinated hydrocarbon solvents such as methylene chloride and chloroform. These solvents may be used alone in 1 kind, or 2 or more kinds may be mixed and used.
The reaction temperature of the above reaction is not particularly limited, but is preferably-20 to 200 ℃, preferably 0 to 80 ℃, more preferably 0 to 50 ℃, and still more preferably 20 to 50 ℃ from the viewpoint of improving the yield.
The method for producing the imino-containing organooxysilane compound represented by general formula (3) may be a method comprising charging a carbonyl-containing compound and a solvent at 25 ℃ in a mass ratio of 1: 1 a method of adding dropwise an aminoorganoxysilane compound to a compound mixed with water (hereinafter simply referred to as a solvent); a method of charging an aminoorganoxysilane compound and a solvent and dropping a carbonyl group-containing compound; a method of batch reaction such as a method of simultaneously dropping a carbonyl group-containing compound and an aminoorganoxysilane compound in a solvent; any method using a continuous reaction method, such as a method of continuously feeding a carbonyl group-containing compound, an aminoorganoxysilane compound, and a solvent to a reactor or a reaction tube and continuously withdrawing the product.
In the present reaction, water is produced as a by-product, and as described above, in the present invention, the reaction is carried out in the presence of by-product water. The water by-produced is preferably removed after the reaction.
The method of removing water after the reaction is not particularly limited, and a method of heating with a solvent under normal pressure or reduced pressure for distillation, a method of adding a dehydrating agent for removal, and the like are exemplified.
From the reaction solution obtained as described above, the target product can be recovered by a usual method such as distillation.
Examples
The present invention will be described more specifically with reference to the following examples and comparative examples, but the present invention is not limited to the following examples.
[ example 1]
53.6g (0.4 mol) of terephthalaldehyde and 240ml of ethanol were charged in a flask equipped with a stirrer, a reflux vessel, a dropping funnel and a thermometer, and 177.1g (0.8 mol) of 3-aminopropyltriethoxysilane was added dropwise at 20 to 50 ℃ over 1 hour, followed by stirring at that temperature for 1 hour. After stirring for 1 hour, no precipitation of solids and no adhesion of solids to the reactor wall were observed.
The resulting reaction solution was heated to 100 ℃ under a reduced pressure of 20kPa to distill off low boiling compounds containing water, whereby 217.5g of N, N-bis [3- (triethoxysilyl) propyl ] -1, 4-xylene- α, α' -diimine was obtained, the product of m and (3-N) in the general formula (3) being 6. Results of gel permeation chromatography analysis: the purity was 95.1% (yield 96%).
[ example 2]
The reaction was carried out in the same manner as in example 1 except that 240ml of ethanol was changed to 240ml of acetonitrile. After stirring for 1 hour, no precipitation of solids and no adhesion of solids to the reactor wall were observed.
The resulting reaction solution was heated to 100 ℃ under a reduced pressure of 20kPa to distill off low boiling compounds containing water, thereby obtaining 219.0g of N, N-bis [3- (triethoxysilyl) propyl ] -1, 4-xylene- α, α' -diimine of the general formula (3) in which the product of m and (3-N) is 6. Results of gel permeation chromatography analysis: the purity was 94.1% (yield 95%).
[ example 3]
The reaction was carried out in the same manner as in example 1 except that 240ml of ethanol was changed to 240ml of tetrahydrofuran. After stirring for 1 hour, no precipitation of solids and no adhesion of solids to the reactor wall were observed.
The resulting reaction solution was heated to 100 ℃ under a reduced pressure of 20kPa to distill off low boiling compounds containing water, thereby obtaining 223.0g of N, N-bis [3- (triethoxysilyl) propyl ] -1, 4-xylene- α, α' -diimine of the general formula (3) in which the product of m and (3-N) is 6. Results of gel permeation chromatography analysis: the purity was 92.2% (yield 95%).
[ example 4]
The reaction was carried out in the same manner as in example 1, except that the amount of ethanol used was changed from 240ml to 80 ml. After stirring for 1 hour, no precipitation of solids and no adhesion of solids to the reactor wall were observed.
The resulting reaction mixture was heated to 100 ℃ under reduced pressure of 20kPa to distill off low boiling compounds containing water, thereby obtaining 218.5g of N, N-bis [3- (triethoxysilyl) propyl ] -1, 4-xylene- α, α' -diimine of the general formula (3) in which the product of m and (3-N) was 6. Results of gel permeation chromatography analysis: the purity was 94.3% (yield 95%).
[ example 5]
53.6g (0.4 mol) of terephthalaldehyde and 240ml of ethanol were charged in a flask equipped with a stirrer, a reflux vessel, a dropping funnel and a thermometer, and 153.0g (0.8 mol) of 3-aminopropyldiethoxymethylsilane was dropped over 1 hour at 20 to 50 ℃ and stirred at that temperature for 1 hour. After stirring for 1 hour, no precipitation of solids and no adhesion of solids to the reactor wall were observed.
The obtained reaction solution was heated to 100 ℃ under a reduced pressure of 20kPa to distill off low boiling point compounds containing water, and 191.1g of N, N-bis [3- (diethoxymethylsilyl) propyl ] -1, 4-xylene- α, α' -diimine was obtained as a product of m and (3-N) in the general formula (3). Results of gel permeation chromatography analysis: the purity was 97.8% (yield 97%).
Comparative example 1
The reaction was carried out in the same manner as in example 1 except that 240ml of ethanol was changed to 240ml of toluene. The adhesion of the solid to the reactor wall was observed from the initial stage of dropping, and the adhesion of the solid to the reactor wall and the precipitation of the solid were observed after stirring for 1 hour.
The reaction mixture was filtered, heated to 100 ℃ under reduced pressure of 5kPa, and the low boiling point compound containing water was distilled off to obtain 194.2g of N, N-bis [3- (triethoxysilyl) propyl ] -1, 4-xylene- α, α' -diimine of the general formula (3) wherein the product of m and (3-N) was 6. Results of gel permeation chromatography analysis: the purity was 96.1% (yield 86%).
Comparative example 2
The reaction was carried out in the same manner as in example 1 except that 240ml of ethanol was changed to 240ml of hexane. The adhesion of the solid to the reactor wall was observed from the initial stage of dropping, and the adhesion of the solid to the reactor wall and the precipitation of the solid were observed after stirring for 1 hour.
The reaction mixture was filtered, heated to 100 ℃ under reduced pressure of 20kPa, and the low boiling point compound containing water was distilled off to obtain 196.3g of N, N-bis [3- (triethoxysilyl) propyl ] -1, 4-xylene- α, α' -diimine of the general formula (3) wherein the product of m and (3-N) was 6. Results of gel permeation chromatography analysis: the purity was 96.6% (yield 88%).
Comparative example 3
A flask equipped with a stirrer, Dean-Stark apparatus, reflux vessel, dropping funnel and thermometer was charged with 53.6g (0.4 mol) of terephthalaldehyde and 240ml of toluene, and heated until the toluene was refluxed. 177.1g (0.8 mol) of 3-aminopropyltriethoxysilane was added dropwise over 1 hour while removing by-produced water under reflux of toluene, and the mixture was stirred under reflux for 1 hour. The adhesion of solids to the reactor wall was observed from the initial stage of dropping, and the adhesion of solids to the reactor wall and the precipitation of a large amount of solids were observed after stirring for 1 hour.
The reaction mixture was filtered, and heated to 100 ℃ under reduced pressure of 5kPa to distill off low boiling compounds, thereby obtaining 203.2g of N, N-bis [3- (triethoxysilyl) propyl ] -1, 4-xylene- α, α' -diimine of the general formula (3) in which the product of m and (3-N) was 6. Results of gel permeation chromatography analysis: the purity was 90.0% (yield 85%).
Comparative example 4
The reaction was carried out in the same manner as in example 5 except that 240ml of ethanol was changed to 240ml of toluene. The adhesion of solids to the reactor wall was observed from the initial stage of dropping, and the adhesion of solids to the reactor wall and the deposition of solids were observed after stirring for 1 hour.
The reaction mixture was filtered, heated to 100 ℃ under reduced pressure of 5kPa, and the low boiling point compound containing water was distilled off to obtain 175.4g of N, N-bis [3- (diethoxymethylsilyl) propyl ] -1, 4-xylene- α, α' -diimine, which was represented by the general formula (3) below and had the product of m and (3-N) of 4. Results of gel permeation chromatography analysis: the purity was 96.8% (yield 88%).
Claims (4)
1. A method for producing an imino-containing organooxysilane compound represented by the following general formula (3) by reacting a carbonyl-containing compound represented by the following general formula (1) with an aminoorganooxysilane compound represented by the following general formula (2), wherein the reaction is carried out at 25 ℃ in a mass ratio of 1: 1 reacting in the presence of water as a by-product, using a compound mixed with water as a solvent,
[ CHEM 1]
In the formula, R1Represents a hydrogen atom or a C1-20 m-valent hydrocarbon group which may contain a hetero atom, R2Represents a hydrogen atom or a C1-valent hydrocarbon group of 1 to 20, m represents an integer of 1 to 10,
[ CHEM 2]
H2N-R3-SiR4 n(OR5)3_n (2)
In the formula, R3R is a C1-20 2-valent hydrocarbon group4And R5Each independently represents a C1-20 1-valent hydrocarbon group, n represents 0, 1 or 2,
[ CHEM 3]
In the formula, R1～R5M and n are as defined above.
2. The method for producing an imino-containing organoxysilane compound according to claim 1, wherein the compound to be mixed with water is 1 or 2 or more selected from the group consisting of an alcohol compound having 1 to 3 carbon atoms, an ether compound, a ketone compound, a nitrile compound, an amide compound, a sulfoxide compound and a phosphoric triamide compound.
3. The method for producing an imino-containing organooxysilane compound of claim 1 or 2, wherein the product of m and (3-n) in the general formula (3) is an integer of 4 or more.
4. The method for producing an imino-containing organoxysilane compound according to any one of claims 1 to 3, wherein R is2Is a hydrogen atom.
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| CN114773376A (en) * | 2022-03-17 | 2022-07-22 | 江苏中新瑞光学材料有限公司 | Process for preparing tris (methyleneoxypropyltrimethoxysilyl) aminomethane |
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| US2942019A (en) * | 1956-10-12 | 1960-06-21 | Union Carbide Corp | Organosilicon methylideneamino compounds and process for producing the same |
| JP2875735B2 (en) | 1994-03-11 | 1999-03-31 | 信越化学工業株式会社 | Method for producing ketimine structure-containing organosilicon compound |
| JP6598458B2 (en) * | 2014-12-23 | 2019-10-30 | ダウ・東レ株式会社 | Silane coupling agent composition, method for producing the same, epoxy resin composition, semiconductor sealing material, and semiconductor device |
| JP2017066335A (en) | 2015-10-02 | 2017-04-06 | 信越化学工業株式会社 | Urethane adhesive composition |
| JP6947084B2 (en) | 2018-03-05 | 2021-10-13 | 信越化学工業株式会社 | Method for Producing Imine Structure-Containing Organoxysilane Compound |
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| CN114773376A (en) * | 2022-03-17 | 2022-07-22 | 江苏中新瑞光学材料有限公司 | Process for preparing tris (methyleneoxypropyltrimethoxysilyl) aminomethane |
| CN114773376B (en) * | 2022-03-17 | 2022-12-23 | 江苏中新瑞光学材料有限公司 | Process for preparing tris (methyleneoxypropyltrimethoxysilyl) aminomethane |
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