JP2017014460A - Manufacturing method of siloxane compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method capable of providing a siloxane compound having a specific structure containing a siloxane bond and an amide bond safely and simply at high yield.SOLUTION: There is provided a manufacturing method of a siloxane compound having a siloxane bond and represented by the following average composition formula (1):XYZSiO, which includes an amidation reaction process of an amino group-containing silane compound and an organic carboxylic acid compound.SELECTED DRAWING: None

Description

The present invention relates to a method for producing a siloxane compound.

A siloxane compound is a compound having a Si—O bond (siloxane bond), and has been widely used as a raw material for various industrial products. And nowadays, it has been applied to various uses due to characteristics such as heat resistance caused by siloxane bonds. Conventional siloxane compounds have been proposed in, for example, Patent Documents 1 and 2 and Non-Patent Document 1.

Japanese Patent No. 5193207 JP 2012-136449 A

Y Kaneko, 5 others, “Chemistry of Materials” (USA), 2004, Vol. 16, p. 3417-3423

Since the characteristics required for the siloxane compound vary depending on the application, it is preferable to further increase the variation of the structure of the siloxane compound from the viewpoint of expanding the range of selection of the siloxane compound having the optimal characteristics depending on the application. Therefore, the present inventor has found that a siloxane compound having a predetermined structure containing a siloxane bond and an amide bond is a material that is effective in terms of insulation and the like. Even if the synthesis method of the amide compound is adopted, there are problems in terms of safety, yield and complicated by-product removal process, and it is difficult to produce industrially with high productivity. It was.

For example, as a method for obtaining a target siloxane compound by employing a conventional method for synthesizing an amide compound, for example, (1) a method of amidation reaction of an amino group-containing silane compound in the presence of a strong acid or a strong base (2) A technique for transesterifying an ester compound and an amino group-containing silane compound, (3) a technique for condensing an amino group-containing silane compound using a carbodiimide compound as a condensing agent, and the like. However, in the method (1), since a strong acid or a strong base may remain in the product at a high concentration, a washing step of the product is necessary, and the yield and the reaction rate are low. In (3), it is necessary to remove a large amount of by-products, and the yield in one reaction is low and the reaction rate is not high.

The present invention has been made in view of the above situation, and provides a production method capable of providing a siloxane compound having a predetermined structure containing a siloxane bond and an amide bond in a safe, simple and high yield. Objective.

The present inventor considered a method for producing a siloxane compound having a predetermined structure containing a siloxane bond and an amide bond, and adopting a production method including an amidation reaction step with an amino group-containing silane compound and an organic carboxylic acid compound, It has also been found that a siloxane compound can be obtained simply and in a high yield. In such a production method of the present invention, the reaction rate between the amino group-containing silane compound and the organic carboxylic acid compound is very high, and there is no deactivation of the catalyst by water as a by-product, so that the desired siloxane compound is obtained in a high yield. Can be obtained. Further, the by-product at the time of production can be almost alcohol only, and the alcohol can be recovered in the dry distillation tower at the time of reaction, so that the by-product removal step is substantially unnecessary. In addition, the product washing step is unnecessary, and it is not necessary to consider hydrolysis of the reaction substrate, so that dehydration of the reaction solvent and drying of the reaction apparatus can be eliminated. Therefore, it can be a very advantageous technique with respect to the above-described techniques (1) to (3).

Here, as a method for obtaining a desired siloxane compound, the present inventor also proposed a method of (4) reacting an amino group-containing silane compound with a hydrophobic acid chloride as a reaction substrate, followed by hydrolysis and condensation. ing. However, the production method of the present invention is very advantageous even when compared with this method (4). This is because the production method of the present invention is low in raw material cost, high in safety and stability of the raw material, easy to remove by-products, and can obtain a siloxane compound in a significantly high yield. It is.

That is, the present invention has a siloxane bond and has the following average composition formula (1):
_{X a Y b Z c SiO d} (1)
(In the formula, X is the same or different and represents an organic group containing an amide bond. Y is the same or different and represents at least one selected from the group consisting of a hydrogen atom, a hydroxyl group, a halogen atom and an OR group. R is the same or different and represents at least one group selected from the group consisting of an alkyl group, an acyl group, an aryl group, and an unsaturated aliphatic residue, and may have a substituent. Are the same or different and represent an organic group that does not contain an amide bond, a is a number of 3 or less that is not 0, b and c are the same or different, and are 0 or less than 3, and d is , A number less than 2 and a + b + c + 2d = 4). The method comprises the steps of amidation with an amino group-containing silane compound and an organic carboxylic acid compound. Including reaction process A method for producing a siloxane compound.

The amidation reaction step is performed in the presence of a metal compound including at least one selected from the group consisting of Fe, Al, In, Zr, Co, Ni, and Zn. It is preferable that it is 0.001-0.2 mol with respect to 1 mol of amino group containing silane compounds. Thereby, reaction advances more and can improve the manufacturing efficiency of a siloxane compound further.

The amidation reaction step preferably includes a reaction step of an amino group-containing silane compound and an organic carboxylic acid compound, and a hydrolysis / condensation step. By using the by-product water generated in the previous reaction step for the sol-gel reaction in the subsequent hydrolysis / condensation step, the by-product during the production can be almost alcohol only. Since it can collect | recover, the filtration collection process of a by-product can be made unnecessary substantially. Therefore, it becomes possible to further increase the production efficiency.

The present invention is described in detail below. In addition, the form which combined each preferable form of this invention described below 2 or 3 or more is also a preferable form of this invention.

〔Production method〕
The production method of the present invention includes an amidation reaction step using an amino group-containing silane compound and an organic carboxylic acid compound. Such an amidation reaction step preferably includes a reaction step of an amino group-containing silane compound and an organic carboxylic acid compound (also simply referred to as “reaction step”) and a hydrolysis / condensation step. By using the by-product water generated in the process for the sol-gel reaction in the subsequent hydrolysis / condensation process, the by-product during the production is almost only alcohol. Since alcohol can be recovered in the dry distillation tower during the reaction, the by-product filtration and recovery step can be eliminated, and the production efficiency is good.

-Reaction process-
In the reaction step, an amino group-containing silane compound and an organic carboxylic acid compound are used, and these reaction raw materials can be used alone or in combination of two or more.

The amino group-containing silane compound is preferably a compound having an amino group and an alkoxysilyl group. For example, any structure of (1) a structure having an alkylene group having 1 to 6 carbon atoms, (2) a structure having a secondary amino group, or (3) a structure having a tertiary amino group on a silicon atom Are preferably bonded and have a structure in which an amino group is bonded to the terminal of the structure opposite to the silicon atom. Among the above (1) to (3), (1) a structure having an alkylene group having 1 to 6 carbon atoms is more preferable.

More preferably, the amino group-containing silane compound is, for example, the following formula (2):

Wherein R ¹ is the same or different and represents at least one group selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an acyl group, an aryl group and an unsaturated aliphatic residue, and a substituent. X and z are the same or different and are an integer of 0 or more and 5 or less, and y is 0 or 1.

In said formula (2), although the sum total of x and z is an integer of 0-10, it is preferable that it is 3-7, More preferably, it is 3-5, More preferably, it is 3. y is preferably 0. As the ^{R 1,} preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.

The amino group-containing silane compound is particularly preferably 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltripropoxysilane, 3-aminopropyltri (isopropoxy) silane, 3-aminopropyl. Tributoxysilane.

The organic carboxylic acid compound is an organic compound having one or more carboxyl groups (COOH) in one molecule, and is not particularly limited. A compound having a hydrophobic group and a carboxyl group is preferable, and a compound represented by R ² —C (═O) —OH (R ² represents a hydrophobic group) is more preferable.

The hydrophobic group represented by R ² is preferably selected in consideration of physical properties (for example, compatibility with a layered inorganic compound or an organic resin) required for the obtained siloxane compound. For example, C1-C30 saturated aliphatic hydrocarbon group (alkyl group), C3-C30 saturated alicyclic hydrocarbon group (cycloalkyl group), C6-C30 aromatic hydrocarbon group, etc. Is preferred. More preferably, it is a linear or branched alkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or an aromatic hydrocarbon group. Among the linear or branched alkyl groups, the linear alkyl group is Is preferred. Among them, when used in applications where heat resistance is required particularly, the hydrophobic group (R ²⁾ is particularly preferably an aromatic hydrocarbon group. Of the aromatic hydrocarbon groups, a phenyl group is preferable.

The hydrophobic group may also have a substituent. Although it does not specifically limit as a substituent, For example, a halogen atom, an alkyl group, etc. are mentioned.

In the said reaction process, the usage-amount (addition amount) of an organic carboxylic acid compound is 0.5-3 mol with respect to 1 mol of amino groups which the amino group-containing silane compound has the amount of the carboxyl group which the said compound has. It is preferable to set so. More preferably, it is 0.8-1.2 mol, More preferably, it is 1 mol.

In the reaction step, the reaction temperature is preferably room temperature to 250 ° C. More preferably, it is room temperature-200 degreeC. The reaction time varies depending on the reaction temperature and reaction composition, but preferably 3 minutes to 24 hours.

The reaction step is preferably performed in the presence of a solvent.
As the solvent, it is preferable to use one or more organic solvents. Specific examples include an amide solvent, an ether solvent, an alcohol solvent, an ester solvent, a ketone solvent, an aromatic solvent, and the like. Among these, an amide solvent and an ether solvent are preferable.

The amide solvent is not particularly limited, and examples thereof include N-methylpyrrolidinone, N, N′-dimethylacetamide, N, N′-dimethylformamide and the like.

Although it is not particularly limited as the ether solvent, for example, tetrahydrofuran, dioxane, dibutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, Ethylene glycol dibutyl ether, ethylene glycol diphenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monophenyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl Ether, diethylene glycol diphenyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dibutyl ether, triethylene glycol diphenyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene Glycol monophenyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, propylene glycol diphenyl ether, dipropylene glycol monomethyl ether, dipropylene group Cole monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monophenyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, dipropylene glycol dipropyl ether, di Propylene glycol diphenyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene Examples include glycol monobutyl ether acetate and propylene glycol monophenyl ether acetate.

-Hydrolysis / condensation process-
The hydrolysis / condensation step is preferably a step of subjecting the alkoxysilyl group in the product obtained in the reaction step to a hydrolysis reaction and then a condensation reaction. A desired siloxane compound can be suitably obtained by a condensation reaction of a silanol group (Si (OH) ₃ ) obtained by a hydrolysis reaction.

In the hydrolysis / condensation step, water is preferably used. At this time, it is preferable to use water produced as a by-product in the reaction step, but water may be added as necessary, and the addition form is not particularly limited, and may be added dropwise, or may be added all at once. Good.
In addition, although management of a water concentration is unnecessary, it is preferable to use 10-2000 mass parts of water with respect to 100 mass parts of solid content in the product by the said reaction process, for example. More preferably, it is 10-500 mass parts, More preferably, it is 20-400 mass parts.

In the hydrolysis / condensation step, it is preferable to use one or more catalysts.
As the catalyst, a metal compound containing at least one selected from the group consisting of Fe, Al, In, Zr, Co, Ni and Zn is suitable. That is, the above production method is preferably performed in the presence of a metal compound containing at least one selected from the group consisting of Fe, Al, In, Zr, Co, Ni, and Zn. Thereby, reaction advances more and can improve the manufacturing efficiency of a siloxane compound further.

The metal compound is not particularly limited as long as it contains at least one metal selected from the group consisting of Fe, Al, In, Zr, Co, Ni and Zn. For example, halides of these metals , Oxides, hydroxides, carbonates, organic carboxylates and the like. Of these, chlorides and organic carboxylates are preferred. In addition, a metal compound can use 1 type (s) or 2 or more types.

It is preferable that the usage-amount (abundance) of the said metal compound is 0.001-0.2 mol with respect to 1 mol of amino group containing silane compounds with which the said reaction process is provided. Thereby, the effect derived from a metal compound can be exhibited more fully. More preferably 0.002 mol or more, further preferably 0.003 mol or more, more preferably 0.15 mol or less, still more preferably 0.1 mol or less, particularly preferably 0.05 mol or less. .

The reaction temperature in the hydrolysis / condensation step is preferably room temperature to 200 ° C. More preferably, the temperature is from room temperature to 160 ° C., and still more preferably, it is maintained under the azeotropic reflux of alcohol, water and solvent from the viewpoint that alcohol is produced as a by-product.

The hydrolysis / condensation step may be carried out under normal pressure, under pressure, or under reduced pressure, but it is less than normal pressure in that the reaction easily proceeds by efficiently distilling the by-product alcohol out of the reaction system. It is preferable to carry out with. The reaction time varies depending on the reaction temperature and reaction composition, but is preferably 2 to 48 hours.

As an example of the amidation reaction step, an example in which benzoic acid is used as the organic carboxylic acid compound and 3-aminopropyltriethoxysilane is used as the amino group-containing silane compound is shown in the following formula (3).

[Product]
The said manufacturing method is a method of manufacturing the compound which has a siloxane bond (Si-O bond) and is represented by the said average composition formula (1). The siloxane skeleton (main chain skeleton in which a siloxane bond is essential) of such a siloxane compound can also be expressed as (SiO _m ) _n . The structures other than (SiO _m ) _n in the siloxane compound are X, Y, and Z, and these are bonded to the silicon atom of the main chain skeleton.
The siloxane compound is preferably polysilsesquioxane.

The siloxane skeleton is preferably in the form of a chain (linear or branched), ladder, network, ring, cage, cubic, or the like. Among these, a ladder shape, a net shape, or a cage shape is preferable from the viewpoint that the effect is easily exhibited even with a small amount of the siloxane compound. More preferably, it is a ladder shape or a bowl shape. In the present specification, the saddle-like structure includes an incomplete-type saddle-like structure.
X, Y and Z may or may not be included in the repeating unit in the form of a “chain”. For example, one or more Xs may be contained in one molecule as a side chain.

In the above (SiO _m ) _n , n represents the degree of polymerization. The degree of polymerization represents the degree of polymerization of the main chain skeleton, but n organic groups X having an amide bond are not necessarily present. In other words, the organic group X having one amide bond does not necessarily exist in one unit of (SiO _m ) _n . In addition, one or more organic groups X having an amide bond may be included in one molecule, but when a plurality of organic groups X are included, an organic group having two or more amide bonds is bonded to one silicon atom. Also good.

In the main chain skeleton (SiO _m ) _n , m is preferably a number of 1 or more and less than 2. More preferably, it is 1.5-1.8. n represents a degree of polymerization and is preferably 1 to 5000. More preferably, it is 1-2000, More preferably, it is 1-1000, Most preferably, it is 1-200.

Here, for example, as a siloxane compound in which n is 2, a structural unit in which at least one organic group (X) having an amide bond is bonded to a silicon atom (also referred to as “structural unit (I)”) And a form in which only one structural unit (I) is contained. Specifically, the following formula:

(Wherein A is Y or Z, and X, Y and Z are each the same as above) and the like, and a homopolymer form containing two identical structural units (I), There are a homopolymer form containing two different structural units (I) and a copolymer form (cocondensed structure form) containing only one of the structural units (I).

In the siloxane compound, the proportion of the siloxane skeleton is preferably 10 to 80% by mass in 100% by mass of the siloxane compound. More preferably, it is 15-70 mass%, More preferably, it is 20-50 mass%.

In the average composition formula (1), X represents an organic group containing an amide bond. The organic group is preferably a group containing an amide bond, a hydrophobic group, and an organic skeleton. Among these, a group including a group represented by “—N (H) —C (═O) —R ² (R ² represents a hydrophobic group)” and an organic skeleton is more preferable. The hydrophobic group represented by R ² is as described above.

Examples of the organic skeleton include (1) a structure having a (poly) alkylene group having 1 to 6 carbon atoms, (2) a structure having a secondary amino group, or (3) a structure having a tertiary amino group, Any one or more of these structures are preferred. In particular, the X is more preferably a structure having a hydrophobic group via an amide bond at the end of any one or more of these organic skeletons. Among these, a structure having a hydrophobic group via an amide bond at the terminal of the (poly) alkylene group having 1 to 6 carbon atoms is more preferable in that the thermal stability of the siloxane compound is further increased.
In addition, when the said siloxane compound takes a bowl-like shape, it is particularly preferable that the organic skeleton layer is a shell portion and the inorganic skeleton layer is a core portion.

X is particularly preferably the following general formula (4):

(Wherein R ² represents the above-described hydrophobic group. X and z are the same or different and are an integer of 0 or more and 5 or less, and y is 0 or 1) ( Group). In formula (4), x, y and z are all the same as the symbols in formula (2), y is preferably 0, and the sum of x and z is preferably 3.

The coefficient a of X is a non-zero number of 3 or less. That is, the number satisfies 0 <a ≦ 3. This a is preferably set so that the proportion of the organic group represented by X falls within the preferred range described below. For example, a is preferably 0.2 or more, whereby heat resistance, hydrolysis resistance and the like are further improved. For example, when used in combination with a layered inorganic compound, the dispersibility of the layered inorganic compound is further increased. Thus, a composition superior in insulation properties, gas barrier properties and the like can be obtained. More preferably 0.5 or more, further preferably 0.7 or more, particularly preferably 0.8 or more, more preferably 2 or less, still more preferably 1.5 or less, and most preferably 1. .

In the siloxane compound, the amide group introduction rate is preferably 20% or more. As a result, the heat resistance, hydrolysis resistance and the like are further improved, and for example, when used in combination with a layered inorganic compound, the dispersibility of the layered inorganic compound is further improved, and a composition excellent in insulation, gas barrier properties, etc. can get. More preferably, it is 50% or more, more preferably 70% or more, particularly preferably 80% or more, preferably 300% or less, more preferably 200% or less, still more preferably 150% or less, most preferably 100% or less.
In the present specification, the amide group introduction rate can be calculated by tracking the consumption amount of the reaction substrate using gas chromatography (GC), as described in Examples described later.

Y is the same or different and represents at least one selected from the group consisting of a hydrogen atom, a hydroxyl group, a halogen atom and an OR group. Among these, a hydroxyl group or an OR group is preferable. More preferred is an OR group, and even more preferred is an OR group when R represents an alkyl group having 1 to 8 carbon atoms.

Z represents an organic group containing no amide bond. Specific examples include alkyl groups; aromatic residues such as aryl groups and aralkyl groups; unsaturated aliphatic residues; These may have a substituent. Preferably, it is a C1-C8 alkyl group which may have a substituent, or an aromatic residue.

The coefficient b of Y and the coefficient c of Z are each 0 or a number less than 3. That is, the numbers satisfy 0 ≦ b <3 and 0 ≦ c <3. The coefficient d of the oxygen atom O is a non-zero number less than 2. That is, the number satisfies 0 <d <2. These coefficients may be set so that the coefficient a of X falls within the preferred range described above, and is not particularly limited.

It is preferable that the siloxane compound has a silanol group amount determined by the following calculation formula (α) of 0.1 or less.
[Si—OH bond moles] / [Si—O bond moles] (α)
As a result, the viscosity of the composition is remarkably lowered, and the composition and a cured product obtained using the composition are extremely excellent in moisture absorption resistance (low moisture absorption). The amount of silanol groups determined by the calculation formula (α) is more preferably 0.05 or less, still more preferably 0.01 or less. Particularly preferably, the siloxane compound does not have residual silanol groups.
Here, [Si—OH bond mole number] represents the bond number between Si and OH in moles. For example, when two OH groups are bonded to each 1 mol of Si atoms, the [number of moles of Si—OH bond] is 2 mol. The number of moles of Si—O bonds is counted similarly.

As described above, the siloxane compound particularly preferably has a cage-like or ladder-like siloxane skeleton (polysiloxane skeleton). When it has a ladder-like siloxane skeleton (polysiloxane skeleton), it becomes more excellent in heat resistance. Moreover, when it has a bowl-like siloxane skeleton (polysiloxane skeleton), it is excellent in heat resistance and low hygroscopicity, and the viscosity is reduced.

Here, the ladder-like siloxane skeleton has two linear siloxane chains composed of siloxane bonds (Si-O bonds) and silicon atoms constituting one linear siloxane chain and other direct siloxane chains. It means a skeleton in which the two linear siloxane chains are located in parallel by bonding silicon atoms constituting the chain siloxane chain via one oxygen atom. The cage-like siloxane skeleton means a skeleton in which siloxane chains composed of siloxane bonds (Si—O bonds) are sterically bonded. For example, [R ^a SiO _1.5 ] _n (n is a multiple of 2). And an integer greater than or equal to 4. ^Ra can be described later.
Hereinafter, these siloxane compounds will be further described.

1) Saddle-shaped polysiloxane compound The cage-like polysiloxane compound is preferably a compound represented by the following formulas (1-a) to (1-d). In the formula, R ^a is the same or different and represents X, Y or Z in the average composition formula (1), and at least one of R ^a is X in the average composition formula (1). .

The weight average molecular weight of the cage-like polysiloxane compound is preferably 300 or more and 5000 or less. Thereby, for example, when the layered inorganic compound is used in combination with the layered inorganic compound, the layered inorganic compound can be more sufficiently dispersed, and therefore, it is more suitable for various uses such as a nanocomposite material. More preferably, it is 500 or more as a minimum of a weight average molecular weight, More preferably, it is 1000 or more, Most preferably, it is 1300 or more. Further, the upper limit of the weight average molecular weight is more preferably less than 5000, further preferably 4000 or less, particularly preferably 3000 or less, and most preferably 2000 or less.

In this specification, a weight average molecular weight and a number average molecular weight can be calculated | required by GPC (gel permeation chromatography) measurement on the measurement conditions mentioned later.
The structure of each polysiloxane compound can be identified by measuring, for example, ¹ H-NMR, ¹³ C-NMR, MALDI-TOF-MS, and FT-IR.

2) Ladder-like polysiloxane compound The ladder-like polysiloxane compound is preferably a compound represented by the following general formula (1-e). In the formula, R ^a is the same or different and represents X, Y or Z in the average composition formula (1), and at least one of R ^a is X in the average composition formula (1). . R ^b is the same or different and represents Y or Z.

In the general formula (1-e), the polymerization degree n is preferably 10 to 1000. If the degree of polymerization is in such a preferable range, the ladder-like polysiloxane compound is excellent in heat resistance. More preferably, it is 15-800, More preferably, it is 20-500.

The weight average molecular weight of the ladder-like polysiloxane compound is preferably larger than the weight average molecular weight of the cage-like polysiloxane compound described above. Specifically, it is preferably 5000 or more, more preferably 6000 or more, and further preferably 8000 or more. Moreover, it is preferable that the upper limit of a weight average molecular weight is 200,000 or less.

[Use]
The siloxane compound obtained by the production method of the present invention is excellent in dispersibility, heat resistance, pressure resistance, mechanical / chemical stability, thermal conductivity, etc. of the layered inorganic compound and imparts excellent properties to various materials. In addition, the material can be a very effective material for suppressing dielectric breakdown and insulation deterioration due to a partial discharge phenomenon. In particular, when the siloxane compound and the layered inorganic compound are used in combination, a composition having excellent insulation properties and gas barrier properties can be provided, and this composition is effective for suppressing dielectric breakdown and insulation deterioration due to partial discharge phenomenon. It will be something. Moreover, the said siloxane compound is useful as a dispersing agent of a layered inorganic compound.

The said siloxane compound can be used suitably for uses, such as an insulating material and a gas barrier material, for example. In addition to various applications such as mounting applications, optical applications, opto device applications, display device applications, etc., mechanical component materials, electrical / electronic component materials, automotive component materials, civil engineering and building materials, molding materials, paints and adhesive materials, etc. Moreover, it can be used conveniently.

Since the production method of the present invention has the above-described configuration, a siloxane compound having a predetermined structure containing a siloxane bond and an amide bond can be provided safely, easily and in a high yield, and is an industrially extremely useful technique. It is.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight” and “%” means “% by mass”. In addition, IR and NMR analyzers and molecular weight measurement conditions (GPC measurement conditions) are shown below. The introduction rate of the amide group was calculated under the following operating conditions by following the consumption amount of the reaction substrate using gas chromatography.

<IR, NMR analyzer>
FT-IR: Thermo-Nicolet, NEXUS-670
¹ H-NMR: manufactured by Varian Instruments, Unity Plus 400 MHz NMR system
¹³ C-NMR: Varian Instruments, Unity Plus 400 MHz NMR system

<GPC measurement conditions>
Measuring instrument: “HLC-8220GPC” manufactured by Tosoh Corporation
Column: Two Shodex GF-7MHQ,
Developing solution: 10 mMol / L LiBr added N, N′-dimethylformamide Flow rate: 0.6 mL / min Temperature: 40 ° C.
Calibration curve: Prepared using polystyrene standard sample (manufactured by Tosoh Corporation).

<GC (gas chromatography) measurement conditions>
Measuring instrument: manufactured by Shimadzu Corporation, product name “GC-2010”
Column: Agilent Technologies capillary column, product name “DB-1”, column length 30 m, column diameter 0.25 mm, film thickness 0.25 μm

Example 1
3-aminopropyltriethoxysilane 88.6 g, benzoic acid 48.9 g and N, N′-dimethyl not subjected to distillation treatment in a 200 mL four-necked flask equipped with a nitrogen inlet tube, a temperature sensor, a stirring blade and a condenser Add 37.0 g of acetamide, 9.3 g of undistilled toluene, and 0.55 g of zinc acetate dihydrate to make a uniform solution while stirring, then heat in an oil bath for 5 hours. The temperature was raised to 160 ° C., held for 3 hours, and then cooled to room temperature. Ethanol began to be collected through a condenser when reaching 120 ° C. during the temperature rise, and 35 g of ethanol was collected when the temperature was maintained at 160 ° C. for 3 hours.
After the reaction solution was once cooled to 110 ° C., 14.4 g of ion exchange water was added. The reaction solution was kept in a dry-distilled state at 110 ° C. for 2 hours, then heated again to 160 ° C. over 2 hours and held for 3 hours. When the holding was completed, 38 g of a mixed solution composed of ethanol, water, and toluene was recovered through a condenser. The resulting reaction solution was dried in a vacuum oven to remove N, N′-dimethylacetamide to obtain Compound A.
The yield was 98%, and the appearance was a white solid, which was poly [3- (benzamido) propyl] silsesquioxane based on the analysis results by FT-IR, ¹ H-NMR, ¹³ C-NMR, and GC. The introduction rate of the group was 98.2%.
In GPC measurement, the number average molecular weight Mn was 4200, the weight average molecular weight Mw was 7340, and the molecular weight distribution Mw / Mn was 1.75.

Example 2
Compound B was obtained in the same manner as in Example 1 except that iron (III) acetylacetonate was used instead of zinc acetate dihydrate of Example 1.
The yield was 98%, and the appearance was a white solid, which was poly [3- (benzamido) propyl] silsesquioxane based on the results of analysis by FT-IR, ¹ H-NMR, and ¹³ C-NMR. The introduction rate was 97.6%.
In GPC measurement, the number average molecular weight Mn was 4150, the weight average molecular weight Mw was 7670, and the molecular weight distribution Mw / Mn was 1.85.

Example 3
Compound C was obtained in the same manner as in Example 1 except that aluminum chloride (III) was used instead of zinc acetate dihydrate of Example 1.
The yield was 98%, and the appearance was a white solid, which was poly [3- (benzamido) propyl] silsesquioxane based on the results of analysis by FT-IR, ¹ H-NMR, and ¹³ C-NMR. The introduction rate was 95.3%.
In GPC measurement, the number average molecular weight Mn was 4330, the weight average molecular weight Mw was 7200, and the molecular weight distribution Mw / Mn was 1.66.

Example 4
Compound D was obtained in the same manner as in Example 1 except that indium (III) acetylacetonate was used instead of zinc acetate dihydrate of Example 1.
The yield is 98% and the appearance is a white solid, which is poly [3- (benzamido) propyl] silsesquioxane based on the results of analysis by FT-IR, ¹ H-NMR, and ¹³ C-NMR. The rate was 96.1%.
In GPC measurement, the number average molecular weight Mn was 4490, the weight average molecular weight Mw was 7810, and the molecular weight distribution Mw / Mn was 1.74.

Example 5
Compound E was obtained in the same manner as in Example 1 except that zirconium (IV) acetylacetonate was used instead of zinc acetate dihydrate of Example 1.
The yield was 98%, and the appearance was a white solid, which was poly [3- (benzamido) propyl] silsesquioxane based on the results of analysis by FT-IR, ¹ H-NMR, and ¹³ C-NMR. The introduction rate was 94.7%.
In GPC measurement, the number average molecular weight Mn was 5400, the weight average molecular weight Mw was 8310, and the molecular weight distribution Mw / Mn was 1.54.

Example 6
Compound F was obtained in the same manner as in Example 1 except that cobalt stearate (II) was used instead of zinc acetate dihydrate of Example 1.
The yield was 98%, and the appearance was a white solid, which was poly [3- (benzamido) propyl] silsesquioxane based on the results of analysis by FT-IR, ¹ H-NMR, and ¹³ C-NMR. The introduction rate was 95.5%.
In GPC measurement, the number average molecular weight Mn was 4150, the weight average molecular weight Mw was 7300, and the molecular weight distribution Mw / Mn was 1.76.

Example 7
Compound G was obtained in the same manner as in Example 1 except that nickel (II) p-toluenesulfonate hexahydrate was used in place of the zinc acetate dihydrate of Example 1.
The yield was 98%, and the appearance was a white solid, which was poly [3- (benzamido) propyl] silsesquioxane based on the results of analysis by FT-IR, ¹ H-NMR, and ¹³ C-NMR. The introduction rate was 97.9%.
In GPC measurement, the number average molecular weight Mn was 5270, the weight average molecular weight Mw was 8160, and the molecular weight distribution Mw / Mn was 1.55.

Example 8
Compound H was obtained in the same manner as in Example 1 except that propylene glycol monopropyl ether was used instead of N, N′-dimethylacetamide in Example 1.
The yield was 98%, and the appearance was a white solid, which was poly [3- (benzamido) propyl] silsesquioxane based on the results of analysis by FT-IR, ¹ H-NMR, and ¹³ C-NMR. The introduction rate was 98.6%.
In GPC measurement, the number average molecular weight Mn was 12900, the weight average molecular weight Mw was 56600, and the molecular weight distribution Mw / Mn was 4.37.

Comparative Synthesis Example 1
3-aminopropyltriethoxysilane (33.21 g), triethylamine (15.18 g), and N, N ′ from which water was removed by distillation in advance in a 200 mL four-necked flask equipped with a nitrogen inlet tube, a temperature sensor, a stirring blade, and a condenser -50 g of dimethylacetamide was added to make a uniform solution while stirring, and it was immersed in an oil bath and kept at room temperature. Next, 21.09 g of benzoyl chloride and 26 g of N, N′-dimethylacetamide, which had been previously distilled to remove water, were put into a glass vial to obtain a homogeneous solution, and then stirring was continued in the four-necked flask. The solution was added dropwise over 10 minutes. The inside of the flask began to become cloudy immediately after the start of dropping and the internal temperature rose to 60 ° C. After completion of dropping, the internal temperature was raised to 80 ° C. while being heated in an oil bath, held for 6 hours, and then cooled to room temperature.
The contents of the flask were in the form of a slurry, and the white precipitate was removed by filtration. The process of washing and filtering the white precipitate with 10 g of toluene was repeated twice to collect the filtrate. The filtrate was returned again to the four-necked flask, 27.03 g of ion-exchanged water and 0.264 g of zinc 2-ethylhexanoate were added, and stirring was continued while heating in an oil bath. When the temperature reached 87 ° C., reflux with by-product ethanol and water started. After maintaining for 2 hours, heating was further performed in an oil bath, and by-product ethanol, excess water and toluene were recovered through a condenser for 160 hours over 6 hours. C. reached and held for another 3 hours. The resulting reaction solution was dried in a vacuum oven to remove diglyme to obtain Compound I.
The yield was 72.0% and the appearance was a white solid, which was poly [3- (benzamido) propyl] silsesquioxane based on the analysis results by FT-IR, ¹ H-NMR, and ¹³ C-NMR. The group introduction rate was 68%.
In GPC measurement, the number average molecular weight Mn was 3800, the weight average molecular weight Mw was 6950, and the molecular weight distribution Mw / Mn was 1.85.

Comparative Synthesis Example 2
When the N, N′-dimethylacetamide used in Comparative Synthesis Example 1 was used without being distilled in advance, the reaction solution gelled when it reached 160 ° C.

Comparative Synthesis Example 3
Compound J was obtained in the same manner as in Example 1 except that iron (III) acetylacetonate was used instead of zinc 2-ethylhexanoate used in Comparative Synthesis Example 1.
The yield was 65.3%, the appearance was a white solid, and it was poly [3- (benzamido) propyl] silsesquioxane from the results of analysis by FT-IR, ¹ H-NMR, and ¹³ C-NMR. The introduction rate of the group was 72%.
In GPC measurement, the number average molecular weight Mn was 3540, the weight average molecular weight Mw was 6770, and the molecular weight distribution Mw / Mn was 1.91.

Comparative Synthesis Example 4
When propylene glycol monopropyl ether was used without distillation instead of N, N′-dimethylacetamide used in Comparative Synthesis Example 1, the reaction solution gelled when it reached 160 ° C.

From the above, it has been confirmed that the production method of the present invention can provide the siloxane compound safely and easily with a high yield.

Claims (3)

It has a siloxane bond and the following average composition formula (1):
_{X a Y b Z c SiO d} (1)
(In the formula, X is the same or different and represents an organic group containing an amide bond. Y is the same or different and represents at least one selected from the group consisting of a hydrogen atom, a hydroxyl group, a halogen atom and an OR group. R is the same or different and represents at least one group selected from the group consisting of an alkyl group, an acyl group, an aryl group, and an unsaturated aliphatic residue, and may have a substituent. Are the same or different and each represents an organic group that does not contain an amide bond, a is a number of 3 or less that is not 0, b and c are the same or different, and are 0 or a number of less than 3, and d is A number less than 2 that is not 0, and a + b + c + 2d = 4).
The method for producing a siloxane compound comprising an amidation reaction step using an amino group-containing silane compound and an organic carboxylic acid compound. The amidation reaction step is performed in the presence of a metal compound containing at least one selected from the group consisting of Fe, Al, In, Zr, Co, Ni, and Zn,
2. The method for producing a siloxane compound according to claim 1, wherein the amount of the metal compound used is 0.001 to 0.2 mol with respect to 1 mol of the amino group-containing silane compound. The method for producing a siloxane compound according to claim 1 or 2, wherein the amidation reaction step includes a reaction step of an amino group-containing silane compound and an organic carboxylic acid compound, and a hydrolysis / condensation step.