KR20170003417A - Aminoalkylalkoxydisiloxane compound and method for preparing the same - Google Patents

Abstract

The present invention relates to an aminoalkyl alkoxydisiloxane compound represented by chemical formula (1). In chemical formula (1), R^1 and R^2 are the same or different and each of R^1 and R^2 represents a C1-C20 non-substituted or substituted monovalent hydrocarbon group which may contain a hetero atom, or R^1 and R^2 may be bound to each other to form a ring together with a nitrogen atom to which they are bound; R^3 represents a C1-C20 linear, branched or cyclic divalent hydrocarbon group which may contain a hetero atom; each of R^4 and R^5 represents a C1-C10 monovalent hydrocarbon group; and n is 0 or 1. The aminoalkyl alkoxydisiloxane compound according to the present invention can exhibit the effects of the amino and alkoxysilyl groups sufficiently upon the application and generates less volatile organic compounds during use. Thus, the aminoalkyl alkoxydisiloxane compound is useful for a silane coupling agent, a resin additive, a surface treating agent, a paint additive and an adhesive.

Description

TECHNICAL FIELD [0001] The present invention relates to an aminoalkylalkoxydisiloxane compound and an aminoalkylalkoxydisiloxane compound,

The present invention relates to a novel alkoxy disiloxane compound having two amino groups and a process for producing the same. This novel compound is useful as a silane coupling agent, a resin additive, a paint additive, an adhesive, a fiber treatment agent, and a surface treatment agent.

The silane compound having an amino group is useful as a silane coupling agent, a resin additive, a paint additive, an adhesive, a fiber treatment agent, and a surface treatment agent. As the silane compound having an amino group, 3-aminopropyltrimethoxysilane or the like is known, but since it contains a large number of hydrolyzable functional groups in the molecule, the amount of volatile organic compounds (VOC) generated during use is large, We are concerned about the load.

To solve this problem, 1,3-bis (3-aminopropyl) -1,1,3,3-tetraalkoxydisiloxane condensed with two molecules of 3-aminopropyltrialkoxysilane has been developed Patent Document 1). Such an alkoxydisiloxane compound has a larger molecular weight as compared with the corresponding monomers, so that volatility is lowered and handling is easier. In addition, since the alkoxy group per molecule is increased, the effect derived from this is expected to increase (Patent Document 1). Further, since the VOC per unit weight is smaller than that of the monomer, the load on the environment is also small.

U.S. Patent No. 4287326

R. Zhongjie, S. Diaming, L. Huihui, M. Dongge, Z. Jianming, Y. Shouke. Shynthesis of Dibenzothiophene-Containing Ladder Polysilsesquioxane as a Blue Phosphorescent Host Material. Chemistry A European Journal. 2012, vol.18, Issue 13, p.4115-4123.

However, the alkoxydisiloxane compounds developed so far are all compounds having a primary or secondary amino group, and have active hydrogens rich in reactivity on nitrogen. Therefore, when it is added to an epoxy resin precursor, a polyurethane precursor, a carbonate resin, or the like, side reactions may occur, which often causes a problem. For example, when the above compound is added to the epoxy resin precursor, the compound itself changes the epoxy group, so that the curing of the resin proceeds. Further, when the above compound is added to a polyurethane precursor, that is, a compound containing an isocyanate group, the alkoxy disiloxane compound is incorporated into the skeleton of the urethane resin itself. Further, when the above compound is added to the carbonate resin, it is considered that the carbonic acid ester skeleton is converted into the amide skeleton and the resin is decomposed. As a result, there has been a demand for a compound which can be used for various purposes while having properties of an alkoxysiloxane compound.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide an aminoalkylalkoxydisiloxane compound having properties of an alkoxydisiloxane compound and being used for various purposes, and a process for producing the same.

DISCLOSURE OF THE INVENTION As a result of intensive investigations to solve the above problems, the present inventors have found that an aminoalkylalkoxydisiloxane compound having no active hydrogen can be used for various purposes and have completed the present invention.

Accordingly, the present invention provides aminoalkylalkoxydisiloxane compounds shown below and a process for their preparation.

〔One〕

(1)

(Wherein, R ^1, R ² are, which may include a hetero atom having 1 to 20 carbon atoms is 1 the unsubstituted or substituted hydrocarbon group, and may be the same or different, respectively, R ¹ and R ² are bonded to each other R ³ is a straight, branched or cyclic divalent hydrocarbon group of 1 to 20 carbon atoms which may contain a heteroatom, and R ⁴ and R ⁵ may be the same or different, A monovalent hydrocarbon group having 1 to 10 carbon atoms, and n is 0 or 1)

Lt; RTI ID = 0.0 > aminoalkylalkoxydisiloxane < / RTI >

〔2〕

(2)

(Wherein R ¹ to R ⁵ and n are as defined above)

(1), wherein the aminoalkylalkoxysilane compound represented by the general formula (1) is hydrolyzed and condensed with the aminoalkylalkoxysilane compound represented by the general formula (1).

[3]

(3)

(Wherein R ³ to R ⁵ and n are as defined above, and X is chlorine, bromine or iodine)

(4): < EMI ID =

(Wherein R ¹ and R ² are as defined above)

Is reacted with an amine compound represented by the following general formula (1): < EMI ID = 1.0 >

The aminoalkylalkoxydisiloxane compound provided by the present invention can sufficiently exert the effects of an amino group and an alkoxysilyl group at the time of use and also has a small amount of volatile organic compounds generated at the time of use so that a silane coupling agent, Coating agents, paint additives, adhesives, and the like.

1 is an IR chart of 1,3-bis (diethylaminopropyl) -1,1,3,3-tetramethoxydisiloxane obtained in Example 1. Fig.
2 is a ¹ H-NMR chart of 1,3-bis (diethylaminopropyl) -1,1,3,3-tetramethoxydisiloxane obtained in Example 1.
3 is an IR chart of 1,3-bis (methylpiperazinopropyl) -1,1,3,3-tetraethoxydisiloxane obtained in Example 2. Fig.
4 is a ¹ H-NMR chart of 1,3-bis (methylpiperazinopropyl) -1,1,3,3-tetraethoxydisiloxane obtained in Example 2. FIG.

The aminoalkylalkoxydisiloxane compound of the present invention is a compound represented by the following general formula (1).

(Wherein R ¹ and R ² are each an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, which may contain a hetero atom, and may be the same or different, and R ¹ and R ² may combine with each other to form a ring together with the nitrogen atom to which they are bonded, R ³ is a straight chain, branched or cyclic alkyl group having 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, R ⁴ and R ⁵ are monovalent hydrocarbon groups of 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms, and n is 0 or 1,

Specific examples of the monovalent hydrocarbon group of 1 to 20 carbon atoms represented by R ¹ and R ² include monovalent hydrocarbon groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, Branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, An alkenyl group such as a propenyl group, and the like, and an ethyl group is particularly preferable from the viewpoint of easiness of procurement of a raw material. The monovalent hydrocarbon group of 1 to 20 carbon atoms represented by R ¹ and R ² may have a hetero atom such as an ester group (-COO-), an ether group (-O-), or a sulfide group (-S-) These may be used in combination. Some or all of the hydrogen atoms of these hydrocarbon groups may be substituted. Specific examples of the substituent include alkoxy groups such as a methoxy group, an ethoxy group, and an (iso) propoxy group; A halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; Cyano; An amino group; Aryl groups having 6 to 10 carbon atoms such as phenyl and tolyl, aralkyl groups having 7 to 10 carbon atoms such as benzyl and phenethyl, and acyl groups having 2 to 10 carbon atoms; Trialkylsilyl group, trialkoxysilyl group, dialkylmonoalkoxysilyl group, monoalkyldialkoxysilyl group and the like in which each alkyl group and each alkoxy group each have 1 to 5 carbon atoms.

When R ¹ and R ² are bonded to each other to form a ring structure together with the nitrogen atom to which they are bonded to form a group represented by the following formula (5), a pyrrolidine group, a piperidine group, a piperazine group, a methyl Piperazinyl group, morpholinyl group and the like.

(Wherein R ¹ and R ² are as defined above)

Specific examples of the divalent hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom of R ³ include a methylene group, an ethylene group, a propylene group, a butylene group, a hexamethylene group, an octamethylene group, a decylene group , Branched alkylene groups such as methylethylene group and methylpropylene group, cyclic alkylene groups such as cyclohexylene group, alkenylene groups such as propenylene group, arylene groups such as phenylene group and the like, methylene phenyl And an aralkylene group such as a methylene group, a methylene group, and a methylene phenylene methylene group. The divalent hydrocarbon group for R ³ may have a hetero atom such as an ester group (-COO-), an ether group (-O-), or a sulfide group (-S-), or a combination thereof may be used. Some or all of the hydrogen atoms of these hydrocarbon groups may be substituted. Examples of the substituent include the same substituent as the substituent which some or all of the hydrogen atoms of the hydrocarbon groups of R ¹ and R ² may be substituted with .

Specific examples of the monovalent hydrocarbon group of R ⁴ and R ⁵ include a straight chain alkyl group such as methyl group, ethyl group, hexyl group, octyl group and decyl group, isopropyl group, tert-butyl group, neopentyl group, A cyclic alkyl group such as cyclopentyl group and cyclohexyl group, an alkenyl group such as vinyl group, allyl group and propenyl group, an aryl group such as phenyl group and tolyl group, a benzyl group, a phenethyl group and the like And an alkyl group is particularly preferable from the viewpoint of ease of procurement of raw materials, and methyl group and ethyl group are preferable from the viewpoint of usability of the product.

Examples of the aminoalkylalkoxydisiloxane compound represented by the general formula (1) include 1,3-bis (dimethylaminopropyl) -1,1,3,3-tetramethoxydisiloxane, 1,3-bis (dimethylaminopropyl) ) -1,3-dimethoxy-1,3-dimethyl-disiloxane, 1,3-bis (dimethylaminopropyl) -1,1,3,3-tetraethoxydisiloxane, 1,3- Aminopropyl) -1,3-diethoxy-1,3-dimethyl-disiloxane, 1,3-bis (diethylaminopropyl) -1,1,3,3-tetramethoxydisiloxane, (Diethylaminopropyl) -1,3-dimethoxy-1,3-dimethyl-disiloxane, 1,3-bis (diethylaminopropyl) -1,1,3,3-tetraethoxydisiloxane, 1 , 3-bis (diethylaminopropyl) -1,3-diethoxy-1,3-dimethyl-disiloxane, 1,3-bis (dibutylaminopropyl) -1,1,3,3- Siloxane, 1,3-bis (dibutylaminopropyl) -1,3-dimethoxy-1,3-dimethyl-disiloxane, 1,3-bis (dibutylaminopropyl) Tetraethoxydisiloxane, 1 , 3-bis (dibutylaminopropyl) -1,3-diethoxy-1,3-dimethyl-disiloxane, 1,3-bis (morpholinopropyl) -1,1,3,3- Siloxane, 1,3-bis (morpholinopropyl) -1,3-dimethoxy-1,3-dimethyl-disiloxane, 1,3-bis (morpholinopropyl) (Morpholinopropyl) -1,3-diethoxy-1,3-dimethyl-disiloxane, 1,3-bis (piperazinopropyl) -1,1, 1,3-bis (piperazinopropyl) -1,3-dimethoxy-1,3-dimethyl-disiloxane, 1,3-bis , 1,3,3-tetraethoxydisiloxane, 1,3-bis (piperazinopropyl) -1,3-diethoxy-1,3-dimethyl-disiloxane, 1,3- 1,3-bis (methylpiperazinopropyl) -1,3-dimethoxy-1,3-dimethyl-disiloxane, 1,3- Bis (methylpiperazinopropyl) -1,1,3,3-tetraethoxydisiloxane, 1,3-bis (methylpiperazin- 1, 3-diethoxy-1,3-dimethyl-disiloxane, 1,3-bis (bis (trimethylsilyl) aminopropyl) -1,1,3,3-tetramethoxydisiloxane, (Bis (trimethylsilyl) aminopropyl) -1,1,3,3-tetraethoxydisiloxane, 1,3-bis (bis (trimethylsilyl) aminopropyl) -1,3-dimethoxy-1 , 3-dimethyldisiloxane, and 1,3-bis (bis (trimethylsilyl) aminopropyl) -1,3-diethoxy-1,3-dimethyldisiloxane.

The aminoalkylalkoxydisiloxane compound represented by the formula (1) does not have reactive hydrogen-rich active hydrogens on nitrogen, so that ring opening polymerization does not occur even when added to the epoxy resin precursor. Further, even when mixed with a polyurethane precursor, that is, an isocyanate group-containing one, it does not react with the isocyanate group, so that the additive can be avoided from being incorporated into the skeleton itself of the resin. Even when added to a carbonate resin, the carbonate skeleton is not decomposed. In addition, since the amino group site and the alkoxysilyl group site are sufficiently separated from each other, the respective functional groups rarely interfere with each other.

Examples of the method for producing the aminoalkylalkoxydisiloxane compound in the present invention include a method in which a compound represented by the following general formula (2)

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and n are as defined above,

Can be prepared by hydrolysis and condensation of an aminoalkylalkoxysilane compound represented by the formula

Examples of the aminoalkylalkoxysilane compound represented by the general formula (2) include dimethylaminopropyltrimethoxysilane, diethylaminopropyltrimethoxysilane, dibutylaminopropyltrimethoxysilane, piperazinopropyltrimethoxysilane , Methylpiperazinopropyltrimethoxysilane, morpholinopropyltrimethoxysilane, dimethylaminopropyltriethoxysilane, diethylaminopropyltriethoxysilane, dibutylaminopropyltriethoxysilane, piperazinopropyl But are not limited to, triethoxysilane, methylpiperazinopropyltriethoxysilane, morpholinopropyltriethoxysilane, dimethylaminopropylmethyldimethoxysilane, diethylaminopropylmethyldimethoxysilane, dibutylaminopropylmethyldimethoxysilane, Piperazinopropylmethyldimethoxysilane, methylpiperazinopropylmethyldimethoxysilane, monopolinopropylmethyldimethoxysilane, di But are not limited to, methylaminopropylmethyldiethoxysilane, diethylaminopropylmethyldiethoxysilane, dibutylaminopropylmethyldiethoxysilane, piperazinopropylmethyldiethoxysilane, methylpiperazinopropylmethyldiethoxysilane, monopolinopropylmethyldi (Trimethylsilyl) aminopropyltrimethoxysilane, bis (trimethylsilyl) aminopropyltriethoxysilane, bis (trimethylsilyl) aminopropylmethyldimethoxysilane, bis (trimethylsilyl) aminopropylmethyldiethoxysilane And the like.

The compounding ratio of the aminoalkylalkoxysilane compound represented by the general formula (2) and water is not particularly limited, but from the viewpoints of reactivity and productivity, water is added in an amount of 0.1 to 4 mols per mol of the compound represented by the general formula (2) , Particularly preferably 0.2 to 1 mole.

The hydrolysis and condensation reaction proceeds without a catalyst, but the reaction rate can be improved by adding a catalyst. Examples of the catalyst to be used include sodium methoxide and sodium ethoxide and their alcohol solutions, potassium methoxide, potassium ethoxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, calcium hydroxide, magnesium hydroxide, triethylamine, tributylamine, Amines and the like; acidic catalysts such as hydrogen chloride, hydrogen bromide, sulfuric acid, methanesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, trifluoromethanesulfonic acid, acetic acid, and trifluoroacetic acid; acid catalysts such as tetrapropylammonium bromide, , Quaternary ammonium salts such as tetrapropylammonium iodide and tetrabutylammonium iodide, quaternary phosphonium salts such as tetrapropylphosphonium bromide, tetrabutylphosphonium bromide, tetrapropylphosphonium iodide and tetrabutylphosphonium iodide And the like.

The amount of the catalyst to be used is not particularly limited, but 0.001 to 1.0 mol, in particular 0.001 to 0.2 mol, in particular 0.005 to 0.1 mol, of the catalyst is used relative to 1 mol of the compound represented by the general formula (2) .

The hydrolysis and condensation reaction proceeds without solvent, but a solvent may also be used. Examples of the solvent to be used include hydrocarbon solvents such as pentane, hexane, cyclohexane, heptane, isooctane, benzene, toluene and xylene; alcohol solvents such as methanol, ethanol and isopropanol; and organic solvents such as diethyl ether, tetrahydrofuran and dioxane Ether solvents, acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, and the like. These solvents may be used alone or in combination of two or more. Particularly, in order to prevent the local presence of water, it is preferable to use an aprotic polar solvent or an alcohol solvent.

The reaction temperature of the hydrolysis and condensation reaction is not particularly limited, but is preferably 20 to 200 ° C, particularly preferably 30 to 100 ° C, and the reaction time is not particularly limited, but is preferably 1 to 30 hours, particularly 3 to 10 hours.

As another method, a compound represented by the following general formula (3)

(Wherein R ³ , R ⁴ , R ⁵ , and n are as defined above, and the same examples as described above may be mentioned.) X is chlorine, bromine or iodine)

(4): < EMI ID =

(Wherein R &^lt; ¹ > and R &^lt; ^{2 >} are as defined above,

Is reacted with an amine compound represented by the general formula (1) to produce an aminoalkylalkoxydisiloxane compound represented by the general formula (1).

Examples of the haloalkylalkoxysiloxane compound represented by the general formula (3) include 1,3-bis (chloropropyl) -1,1,3,3-tetramethoxydisiloxane, 1,3-bis (chloropropyl) 1,3-dimethyl-disiloxane, 1,3-bis (chloropropyl) -1,1,3,3-tetraethoxydisiloxane, 1,3-bis (chloropropyl) 1,3-diethoxy-1,3-dimethyl-disiloxane, 1,3-bis (chlorobutyl) -1,1,3,3-tetramethoxydisiloxane, 1,3-bis (chlorobutyl) -1 1,3-dimethyl-disiloxane, 1,3-bis (chlorobutyl) -1,1,3,3-tetraethoxydisiloxane, 1,3-bis (chlorobutyl) -1 1,3-dimethyl-disiloxane, 1,3-bis (bromopropyl) -1,1,3,3-tetramethoxydisiloxane, 1,3-bis (bromopropyl) 1,3-dimethyl-disiloxane, 1,3-bis (bromopropyl) -1,1,3,3-tetraethoxydisiloxane, 1,3-bis (bromopropyl ) -1,3-diethoxy-1,3-dimethyl-disiloxane, 1,3-bis (bromobutyl) -1,1,3,3- Tetramethoxydisiloxane, 1,3-bis (bromobutyl) -1,3-dimethoxy-1,3-dimethyl-disiloxane, 1,3-bis (bromobutyl) -Tetraethoxydisiloxane, 1,3-bis (bromobutyl) -1,3-diethoxy-1,3-dimethyl-disiloxane, 1,3-bis (iodopropyl) 1,3-bis (iodopropyl) -1,1,3,3-tetramethoxydisiloxane, 1,3-bis (iodopropyl) -1,3-dimethoxy- -Tetraethoxydisiloxane, 1,3-bis (iodopropyl) -1,3-diethoxy-1,3-dimethyl-disiloxane, 1,3-bis (iodobutyl) (Iodobutyl) -1,3-dimethoxy-1,3-dimethyl-disiloxane, 1,3-bis (iodobutyl) -1,1,3,3-tetramethyldisiloxane, Tetraethoxydisiloxane, and 1,3-bis (iodobutyl) -1,3-diethoxy-1,3-dimethyl-disiloxane.

Examples of the amine compound represented by the general formula (4) include dimethylamine, diethylamine, dibutylamine, piperazine, methylpiperazine, morpholine, pyrrolidine, piperidine and the like.

The reaction ratio of the haloalkylalkoxy disiloxane compound represented by the general formula (3) to the amine compound represented by the general formula (4) is preferably from 1 to 20, (4) is preferably used in an amount of from 4 to 20 mol, especially from 4 to 8 mol, per mol of the compound represented by the general formula (3).

Although the reaction of the haloalkylalkoxysilane compound represented by the general formula (3) with the amine compound represented by the general formula (4) proceeds without a catalyst, the reaction rate may be improved by adding a catalyst. Examples of the catalyst to be used include quaternary ammonium salts such as tetrapropylammonium bromide, tetrabutylammonium bromide, tetrapropylammonium iodide and tetrabutylammonium iodide, tetrapropylphosphonium bromide, tetrabutylphosphonium bromide, tetrapropylphosphonium iodide , Tetrabutylphosphonium iodide, and other quaternary phosphonium salts.

The amount of the catalyst to be used is not particularly limited, but 0.001 to 1.0 mol, particularly 0.001 to 0.2 mol, in particular 0.005 to 0.1 mol, of the catalyst is used relative to 1 mol of the compound represented by the general formula (3) from the viewpoint of the reaction promoting effect .

The reaction of the haloalkylalkoxydisiloxane compound represented by the general formula (3) with the amine compound represented by the general formula (4) proceeds with no solvent, but a solvent may also be added. Examples of the solvent to be used include hydrocarbon solvents such as pentane, hexane, cyclohexane, heptane, isooctane, benzene, toluene and xylene; alcohol solvents such as methanol, ethanol and isopropanol; and organic solvents such as diethyl ether, tetrahydrofuran and dioxane Ethereal solvents, aprotic polar solvents such as acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone. These solvents may be used alone or in combination of two or more. In particular, it is preferable to use an ether solvent or an aprotic polar solvent which can be expected to improve the reaction rate.

The reaction temperature is not particularly limited, but is preferably from 20 to 200 DEG C, particularly preferably from 50 to 150 DEG C, and the reaction time is not particularly limited, but is preferably from 1 to 30 hours, particularly from 3 to 10 hours.

[Example]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

[Example 1] Synthesis of 1,3-bis (diethylaminopropyl) -1,1,3,3-tetramethoxydisiloxane

1,500 g (6.372 mol) of diethylaminopropyltrimethoxysilane and 34.9 g (1.94 mol) of water were added to a flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, and the mixture was stirred at 70 DEG C for 5 hours. The reaction mixture was distilled to obtain 296.3 g of a fraction (1,3-bis (diethylaminopropyl) -1,1,3,3-tetramethoxydisiloxane) at 158 ° C / 0.2 ° C.

The mass spectrum, ¹ H-NMR spectrum and IR spectrum of the obtained oil were measured.

Mass spectrum

m / z 424 363 167 86

IR spectrum

  The chart is shown in Fig.

≪ ¹ > H-NMR spectrum (heavy chloroform solvent)

  2 as a chart.

From the above results, it was confirmed that the obtained compound was 1,3-bis (diethylaminopropyl) -1,1,3,3-tetramethoxydisiloxane.

[Example 2] Synthesis of 1,3-bis (methylpiperazinopropyl) -1,1,3,3-tetraethoxydisiloxane

722.6 g (3.001 mol) of chloropropyltriethoxysilane, 27.1 g (1.51 mol) of water and 2.9 g (0.031 mol) of methanesulfonic acid were added to a flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, And stirred for 13 hours. To the reaction mixture was added 11.4 g (0.0344 mol) of a 20 mass% ethanol solution of sodium ethylate and the mixture was stirred for 30 minutes. Subsequently, 0.9 g (0.02 mol) of acetic acid was added, and the mixture was stirred for 30 minutes. The obtained reaction solution was distilled to obtain 142.8 g of an oil fraction (1,3-bis (chloropropyl) -1,1,3,3-tetraethoxydisiloxane) at 150 ° C / 0.4 ° C.

60.1 g (0.600 mol) of methylpiperazine, 6.0 g of hexane and 6.0 g of N-methylpyrrolidone were put into a flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, and heated to 110 캜. To the resulting reaction solution, 40.8 g (0.100 mol) of the 1,3-bis (chloropropyl) -1,1,3,3-tetraethoxydisiloxane was dropwise added over 2 hours while maintaining the temperature at 110 to 120 ° C And further stirred at the same temperature for 5 hours. The reaction mixture was cooled to 50 캜, 18.0 g (0.300 mol) of ethylenediamine was added, and the mixture was stirred at the same temperature for 30 minutes. After removal by the operation of separating the resulting ethylenediamine hydrochloride salt, 1.2 g (0.0035 mol) of a 20 mass% ethanol solution of sodium ethoxide was added to the upper layer, and the solution was inversely neutralized with 0.2 g (0.003 mol) of acetic acid. The obtained reaction solution was distilled to obtain 36.1 g of an oil fraction (1,3-bis (methylpiperazinopropyl) -1,1,3,3-tetraethoxydisiloxane) at 219 ° C / 0.3 ° C.

The mass spectrum, ¹ H-NMR spectrum and IR spectrum of the obtained oil were measured.

Mass spectrum

m / z 534 490 372 113

IR spectrum

  3 as a chart.

≪ ¹ > H-NMR spectrum (heavy chloroform solvent)

  4 as a chart.

From the above results, it was confirmed that the obtained compound was 1,3-bis (methylpiperazinopropyl) -1,1,3,3-tetraethoxydisiloxane.

[Examples 3 and 4 and Comparative Example 1]

Addition experiment to epoxy resin

(Diethylaminopropyl) -1,1,3,3-tetramethoxydisiloxane synthesized in Example 1 above was added to 40 g of an epoxy resin (Tokyo Epoxy Resin Co., Ltd.: JER-828) Bis (methylpiperazinopropyl) -1,1,3,3-tetraethoxydisiloxane synthesized in Example 2, or 1,3-bis (aminopropyl) -1,1,3,3 -Tetramethoxydisiloxane was added, and the mixture was stirred at room temperature for 5 minutes. The resulting mixture was allowed to stand at room temperature, and the properties after 12 hours were confirmed. Regarding the property change, the container containing the mixture was tilted at 45 degrees, and whether the contents were flowing within 5 seconds was visually confirmed. When the contents flowed within 5 seconds, it was judged to have fluidity, and when there was no change, it was judged that there was no fluidity.

From the results shown in Table 1, it was confirmed that the aminoalkylalkoxy disiloxane compound of the present invention can be added to the epoxy resin.

Claims (3)

(1)

(Wherein, R ^1, R ² are, which may include a hetero atom having 1 to 20 carbon atoms is 1 the unsubstituted or substituted hydrocarbon group, and may be the same or different, respectively, R ¹ and R ² are bonded to each other R ³ is a straight, branched or cyclic divalent hydrocarbon group of 1 to 20 carbon atoms which may contain a heteroatom, and R ⁴ and R ⁵ may be the same or different, A monovalent hydrocarbon group having 1 to 10 carbon atoms, and n is 0 or 1)
Lt; RTI ID = 0.0 > aminoalkylalkoxydisiloxane < / RTI > (2)

(Wherein R ¹ to R ⁵ and n are as defined above)
Wherein the aminoalkylalkoxysilane compound represented by the general formula (1) is hydrolyzed and condensed with an aminoalkylalkoxysilane compound represented by the general formula (1). (3)

(Wherein R ³ to R ⁵ and n are as defined above, and X is chlorine, bromine or iodine)
(4): < EMI ID =

(Wherein R ¹ and R ² are as defined above)
Is reacted with an amine compound represented by the general formula (1): " (1) "

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