KR850000074B1 - Phenoxy alkyl trialkoxy silanes and method for preparing same - Google Patents

Abstract

Organic silicon compds.(I; R1 = -NH2, -NR4H, -CHO, -CN, -COR, Cl, Br, I, -SO2R4, -SOR4, -NO2, -SR4 or -OR4; R2 = methylene or C3-12 alkylene; R3, R4 = alkyl, cycloalkyl or aryl; Z = O or S) were prepd. by the reaction of II and XR2Si(OR3)3 (X = Cl, Br or I) at 40-20≰C. Thus, 300 g m-aminophenol, 560 cc dimethylsulfoxide, 600 cc toluene and 216cc NaOH soln. were reacted for 6 hrs. The product was supplied with 545 g 3-chloropropyl trimethoxysilane to give 630 g 3(m- aminophenoxy)propyl trimethoxysilane (85% yield).

Description

Process for preparing phenoxyalkyl trialkoxysilane

The present invention relates to a novel organosilicon compound, and in particular, the present invention relates to a process for producing a novel phenoxyalkyl-, thiophenoxy alkylsilane.

알카리금속 펜옥사이드나 티오펜옥사이드를 상온 내지 200℃사이의 온도로 상압하에 비점이 40-200℃인 최소한 하나의 액체탄화수소와 쌍극성, 비양성자성 용매로 이루어진 액체반응매체의 존재하에 비활성기체하에서 반응시키고 생성된 반응혼합물을 40-200℃에서 충분한 시간동안 유지하여 다음 일반식의 화합물을 생성시키고 :The present invention provides a method for preparing a new kind of organosilicon compound, which method is a general formula of the same molecular weight with haloalkylsilane of the general formula XR ² Si (OR ³ ) _S

Alkali metal phenoxide or thiophene oxide at a temperature between room temperature and 200 ° C under an inert gas in the presence of a liquid reaction medium consisting of at least one liquid hydrocarbon having a boiling point of 40-200 ° C and a bipolar, aprotic solvent. Reaction and the resulting reaction mixture is maintained at 40-200 ℃ for a sufficient time to give a compound of the general formula:

The product is isolated from the reaction mixture.

A new kind of organosilicon compound produced by the present invention can be represented as having the following general formula.

Wherein R ¹ is -NH ₂ , -NR ⁴ H, -CHO, -CN, -COR, Cl, Br, I, -SO ₂ R ⁴ , -SOR ⁴ , -NO ₂ , -SR ⁴ or -OR ⁴ , R ² is methylene or alkylene having 3-12 carbon atoms, R ³ and R ⁴ are each alkyl, cycloalkyl, aryl, alkaryl and alalkyl, wherein an alkyl group present at R ³ or R ⁴ Contains 1-12 carbon atoms and Z is oxygen or sulfur)

할로겐(염소, 취소 또는 옥소), SO₂R⁴, SOR⁴,니트로(-NO₂), SR⁴, OR⁴이다. 아미노기가 본 화합물을 여러방면에서 유용하게 하기 때문에 바람직하며 치환분은 산소원자에 대해서 오르토, 메타, 파라에 위치할 수 있다. 펜옥시, 티오펜옥시는 메틸렌 또는 선상 또는 분지상의 3-12개의 탄소원자를 갖는 알킬렌기에 의해서 규소원자에 결합된다. R²가 에틸렌인 화합물은 수성 산이나 염기가 미량존재하여도 불안정하기 때문에 실제적으로는 사용할 수 없다. 상술한 알킬렌기와 함께 규소원자는 전술한 일반식 OR³로 표시되는 새 알콕사이드나 아릴옥사이드기에 결합된다.Compounds prepared by the process of the invention are organosubstituted penoxyalkyl-, thiophenoxyalkylsilane compounds represented by the general formulas described above. Substituents of the phenyl group represented by R ¹ in the aforementioned general formula are -NH ₂ , dialkylamino, alkylamino, formylcarbalkoxy (-COOR ⁴ ), cyano (-CN),

Halogen (chlorine, canceled or oxo), SO ₂ R ⁴ , SOR ⁴ , nitro (—NO ₂ ), SR ⁴ , OR ⁴ . Amino groups are preferred because they make the compound useful in many ways, and substitutions may be located in ortho, meta, or para relative to the oxygen atom. Phenoxy and thiophenoxy are bonded to silicon atoms by methylene or by alkylene groups having 3-12 carbon atoms in linear or branched form. Compounds in which R ² is ethylene cannot be used practically because they are unstable even in the presence of trace amounts of aqueous acids or bases. The silicon atom together with the alkylene group described above is bonded to the new alkoxide or aryloxide group represented by the general formula OR ³ described above.

The present compounds are readily prepared by reacting alkali metal salts, preferably sodium salts of phenol and thiophenol with haloalkyl silanes of the general formula XR ² Si (OR ³ ) ₃ . Since this reaction is a high exothermic reaction, it is preferable to carry out in an inert gas, and even a small amount of moisture should not be present. This is because water readily reacts with trialkoxy- and triaryloxysilane to form a polymer. The reaction medium is a mixture of at least one liquid hydrocarbon having a boiling point of 40 to about 200 ° C. with a bipolar, aprotic, liquid such as dimethyl sulfoxide, N, N-dimethylformamide, tetramethyl urea or hexamethylphosphoramide . Preferably, the trialkoxyhaloalkyl silane is slowly added to the reaction medium containing the alkali metal salt. After the addition is complete and the exothermic reaction is complete, the reaction mixture is heated to about 70-150 ° C. for several hours to completely convert the reactants to the desired phenoxyalkyl- and thiophenoxyalkyl trihydrocarbyloxysilanes. Most of the compounds are colorless, viscous oils with high boiling points, are soluble in the reaction medium, and are easily isolated by the removal of the aforementioned liquid hydrocarbons and dipolar solvents. Some compounds become darker after prolonged exposure to air or light.

The trihydro carbyloxyhaloalkylsilanes used as one of the reagents in the present invention may be ones that are commercially available or used in the corresponding haloalkyl trihalosilanes, X ¹ R ² SiX ² ₃ , wherein X ¹ and X ² are chlorine , Cancelled, oxo) can be readily prepared by reacting with alcohol, R ³ OH (containing 1-12 carbon atoms). The hydroxyl group is also bonded to a carbocyclic or heterocyclic ring such as cyclohexyl, pyridyl, phenyl group. Hydrocarbyl oxytrihalosilane is prepared by reacting a haloalkene such as allyl chloride with trihalosilane and HSiX ² ₃ at room temperature under a platinum catalyst. Methods of making intermediate silanes are known in the art. Details of the reaction conditions are not necessary herein.

Examples of the phenols and thiophenols used in the present invention include aminophenols and aminothiophenols, wherein the amino group is an isomer of hydroxyl group, hydroxybenzaldehyde, hydroxybenzoic acid and mercaptobenzoic acid (where the alcohol residue of ester is 1). -12 carbon atoms are present in the ortho, meta and para positions. If the alcohol contains a phenyl group, the number of carbon atoms is 7-8. Other substitutions that may be present in the phenyl group are described herein and in the claims.

The organosubstituted silanes produced by the present invention are useful as binders for glass fiber reinforcement compositions and as condensing agents for water purification or sizing for glass fibers or textiles. The compounds of the present invention react with liquid hydroxy- or alkoxy group-terminated organopolysiloxanes with optional fillers to form elastomers useful as coatings, sealants, and molding compositions. The compound wherein R ¹ is amino or dialkylamino (-NH ₂ -NH ⁴ ₂ ) in the general formula shows washing resistance against waxes and polishes.

The present invention will be described by way of examples, which are not intended to limit the scope of the invention. All units and ratios mentioned refer to weight unless otherwise specified.

Example 1

Preparation of 3 (p-aminophenoxy) propyl trimethoxysilane

The glass reactor is charged with 60 g (0.55 mole) of p-aminophenol, 43.2 g of 50% aqueous sodium hydroxide solution (0.54 mole NaOH), 112 cc of dimethylsulfoxide and 120 cc of toluene. The resulting mixture is heated to boiling point for 6 hours under nitrogen gas to remove all moisture by azeotropic distillation. The reaction mixture is cooled to about 75 ° C., at which time 109 g (0.55 mole) of 3-chloropropyl trimethoxysilane are added dropwise and the reaction mixture is stirred. The temperature of the reaction mixture naturally increases to 85 ° C. during the addition. The temperature of the reaction mixture is increased to 75-85 ° C. by heating and rate of addition. The temperature of the reaction mixture is maintained at 75-85 ° C. by heating and rate of addition. After the addition, the reaction mixture is heated to 115 ° C. for 16 hours, then the mixture is cooled and filtered to remove solids. The solvent is removed at a temperature of about 60 ° C. under 15 mm Hg atmosphere. Lower the pressure to 3-4mmHg and recover the material with boiling point 170-180 ° C. This fraction (70 g in weight) was distilled using a fractional distillation tube to obtain 50 g of oil boiled at 175-177 ° C. under a pressure of 3 mmHg. This colorless liquid contained 10.19% of silicon and 5.20% of nitrogen. Can be. The found value of 3 (p-aminophenoxy) propyl trimethoxysilane is 10.33% silicon and 5.17% nitrogen. Infrared and nuclear magnetic resonance spectra of the product can be seen to match the expected structure.

Example 2

Preparation of 3 (m-aminophenoxy) propyl trimethoxysilane

The reactor is charged with 300 g (2.75 moles) of m-aminophenol, 560 cc of dimethylsulfoxide, 600 cc of toluene, and 216 cc of 50% aqueous sodium hydroxide solution (2.70 moles NaOH) using the general method described in Example 1 above. Water in the reactor is removed by azeotropic distillation at a temperature of 120 ° C. under nitrogen gas. Lower the temperature of the reaction mixture by 90 ° C and add 545 g (2.75 moles) of 3-chloropropyl trimethoxysilane little by little while maintaining this temperature. After the addition is complete over about 2 hours, the reaction mixture is heated at the boiling point for 16 hours. The product is recovered and fractional distillation as described in the previous examples. Collecting an oil with a boiling point of 178-180 ° C at 3mmHg pressure gives a weight of 630g (85% yield). Infrared and nuclear magnetic resonance spectra of the recovered product were consistent with the expected structure as follows.

The gas phase chromatogram of the product showed a purity of at least 98%.

Example 3

Preparation of 3 (p-formylphenoxy) propyl phenoxypropyltrimethoxysilane

62.2 g (0.55 mole) of p-hydroxybenzaldehyde 112 cc of dimethylsulfoxide, 120 cc of toluene, 43.2 g of 50% aqueous sodium hydroxide solution (0.54 mole NaOH) were added to the reactor using the general method described in Example 1. Fill it. All water present is removed by azeotropic distillation at a temperature of about 110-115 ° C. The reaction mixture is heated to the boiling point while 109 g (0.55 mole) 3-chloropropyl trimethoxysilane is added. The product, 3 (p-formylphenoxy) propyl trimethoxysilane, is isolated by filtration, and the solvent is isolated under reduced pressure in the recovered liquid phase, and then the residue is removed by fractional distillation. Collect oil with a boiling point of 208 ° C. under a pressure of 3 mmHg (yield 85%, mainly silane). Infrared absorption and nuclear magnetic resonance spectra of the recovered product showed the following expected structure.

Gas phase chromatogram of the product showed purity of 98% or more.

Example 4

Preparation of 3 (m-diethylaminophenoxy) propyl trimethoxysilane

The reactor is charged with 90.75 g (0.55 mole) of m-diethylaminophenol, 112 cc of dimethylsulfoxide, 120 cc of toluene, 43.2 g of 50% aqueous sodium hydroxide solution using the general method described in Example 1 above. All moisture present in the reactor is removed by azeotropic distillation. The reaction mixture is cooled to 80 ° C. and chloropropyl trimethoxysilane is added in portions over 2 hours. The temperature of the reaction mixture is raised to 88 ° C. during the addition. After the addition was completed, it was heated externally to maintain the temperature of the reaction mixture at 80 ° C. for 16 hours. The reaction mixture is cooled and then filtered. The liquid phase is recovered and evaporated at 5 mmHg to remove toluene and dimethyl sulfoxide. Lower the reactor internal pressure to 2 mmHg and collect product 3 (m-diethylaminophenoxy) propyl trimethoxy silane at 185-187 ° C. Analysis by gas phase chromatography gives a product with 97% purity.

Claims (1)

Alkali metal compounds having the same molecular weight represented by the following general formula:

(Wherein Z is oxygen or sulfur and R ¹ is as follows) in a liquid reaction medium containing a liquid hydrocarbon having a boiling point of 40-200 ° C. and a bipolar, aprotic solvent at room temperature to 200 under anhydrous conditions. React with a haloalkylsilane of the general formula XR ² Si (OR ³ ) ₃ (where X is chlorine, cancel or oxo) at a temperature between < RTI ID = 0.0 > A process for producing an organosilicon compound represented by the following general formula, characterized in that the silane is converted to the desired phenoxyalkyl- and thiophenoxyalkylsilane and recovered from the reaction mixture.

Wherein R ¹ is -NH ₂ , -NR ⁴ H, -NR ⁴ ₂ , -CHO, -CN, -COR, Cl, Br, I, -SO ₂ R ⁴ , -SOR ⁴ , -NO ₂ ,- SR ⁴ or —OR ⁴ , R ² is methylene or alkylene containing 3-12 carbon atoms, and R ³ and R ⁴ are each alkyl, cycloalkyl, aryl, alkaryl, wherein R ³ or R ⁴ is Alkyl groups present contain 1-12 carbon atoms, Z represents oxygen or sulfur)