JPS6352629B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel organosilicon compound and a method for producing the same. According to the invention, the general formula (): [In the formula, R ¹ is -COOR ⁸ (R ⁸ is a lower alkyl group), a C ₂ to _{C 5} alkenyl group, or

[Formula], R ⁵ represents a lower alkylene group, R ⁶ and R ⁷ each represent a lower alkyl group, m is 1 or 2, and p is 2 or 3.
A novel organosilicon compound is provided. According to the invention, furthermore, the general formula: An anhydrous alkali metal or alkaline earth metal compound represented by the formula (wherein M represents an alkali metal or alkaline earth metal, and R ¹ and m have the above-mentioned meanings); (In the formula, X represents chlorine, bromine or iodine, R ⁵ ,
R ⁶ , R ⁷ and p have the above-mentioned meanings) in substantially equimolar amounts under substantially anhydrous conditions, and at least a portion of which is at least one dipolar neutral liquid. reacted at a temperature between ambient temperature and 200°C in a liquid reaction medium consisting mainly of liquid hydrocarbons having a boiling point of 40-200°C; holding the compound and the silane compound at a temperature of 40 to 200° C. for a period sufficient to substantially completely convert the compound and the silane compound to the desired functional phenoxyalkyl silane, and then isolating the resulting silane compound; There is provided a method for producing an organosilicon compound represented by the general formula (), characterized by: The method of the present invention can also be used to prepare known silanes containing functional groups, including aminophenoxypropylsilanes, such as those described in US Pat. No. 4,049,691. The compound of the present invention is a phenooxyalkylsilane substituted with a functional group represented by the above general formula. The functional substituent represented by R ¹ in the above general formula is -COOR ⁸ , C ₂ -C ₅ alkenyl group and

It can be [Formula]. Substituents may be present in the ortho, meta or para position to the oxygen atom in the general formula. The phenoxy group is linked to the silicon atom by an alkylene group. It has been found that compounds in which R ⁵ is an ethylene group are unstable in the presence of trace amounts of aqueous acids or bases and are of no use in practical applications. In addition to the alkylene group, three alkoxy groups represented by OR ⁶ in the general formula above are bonded to the silicon atom, or two alkoxy groups and one alkyl group are bonded to the silicon atom. The organosilicon compounds of the present invention are prepared with an alkali metal or alkaline earth metal salt, preferably a sodium salt or a potassium salt, of the desired phenol and the general formula: It is conveniently prepared by reacting a haloalkylsilane with a haloalkylsilane. This reaction is highly exothermic and is therefore preferably carried out under an inert atmosphere and in the absence of traces of water; the reason is that the silicon atom contains two or three alkoxy groups bonded to the silicon atom. This is because silanes are known to readily react with water to form polymeric products. The reaction medium was dimethyl sulfoxide, N,N
-dimethylformamide, tetramethylurea, N
- dipolar neutral solvents such as methylpyrrolidone or hexamethylphosphoramide. The dipolar neutral solvent accounts for 1 to about 100% of the reaction medium, preferably 20 to 50%.
Makes up % by weight. The remainder of the reaction medium consists primarily of at least one liquid hydrocarbon having a boiling point of 40 DEG to about 200 DEG C. at atmospheric pressure. The purpose of using liquid hydrocarbons is to facilitate the removal of water present in the reaction mixture by azeotropic distillation. Preferably, the haloalkylsilane is added gradually to the reaction mixture containing the alkali metal salt. When the addition is complete and the exothermic reaction has subsided, the reaction mixture is
Preferably, heating at 70 to about 150°C for several hours substantially completes the conversion of the reactants to the phenoxyalkylsilane having the desired functional substituents.
The organosilicon compounds of the present invention, most of which are colorless, high-boiling, highly viscous oils, are soluble in the reaction medium and are therefore easily isolated by evaporation of the liquid hydrocarbon and dipolar neutral solvent. be separated. The compounds of this invention become dark in color when exposed to light or air for extended periods of time. As mentioned above, the method of the present invention can be applied to the production of any phenoxyalkylsilane, some of which are known compounds. The tri(hydrocarbyloxy)haloalkylsilane or di(hydrocarbyloxy)haloalkylsilane used as one of the reactants for producing the organosilicon compounds of the present invention may be commercially available or have a corresponding Haloalkyltrihalosilane or formula (wherein X ¹ and X ² represent chlorine, bromine or iodine) and an alcohol R ⁶ OH having 1 to 12 carbon atoms. Alternatively, the hydroxyl group may be attached to a carbocyclic or heterocyclic structure such as a cyclohexyl or phenyl group. Haloalkyltrihalosilanes may be prepared by reacting a haloalkene, such as allyl chloride or metaallyl chloride, with a trihalosilane HSIX ² ₃ in the presence of platinum contact at ambient temperature. Methods for making intermediate silanes are well known to those skilled in the art. Therefore, details of the reaction conditions are omitted in this specification. Anhydrous alkali metal or alkaline earth metal salts of phenols may be prepared using the free metal or metal hydride or alkoxide, such as sodium hydride or sodium methoxide. All of these compounds are added to a solution consisting of the desired phenolic derivative and a dipolar neutral liquid which may optionally contain liquid hydrocarbons.
The metals, metal hydrides or metal alkoxides are conveniently used in the form of dispersions or slurries in liquid hydrocarbons. The temperature of the reaction medium should be kept between ambient temperature and approximately 50℃ to prevent uncontrollable exothermic reactions.
is maintained. The organosilicon compounds of the present invention can be used as coupling agents for bonding organic polymers with inorganic materials such as glass fibers or metals, as flocculants for water purification, as sizing agents for glass fibers or fabrics, and in particular for automotive polishes. It is useful as an ingredient in solvents and waxes. Elastomeric compounds useful as coating materials, sealants, and molding materials are prepared by reacting the organosilicon compounds of the present invention with liquid, hydroxy- or alkoxy-terminated organopolysiloxanes and optionally fillers. obtain. Examples of the present invention are shown below. In the examples, all parts and percentages are by weight unless otherwise specified. Example 1 Preparation of 3,5-bis(carbomethoxy)phenoxypropyl trimethoxysilane In a reactor, 115.5 g (0.55 mol) of 3,5-bis(carbomethoxy)aminophenol, 43.28 g of
50% sodium hydroxide aqueous solution (NaOH0.54 mol),
112 c.c. of dimethyl sulfoxide and 120 c.c. of toluene were charged. The resulting mixture was heated to boiling point for 6 hours under a nitrogen atmosphere to remove substantially all of the water present in the mixture by azeotropic distillation. After cooling the reaction mixture to approximately 75 °C, it was heated to 109 °C with stirring.
g (0.555 mol) of chloropropyltrimethoxysilane were added dropwise. After the addition was complete, the temperature of the reaction mixture was raised to 115° C. and held at this temperature for about 16 hours, then the reaction mixture was cooled to room temperature. After filtering the reaction mixture, toluene, dimethyl sulfoxide and other volatile components were then removed under reduced pressure with a water aspirator. The liquid residue was distilled under reduced pressure of 3-4 mmHg to obtain 95 g of a fraction with a boiling point of 240-270°C. Fractional distillation of this fraction yields a boiling point of 250 to 252 under a pressure of 3 mmHg.
75 g of a viscous colorless oil at 0.degree. C. was obtained. The infrared absorption spectrum and nuclear magnetic resonance spectrum of this product were consistent with the structure of the target compound. Gas phase chromatography of this product revealed a purity of over 98%. This compound gradually solidified upon standing. Example 2 Preparation of O-propynylphenoxypropyltrimethoxysilane In a glass reactor, 73.7 g (0.55 mol) o-allylphenol, 43.28 g 50% aqueous sodium hydroxide solution (0.54 mol NaOH), 112 c. c. of dimethyl sulfoxide and 120 c.c. of toluene were charged.
The resulting mixture was heated to boiling point for 6 hours under nitrogen atmosphere to remove all the water present in the mixture by azeotropic distillation. After the reaction mixture was cooled to about 75° C., 109 g (0.55 mol) of 3-chloropropyltrimethoxyrane was added dropwise with stirring. After the addition was complete, the reaction mixture was heated at 115° C. for 16 hours. After the reaction mixture was cooled, it was filtered to remove solid material. Then, the solvent was heated to about 60°C under a pressure of about 15 mmHg.
It was removed at a temperature of The pressure was then reduced to 2 mmHg and a fraction with a boiling point of 146°C was collected. The weight was equivalent to a yield of 90% based on the starting material. The results of gas phase chromatography showed that the purity of the above product was over 98%.
The infrared absorption spectrum and nuclear magnetic resonance spectrum of this product were consistent with the structure of the target compound. Example 3 Production of p-carbomethoxyphenoxypropylmethyldimethoxysilane In a reactor, 83.7 g (0.55 mol) of methyl p-hydroxybenzoate, 43.28 g of 50% aqueous sodium hydroxide solution (NaOH 0.54 mol), 112c .c. of dimethyl sulfoxide and 120 c.c. of toluene were charged. The resulting mixture was heated to boiling point for 6 hours under nitrogen atmosphere to remove all the water present in the mixture by azeotropic distillation. After the reaction mixture was cooled to about 75° C., 109 g (0.55 mol) of 3-chloropropyltrimethoxysilane was added dropwise with stirring. After the addition was complete, the reaction mixture was heated at 115° C. for 16 hours.
After the reaction mixture was cooled, it was filtered to remove solid material. Then, apply the solvent under a pressure of about 15 mmHg, about 60
It was removed at a temperature of °C. The pressure was then reduced to 2 mm Hg and material with a boiling point of 230-235°C was collected.
The weight of this fraction was equivalent to a yield of 92% based on starting material. Gas phase chromatography showed that the purity of this product was over 98%. The infrared absorption spectrum and nuclear magnetic resonance spectrum of the above product were consistent with the structural formula of the target compound. Example 4 Preparation of m-succinimidophenoxypropyltrimethoxysilane A solution containing 200 g of succinic anhydride, 218 g of m-aminophenol and 1 part of glacial acetic acid was heated with a mechanically driven stirrer and a water-cooled reflux condenser. and heated at boiling point for 16 hours in a reactor equipped with. The reaction mixture solidified upon cooling to ambient temperature. This solid was pulverized, washed with water to remove acetic acid, and then dried. 50% of the thus obtained m-succinimidophenol (105, 1 g, 0.55 mol), 43.28 g
of NaOH, 112 c.c. of dimethyl sulfoxide, and 120 c.c. of toluene were charged into a reactor equipped with a nitrogen inlet, a water-cooled reflux condenser, and a Dean-Stark trap. The resulting mixture was heated to boiling point for 6 hours under nitrogen atmosphere to remove all the water present in the mixture by azeotropic distillation. After the reaction mixture was cooled to about 75° C., 109 g (0.55 mol) of 3-chloropropyltrimethoxysilane was added dropwise with stirring. After the addition was complete, the reaction mixture was heated at 115° C. for 16 hours. After the reaction mixture was cooled, it was filtered to remove solid material. The solvent was then removed under a pressure of about 15 mm Hg and a temperature of about 60°C. The pressure was then reduced to 0.5 mm Hg and material with a boiling point of 228°C was collected. Gas phase chromatography showed that the purity of this product was over 98%. The infrared absorption spectrum and nuclear magnetic resonance spectrum of the above product were consistent with the structural formula of the target compound.

Claims (1)

[Claims] 1 General formula (): (In the formula, R ¹ represents -COOR ⁸ (R ⁸ is a lower alkyl group), a C ₂ to C ₅ alkenyl group, or [Formula], R ⁵ represents a lower alkylene group, and R ⁶ and R ⁷ , each represents a lower alkyl group, m is 1 or 2, p is 2 or 3
A novel organosilicon compound represented by 2. The compound according to claim 1, wherein R ⁵ is a propylene group. 3. The compound according to claim 1, wherein R ⁶ and R ⁷ are alkyl groups having 1 to 4 carbon atoms. 4. The compound according to claim 3, wherein R ⁶ and R ⁷ are methyl groups. 5 General formula: (wherein M represents an alkali metal or alkaline earth metal, and R ¹ and m have the meanings given below); and an anhydrous alkali metal or alkaline earth metal compound represented by the general formula: (In the formula, X represents chlorine, bromine or iodine, R ⁵ ,
R ⁶ , R ⁷ and p have the meanings given below) in substantially equimolar amounts under substantially anhydrous conditions, and at least a portion of the haloalkylsilane represented by at least one dipolar neutral liquid. reacted at a temperature between ambient temperature and 200°C in a liquid reaction medium consisting mainly of liquid hydrocarbons having a boiling point of 40-200°C; holding the compound and the silane compound at a temperature of 40 to 200° C. for a period sufficient to substantially completely convert the compound and the silane compound to the desired functional phenoxyalkyl silane, and then isolating the resulting silane compound; The general formula (), characterized by: [In the formula, R ¹ represents -COOR ⁸ (R ⁸ is a lower alkyl group), a C ₂ to C ₅ alkenyl group, or [Formula], R ⁵ represents a lower alkylene group, and R ⁶ and R ⁷ are , each represents a lower alkyl group, m is 1 or 2, p is 2 or 3
A method for producing an organosilicon compound represented by 6. The method according to claim 5, wherein R ⁵ is a propylene group. 7. The method according to claim 5, wherein R ⁶ and R ⁷ are alkyl groups having 1 to 4 carbon atoms. 8. The method according to claim 7, wherein R ⁶ and R ⁷ are methyl groups. 9. The method according to claim 5, wherein X is chlorine. Claim 5 in which 10 M is sodium
The method described in section. 11 The bipolar neutral liquid is dimethyl sulfoxide,
6. The method of claim 5, wherein the compound is selected from the group consisting of N,N-dimethylformamide, tetramethylurea and hexamethylphosphoramide. 12. The method according to claim 5, wherein the reaction between the alkali metal or alkaline earth metal compound and the silane compound is carried out in an inert atmosphere. 13 Bipolar neutral liquid 1-100% by weight of reaction medium
The method according to claim 5, which comprises: