Method for producing cyclic oligosaccharide-modified organopolysiloxanes

Abstract

To provide an efficient method for producing a non-cross-linked cyclic oligosaccharide-modified organopolysiloxane soluble in solvents despite its high molecular weight, by removing unreacted cyclic oligosaccharides.SOLUTION: A method for producing a cyclic oligosaccharide-modified organopolysiloxane comprises the following steps: [Step 1] obtaining an oligosaccharide-modified organopolysiloxane by hydrosilylation of a composition containing (A) to (D) in the following, namely, (A) an organohydrogen polysiloxane having one or more hydrosilyl groups per molecule having a kinematic viscosity of 50 mm2 / s or more at 25°C and a number average molecular weight of 8,000 or more, (B) a cyclic oligosaccharide derivative having an unsaturated group represented by the specified general formula (1), (C) a hydrosilylation catalyst, and (D) an organic solvent; [Step 2] cleaning and filtering the cyclic oligosaccharide-modified organopolysiloxane obtained in the Step 1 with a cleaning organic solvent having a relative permittivity of 23 or more at 25°C or a mixture of such solvents; and [Step 3] removing the organic solvents used in the Steps 1 and 2.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to a method for producing cyclic oligosaccharide-modified organopolysiloxanes. [Background technology]

[0002] Organopolysiloxanes can possess diverse functions by modifying their terminal or side chain chemical structures. On the other hand, cyclic oligosaccharides are known to interact with various compounds due to the vacancies in their molecular structure. Utilizing this characteristic, they are used in industrial fields such as food and cosmetics, and their introduction into various polymer materials is being considered to develop functional materials. In fact, the introduction of cyclic oligosaccharides into organopolysiloxanes has been investigated, and a gel material crosslinked with a cyclic oligosaccharide derivative has been disclosed (Patent Document 1).

[0003] However, because the above-mentioned cyclic oligosaccharide-modified organopolysiloxanes are crosslinked products, they swell in solvents but are poorly soluble, limiting their application as film-forming agents and coating materials.

[0004] Patent Document 2 and Non-Patent Document 1 disclose a method for producing a cyclic oligosaccharide-modified organopolysiloxane that is not a crosslinked product, using a derivative in which only one hydroxyl group of a cyclic oligosaccharide is modified with a reactive functional group.

[0005] However, since cyclic oligosaccharides and organopolysiloxanes generally do not mix well, the addition of these to high molecular weight organopolysiloxanes has not been sufficiently investigated. In fact, the number-average molecular weight of the organopolysiloxanes used in Patent Document 2 and Non-Patent Document 1 is relatively low, ranging from about 1,000 to 7,500.

[0006] Furthermore, when considering applications as film-forming agents or coating materials, the presence of unreacted cyclic oligosaccharide derivatives can lead to problems such as stickiness on the film surface. Examples of unreacted cyclic oligosaccharide derivatives include those that do not contain the reactive functional groups present in the raw materials, and those that do contain unreacted reactive functional groups.

[0007] Patent Document 2 discloses a purification method in which a cyclic oligosaccharide-modified organopolysiloxane is dissolved in isododecane, and the poorly soluble, unreacted cyclic oligosaccharide derivative is removed by ethyl acetate extraction. However, when the number-average molecular weight of the organopolysiloxane is 8,000 or more, this method makes it difficult to increase the purity of the cyclic oligosaccharide-modified organopolysiloxane.

[0008] Non-patent document 1 discloses a purification method for removing unreacted cyclic oligosaccharide derivatives using silica gel column chromatography. However, this method is not efficient when considering its application on an industrial scale. [Prior art documents] [Patent Documents]

[0009] [Patent Document 1] Special Publication No. 2022-503533 [Patent Document 2] International Publication No. 2021 / 172468 [Non-patent literature]

[0010] [Non-Patent Document 1] Ahlem Noomen et al., Emulsions of β-cyclodextrins grafted to silicone for the transport of antifungal drugs,Materials Science and Engineering C,2008,28,p.705-715 [Overview of the project]

Problems to be Solved by the Invention

[0011] In view of the above circumstances, the present invention provides an efficient method for removing unreacted cyclic oligosaccharides in the production of non-crosslinked cyclic oligosaccharide-modified organopolysiloxanes that are soluble in solvents while having a high molecular weight.

Means for Solving the Problems

[0012] In order to achieve the above object, the present invention provides a method for producing the following cyclic oligosaccharide-modified organopolysiloxane.

[0013] That is, the present invention provides a step [Step 1] of obtaining an oligosaccharide-modified organopolysiloxane by hydrosilylation of a composition containing the following (A) to (D). (A) An organohydrogenpolysiloxane having one or more hydrosilyl groups in one molecule, with a kinematic viscosity at 25°C of 50 mm 2 / s or more and a number average molecular weight of 8,000 or more. (B) A cyclic oligosaccharide derivative having an unsaturated group represented by the following general formula (1). (C) A hydrosilylation catalyst. (D) An organic solvent. [Step 2] A step of washing and filtering the cyclic oligosaccharide-modified organopolysiloxane obtained in Step 1 with a washing organic solvent having a relative permittivity at 25°C of 23 or more, or a mixture thereof. [Step 3] A step of removing the organic solvents used in Step 1 and Step 2. The present invention provides a method for producing a cyclic oligosaccharide-modified organopolysiloxane, characterized by including the above steps.

Chemical Formula

[0014] The manufacturing method of the present invention allows for the efficient removal of unreacted cyclic oligosaccharides by adding a high molecular weight organopolysiloxane and a cyclic oligosaccharide via a hydrosilylation reaction, followed by washing with a washing organic solvent with a dielectric constant of 23 or higher at 25°C. By removing the unreacted cyclic oligosaccharides, a transparent, non-sticky, flexible, and tough film is obtained, making it useful as a film-forming agent or coating material.

[0015] In this case, in step 1, it is preferable to further add an addition reaction by hydrosilylation of an α-olefin having 2 to 16 carbon atoms after the hydrosilylation reactions of (A) and (B). Such cyclic oligosaccharide-modified organopolysiloxanes exhibit increased compatibility with cyclic oligosaccharides.

[0016] Furthermore, in the general formula (1) above, R 1 is a methyl group, R 3 It is preferable that the method is for producing a cyclic oligosaccharide-modified organopolysiloxane in which the group is an acetyl group.

[0017] It is even more preferable that the method is for producing a cyclic oligosaccharide-modified organopolysiloxane in the general formula (1) above, where x is 1. Such a design would more reliably achieve the effects of the present invention.

[0018] The preferred method for producing the cyclic oligosaccharide-modified organopolysiloxane is one in which the glass transition temperature, as measured by dynamic viscoelasticity measurement, is 50 to 100°C.

[0019] This method makes it possible to obtain cyclic oligosaccharide-modified organopolysiloxanes that have sufficient mechanical properties and flexible film-forming ability at room temperature.

[0020] It is even more preferable that the method for producing the cyclic oligosaccharide-modified organopolysiloxane is one or more organic solvents selected from methanol, ethanol, and acetonitrile in step 2. Washing with such a solvent can more reliably and efficiently remove unreacted cyclic oligosaccharides. [Effects of the Invention]

[0021] According to the manufacturing method of the present invention, after adding a high molecular weight organopolysiloxane and a cyclic oligosaccharide by a hydrosilylation reaction, unreacted cyclic oligosaccharides can be efficiently removed by washing with a washing organic solvent with a dielectric constant of 23 or higher at 25°C. By removing the unreacted cyclic oligosaccharides, a film is obtained that is transparent, non-sticky, flexible, and tough, despite having a high molecular weight, making it useful as a film-forming agent or coating material. [Modes for carrying out the invention]

[0022] The present invention will be described in detail below, but the present invention is not limited to these descriptions.

[0023] As a result of diligent research to achieve the above objective, the present inventors have discovered that unreacted cyclic oligosaccharides can be efficiently removed by adding a high molecular weight organopolysiloxane and a cyclic oligosaccharide by a hydrosilylation reaction, followed by washing with methanol, ethanol, acetonitrile, or a mixture thereof, thus completing the present invention.

[0024] In other words, the present invention provides an oligosaccharide-modified organopolysiloxane obtained by hydrosilylation of a composition containing (A) to (D) below in [Step 1] with a kinematic viscosity of 50 mm at 25°C. 2 Organohydrogenpolysiloxane having a molecular weight of 8,000 or more and containing one or more hydrosilyl groups per molecule. (B) Cyclic oligosaccharide derivatives having an unsaturated group represented by the following general formula (1) (C) Hydrosilylation catalyst (D) Organic solvent [Step 2] A step of washing and filtering the cyclic oligosaccharide-modified organopolysiloxane obtained in Step 1 with a washing organic solvent having a relative permittivity of 23 or more at 25°C or a mixture thereof [Step 3] A step of removing the organic solvent used in Step 1 and Step 2 A method for producing a cyclic oligosaccharide-modified organopolysiloxane, comprising the above steps. [Chemical formula] (In the formula, A is an alkenyl group having 2 to 12 carbon atoms, R 1 is independently a group selected from an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms, and R 2 is an alkylene group having 1 to 4 carbon atoms, R 3 is independently a group selected from an alkyl group having 1 to 4 carbon atoms or an acyl group having 1 to 4 carbon atoms, a is an integer of 0 to 8, b is an integer of 5 to 7, and x is 0 or 1.)

[0025] [Step 1] Step 1 in the production method of the present invention is a step of obtaining an oligosaccharide-modified organopolysiloxane by hydrosilylation of a composition containing the following (A) to (D). (A) An organohydrogenpolysiloxane having one or more hydrosilyl groups in one molecule, having a kinematic viscosity at 25°C of 50 mm 2 / s or more and a number average molecular weight of 8,000 or more (B) A cyclic oligosaccharide derivative having an unsaturated group represented by the above general formula (1) (C) A hydrosilylation catalyst (D) Organic solvent Hereinafter, each component of the composition will be described in detail.

[0026] [(A) Organohydrogenpolysiloxane] In the above (A), the kinematic viscosity at 25°C is 50 mm 2 / s or more, and from the viewpoint of ease of handling, it is 50 to 25,000 mm 2It is preferable that the value be / s, and the range is 50 to 10,000 mm. 2 It is more preferable that the value is / s. In this invention, the kinematic viscosity is the value measured at 25°C using a Cannon-Fenske viscometer as described in JIS Z8803:2011.

[0027] Furthermore, the number of hydrosilyl groups contained in one molecule of organohydrogenpolysiloxane is one or more, preferably 1 to 40, and more preferably 1 to 20, from the viewpoint of the resulting film properties. In addition, the number average molecular weight is 8,000 or more, preferably 8,000 to 50,000, and more preferably 8,000 to 35,000, from the viewpoint of ease of handling. In this invention, the number average molecular weight is the value obtained by GPC (gel permuration chromatography) analysis using polystyrene as a standard substance under the following conditions.

[0028] [Measurement conditions] Developing solvent: Toluene Flow rate: 0.6mL / min Detector: Differential refractive index detector (RI) Column: TSK Guardcolumn SuperH-H TSKgel SuperH5000(6.0mmI.D.×15cm×1) TSKgel SuperH4000(6.0mmI.D.×15cm×1) TSKgel SuperH3000(6.0mmI.D.×15cm×1) TSKgel SuperH2000(6.0mmI.D.×15cm×1) (All manufactured by Tosoh Corporation) Column temperature: 40℃ Sample injection volume: 50 μL (toluene solution with a concentration of 0.3% by mass)

[0029] [(B) Cyclic oligosaccharide derivatives] The cyclic oligosaccharide derivative (B) used in the present invention is represented by the general formula (1) above. In formula (1) of (B) above, A is an alkenyl group having 2 to 12 carbon atoms, and from the viewpoint of procuring raw materials for synthesis, an alkenyl group having 2 to 4 carbon atoms is preferred, and a vinyl group is more preferred. 1 R is independently selected from alkyl groups having 1 to 4 carbon atoms, aryl groups having 6 to 10 carbon atoms, and aralkyl groups having 7 to 10 carbon atoms. From the viewpoint of procuring synthetic raw materials, a methyl group or an ethyl group is preferred, and a methyl group is more preferred. 2 R is an alkylene group having 1 to 4 carbon atoms, and from the viewpoint of procuring raw materials for synthesis, an alkylene group having 2 to 3 carbon atoms is preferred, and a propylene group is more preferred. 3 is independently selected from an alkyl group having 1 to 4 carbon atoms or an acyl group having 1 to 4 carbon atoms, with an acyl group having 1 to 4 carbon atoms being preferred from the viewpoint of reaction conditions, and an acetyl group being more preferred. a is an integer from 0 to 8, with 0 to 2 being preferred from the viewpoint of procuring synthesis raw materials, and 0 being more preferred. b is an integer from 5 to 7. x is 0 or 1, and x is preferably 1 because of its excellent compatibility with component (A). The amount of component (B) is preferably such that the amount of alkenyl groups in component (B) is 0.01 to 5 moles per mole of hydrosilyl groups in component (A). More preferably, it is 0.5 to 3 moles, and even more preferably, 0.8 to 1.2 moles. This range is preferable because the reaction proceeds smoothly.

[0030] [(C) Hydrosilylation catalyst] The (C) hydrosilylation catalyst used in the present invention is for promoting the hydrosilylation reaction between the hydrosilyl group in component (A) and the alkenyl group in component (B). The hydrosilylation catalyst in (C) is preferably a platinum catalyst or a rhodium catalyst. Specifically, catalysts such as chloroplatinic acid, alcohol-modified chloroplatinic acid, and chloroplatinic acid-vinylsiloxane complexes are suitably used. The amount of catalyst used can be a catalytic amount, but it is preferable that the amount of platinum or rhodium is 100 ppm or less, and particularly preferably 50 ppm or less, relative to the total amount of components (A) to (D). Within this range is preferable because the appearance of the cyclic oligosaccharide-modified organopolysiloxane does not become discolored.

[0031] [(D) Organic solvents] The organic solvent (D) used in this invention is intended to uniformly miscible components (A) to (C) above, to promote the reaction, and to reduce the viscosity of the composition and improve stirring efficiency. Examples of the organic solvents in (D) above include aliphatic alcohols such as methanol, ethanol, 2-propanol, and butanol; aromatic hydrocarbons such as toluene and xylene; aliphatic or alicyclic hydrocarbons such as n-pentane, n-hexane, and cyclohexane; and halogenated hydrocarbons such as dichloromethane, chloroform, and carbon tetrachloride. Component (D) is preferably compatible with components (A) and (B), and among these, toluene is preferred from the viewpoint of compatibility with the raw materials. The amount of component (D) is preferably 10 to 90% by mass, and more preferably 30 to 70% by mass, relative to the total amount of components (A) to (D).

[0032] The hydrosilylation reaction conditions are not particularly limited, but it is preferable to carry out the reaction at 70-110°C for 1-10 hours. Furthermore, before proceeding to the next step, step 2, after completing step 1, the organic solvent of component (D) may be removed before proceeding to step 2. The internal pressure when removing component (D) may be at atmospheric pressure or under reduced pressure. The temperature is not particularly limited, but it is preferably between 20°C and 100°C.

[0033] The method for producing the cyclic oligosaccharide-modified organopolysiloxane of the present invention may also include a step of adding a carbon 2- to carbon 16 α-olefin after the hydrosilylation reaction described above. From the viewpoint of compatibility with the cyclic oligosaccharide-modified organopolysiloxane obtained above, the carbon 2- to carbon 16 α-olefin is preferably a carbon 5- to carbon 12 alkyl group, more preferably a carbon 6- to carbon 8 alkyl group, and even more preferably an octyl group. Preferably, for every mole of hydrosilyl groups in (A) organohydrogenpolysiloxane, the amount of alkenyl groups in (B) cyclic oligosaccharide derivative is 0.02 to 1.2 moles, and the amount of alkenyl groups in α-olefin is 0.02 to 1.98 moles. However, it is preferable that the total amount of components (B) and α-olefin is in the range of 0.8 to 2.0 moles per mole of hydrosilyl groups in (A).

[0034] [Process 2] Step 2 in the manufacturing method of the present invention is a step of washing and filtering the cyclic oligosaccharide-modified organopolysiloxane obtained in Step 1 with a washing organic solvent with a relative permittivity of 23 or more at 25°C, or a mixture thereof. The dielectric constant of an organic solvent is known as an indicator of the solvent's polarity. By using a washing organic solvent with a dielectric constant of 23 or higher at 25°C, only the unreacted component (B) can be dissolved, and the target cyclic oligosaccharide-modified organopolysiloxane can be recovered by filtration. The dielectric constant of the washing organic solvent is characterized by being 23 or higher, preferably between 23 and 50, and more preferably between 23 and 40. In this invention, the dielectric constant at 25°C is taken from the values ​​listed in the Chemical Handbook Basic Edition, 5th Revised Edition (edited by the Chemical Society of Japan, published in 2004). Examples of cleaning organic solvents with a relative permittivity of 23 or higher at 25°C include methanol (32.66), ethanol (24.55), ethylene glycol (37.7), propylene glycol (32.0), N,N-dimethylformamide (36.71), N,N-dimethylacetamide (37.78), and acetonitrile (35.94) (the values ​​in parentheses are the relative permittivity). Among these, methanol, ethanol, and acetonitrile are preferred. These organic solvents may be used individually or as a mixture of two or more. When used as a mixture, the weighted average relative permittivity of the mixture is considered to be the relative permittivity of the mixture. The dissolution temperature is not particularly limited and should be below the boiling point of the solvent, but is preferably between 20°C and 70°C. Furthermore, since high transparency is required when used as a film-forming agent, the residual amount of component (B) is preferably 10% or less, more preferably 5% or less, and even more preferably 1% or less of the obtained cyclic oligosaccharide-modified organopolysiloxane. The present invention has revealed that residual component (B) leads to stickiness of the film and a decrease in its mechanical properties.

[0035] [Process 3] Step 3 in the manufacturing method of the present invention is a step of removing the organic solvent used in steps 1 and 2. In step 3, the internal pressure when removing the organic solvent may be at atmospheric pressure or under reduced pressure. The temperature is not particularly limited, but it is preferably between 20°C and 100°C.

[0036] The glass transition temperature of the cyclic oligosaccharide-modified organopolysiloxane obtained by the method of the present invention is preferably 50 to 100°C, more preferably 60 to 95°C, and even more preferably 65 to 90°C, from the viewpoint of the properties of the formed film. Within the above range, a flexible film is formed with sufficient mechanical properties at room temperature. The glass transition temperature in the present invention is a value obtained by dynamic viscoelasticity measurement under the conditions shown in the examples described later.

[0037] [Film-forming agent] The cyclic oligosaccharide-modified organopolysiloxane obtained by the method of the present invention forms a highly transparent, flexible, non-sticky, and tough film, and can therefore be used as a film-forming agent.

[0038] While the cyclic oligosaccharide-modified organopolysiloxane can be used alone as a film-forming agent, it is preferable to dilute it with an organic solvent for reasons such as film-forming properties and workability.

[0039] The organic solvent can be selected from volatile siloxanes, saturated aliphatic hydrocarbons, saturated alicyclic hydrocarbons, aromatic hydrocarbons, chloride hydrocarbons, chloride fluorinated hydrocarbons, alcohols, and the like. Particularly preferred are volatile organosiloxanes and light liquid isoparaffins having a boiling point of 100 to 270°C at atmospheric pressure (1013 hPa). Examples of volatile siloxanes include cyclic siloxanes such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriethylcyclotrisiloxane, hexaethyltricyclosiloxane, diethyltetramethylcyclotrisiloxane, dimethyltetraethylcyclotrisiloxane, diethylhexamethylcyclotetrasiloxane, and tetraethyltetramethylcyclotetrasiloxane; linear siloxanes such as hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, hexaethyldisiloxane, and octaethyltrisiloxane; and branched siloxanes such as methyltris(trimethylsiloxy)silane and phenyltris(trimethylsiloxy)silane. Furthermore, examples of light liquid isopaline include those whose main component is isoparaffin having 8 to 16 carbon atoms.

[0040] When using an organic solvent, the amount of cyclic oligosaccharide-modified organopolysiloxane is preferably 0.1 to 80%, and more preferably 0.5 to 20%.

[0041] As for the coating method, a known method can be used depending on the type of substrate to be coated.

[0042] The cyclic oligosaccharide-modified organopolysiloxane film-forming agent obtained by the method of the present invention can be used as a damage protectant, water repellent, and release agent for cosmetics, paints, paper, plastic sheets, and rubber articles; a damage protectant, water repellent, waterproofing agent, texture improver, and sealant for fabrics; and a water repellent, waterproofing agent, and release agent for concrete, mortar, and wood. It can be used to impart cosmetic durability, slipperiness, water repellency, and other properties. [Examples]

[0043] The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples.

[0044] [Measurement method] The various measurements were performed using the following methods.

[0045] <Glass transition temperature> The glass transition temperature is obtained by analyzing dynamic viscoelastic data measured using a Hitachi High-Tech Science "DMA7100" with a thickness of 0.25 mm, under tensile mode, frequency of 1 Hz, and heating rate of 5 °C / min in the range of 25 to 120 °C. The temperature at which tanδ (loss tangent), expressed as E'' (loss modulus) / E' (storage modulus), is maximized is identified, and this temperature is defined as the glass transition temperature.

[0046] < 1 H-NMR> Measurements were performed using an AVANCE-III 400MHz (BRUKER) and deuterated chloroform as the measurement solvent.

[0047] [Synthesis Example 1: Synthesis of Cyclic Oligosaccharide Derivatives Containing Unsaturated Bonds] 50.0 g of mono-6-O-(p-toluenesulfonyl)-β-cyclodextrin (C6-Ts-β-CD) and 500.0 g of allylamine were charged into a four-necked flask equipped with a stirrer, thermometer, reflux condenser, and dropping funnel. After purging the flask with nitrogen, the mixture was stirred at 53°C for 7 hours, cooled to room temperature, and stirred overnight. The mixture was concentrated using an evaporator, and 1,000 mL of acetonitrile was added to the resulting solid. The precipitate was collected by filtration. 1,000 mL of distilled water was added to the precipitate to dissolve it, and this solution was added dropwise to 1,000 mL of acetonitrile. The precipitate was collected by filtration. After washing the precipitate with acetone, it was dried in a vacuum dryer at 40°C to obtain vinyl-modified compound A (white solid, 42.7 g).

[0048] [ka]

[0049] [Synthesis Example 2: Synthesis of Cyclic Oligosaccharide Derivatives Containing Unsaturated Bonds] A four-necked flask equipped with a stirrer, thermometer, reflux condenser, and dropping funnel was charged with 30.0 g of vinyl-modified compound A, 110.0 g of acetic anhydride, and 170.0 g of pyridine. After purging the flask with nitrogen, the mixture was stirred at 60°C for 7 hours, cooled to room temperature, and stirred overnight. 170 mL of toluene was added to the solution in the flask, and the mixture was washed twice with 170 mL of 1 mM hydrochloric acid and once with 170 mL of saturated saline solution. The resulting solution was separated and concentrated using an evaporator. The recovered solid was then dissolved in 50 mL of acetone, and the solution was added dropwise to 500 mL of distilled water. The precipitate was collected by filtration. The precipitate was dried in a vacuum dryer at 40°C to obtain vinyl-modified compound B (white solid, 31.8 g).

[0050] [ka]

[0051] [Synthesis Example 3: Synthesis of Cyclic Oligosaccharide Derivatives Containing Unsaturated Bonds] A four-necked flask equipped with a stirrer, thermometer, reflux condenser, and dropping funnel was charged with 48.0 g of mono-6-O-(p-toluenesulfonyl)-β-cyclodextrin (C6-Ts-β-CD), 300.0 g of 1-vinyl,3-(3-aminopropyl)tetramethyldisiloxane, and 60.0 g of N,N-dimethylformamide. After purging the flask with nitrogen, the mixture was stirred at 75°C for 7 hours, cooled to room temperature, and stirred overnight. The solution in the flask was added dropwise to 1,200 mL of acetonitrile, and the precipitate was collected by filtration. 60.0 g of N,N-dimethylformamide was added to the obtained precipitate and dissolved. This solution was added dropwise to 1,200 mL of toluene, and the precipitate was collected by filtration. After washing the precipitate with acetone, it was dried in a vacuum dryer at 40°C to obtain vinyl-modified compound C (white solid, 42.5 g).

[0052] [ka]

[0053] [Synthesis Example 4: Synthesis of Cyclic Oligosaccharide Derivatives Containing Unsaturated Bonds] A four-necked flask equipped with a stirrer, thermometer, reflux condenser, and dropping funnel was charged with 42.0 g of vinyl-modified compound C, 134.4 g of acetic anhydride, and 210.0 g of pyridine. After purging the flask with nitrogen, the mixture was stirred at 60°C for 7 hours, cooled to room temperature, and stirred overnight. 210 mL of toluene was added to the solution in the flask, and the mixture was washed twice with 210 mL of 1 mM hydrochloric acid and once with 210 mL of saturated saline solution. The resulting solution was separated and concentrated using an evaporator. The recovered solid was then dissolved in 150 mL of toluene, and the solution was added dropwise to 300 mL of hexane. The precipitate was collected by filtration. The precipitate was dried in a vacuum dryer at 40°C to obtain vinyl-modified compound D (white solid, 50.1 g).

[0054] [ka]

[0055] [Example 1] A four-necked flask equipped with a stirrer, thermometer, reflux condenser, and dropping funnel contains 100.0 g of polyorganohydrogensiloxane represented by formula (2) below (kinematic viscosity: 3,340 mmHg). 2 A mixture of 24.9 g of the aforementioned vinyl-modified compound B (number average molecular weight: 31,100, hydrosilyl group content: 0.040 mol), 200.0 g of toluene was charged. After purging the flask with nitrogen, the temperature was raised to 90°C, and 1.3 g of a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum concentration 0.5 wt%) was added to the flask and stirred at 90°C for 4 hours. 1 The reaction was confirmed by the disappearance of the vinyl group peak (5.6-6.1 ppm) by 1H-NMR. Subsequently, 6.4 g (0.057 mol) of 1-octene and 0.7 g of a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum concentration 0.5 wt%) were added to the flask and stirred at 90°C for 4 hours. The reaction mixture was then cooled to room temperature, and toluene was removed under reduced pressure using an evaporator. 250 g of methanol was added to the resulting solid, and the washing of the solid at 50°C was repeated three times. Finally, the mixture was dried in a vacuum dryer at 40°C to obtain cyclic oligosaccharide-modified organopolysiloxane E (light brown solid, 119.7 g).

[0056] [ka]

[0057] [Example 2] A four-necked flask equipped with a stirrer, thermometer, reflux condenser, and dropping funnel was charged with 128.3 g of polyorganohydrogensiloxane represented by formula (2) below (hydrosilyl group amount: 0.052 mol), 45.0 g of the aforementioned vinyl-modified compound D (vinyl group amount: 0.016 mol), and 256.0 g of toluene. After purging the flask with nitrogen, the temperature was raised to 90°C, and 1.7 g of a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum concentration 0.5 wt%) was added to the flask and stirred at 90°C for 2 hours.1 The progress of the reaction was confirmed by the disappearance of the vinyl group peak (5.6-6.1 ppm) by 1H-NMR. Subsequently, 8.2 g (0.073 mol) of 1-octene and 0.9 g of a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum concentration 0.5 wt%) were added to the flask and stirred at 90°C for 4 hours. The reaction mixture was then cooled to room temperature, and toluene was removed under reduced pressure using an evaporator. 300 g of methanol was added to the resulting solid, and the washing of the solid at 50°C was repeated three times. Finally, the mixture was dried in a vacuum dryer at 40°C to obtain cyclic oligosaccharide-modified organopolysiloxane F (light brown solid, 148.3 g).

[0058] [ka]

[0059] [Example 3] A four-necked flask equipped with a stirrer, thermometer, reflux condenser, and dropping funnel was charged with 128.3 g of polyorganohydrogensiloxane represented by formula (2) below (hydrosilyl group amount: 0.052 mol), 45.0 g of the aforementioned vinyl-modified compound D (vinyl group amount: 0.016 mol), and 256.0 g of toluene. After purging the flask with nitrogen, the temperature was raised to 90°C, and 1.7 g of a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum concentration 0.5 wt%) was added to the flask and stirred at 90°C for 2 hours. 1The progress of the reaction was confirmed by the disappearance of the vinyl group peak (5.6-6.1 ppm) by 1H-NMR. Subsequently, 8.2 g (0.073 mol) of 1-octene and 0.9 g of a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum concentration 0.5 wt%) were added to the flask and stirred at 90°C for 4 hours. The reaction mixture was then cooled to room temperature, and toluene was removed under reduced pressure using an evaporator. 300 g of ethanol was added to the resulting solid, and the washing of the solid at 50°C was repeated three times. Finally, the mixture was dried in a vacuum dryer at 40°C to obtain cyclic oligosaccharide-modified organopolysiloxane G (light brown solid, 147.8 g).

[0060] [ka]

[0061] [Example 4] A four-necked flask equipped with a stirrer, thermometer, reflux condenser, and dropping funnel was charged with 128.3 g of polyorganohydrogensiloxane represented by formula (2) below (hydrosilyl group amount: 0.052 mol), 45.0 g of the aforementioned vinyl-modified compound D (vinyl group amount: 0.016 mol), and 256.0 g of toluene. After purging the flask with nitrogen, the temperature was raised to 90°C, and 1.7 g of a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum concentration 0.5 wt%) was added to the flask and stirred at 90°C for 2 hours. 1 The reaction was confirmed by the disappearance of the vinyl group peak (5.6-6.1 ppm) by 1H-NMR. Subsequently, 8.2 g (0.073 mol) of 1-octene and 0.9 g of a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum concentration 0.5 wt%) were added to the flask and stirred at 90°C for 4 hours. The reaction mixture was then cooled to room temperature, and toluene was removed under reduced pressure using an evaporator. 300 g of acetonitrile was added to the resulting solid, and the process of washing the solid at 50°C was repeated three times. Finally, the mixture was dried in a vacuum dryer at 40°C to obtain cyclic oligosaccharide-modified organopolysiloxane H (light brown solid, 148.0 g).

[0062] [ka]

[0063] [Example 5] A four-necked flask equipped with a stirrer, thermometer, reflux condenser, and dropping funnel was charged with 77.0 g of polyorganohydrogensiloxane represented by formula (2) below (hydrosilyl group amount: 0.031 mol), 45.0 g of the aforementioned vinyl-modified compound D (vinyl group amount: 0.016 mol), and 154.0 g of toluene. After purging the flask with nitrogen, the temperature was raised to 90°C, and 1.1 g of a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum concentration 0.5 wt%) was added to the flask and stirred at 90°C for 2 hours. 1 The progress of the reaction was confirmed by the disappearance of the vinyl group peak (5.6-6.1 ppm) by 1H-NMR. Subsequently, 3.5 g (0.031 mol) of 1-octene and 0.6 g of a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum concentration 0.5 wt%) were added to the flask and stirred at 90°C for 4 hours. The reaction mixture was then cooled to room temperature, and toluene was removed under reduced pressure using an evaporator. 240 g of methanol was added to the resulting solid, and the washing of the solid at 50°C was repeated three times. Finally, the mixture was dried in a vacuum dryer at 40°C to obtain cyclic oligosaccharide-modified organopolysiloxane I (light brown solid, 113.3 g).

[0064] [ka]

[0065] [Example 6] A four-necked flask equipped with a stirrer, thermometer, reflux condenser, and dropping funnel was charged with 35.0 g of polyorganohydrogensiloxane represented by formula (2) below (hydrosilyl group amount: 0.014 mol), 45.0 g of the aforementioned vinyl-modified compound D (vinyl group amount: 0.016 mol), and 70.0 g of toluene. After purging the flask with nitrogen, the temperature was raised to 90°C, and 0.6 g of a toluene solution of the platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum concentration 0.5 wt%) was added to the flask and stirred at 90°C for 2 hours. 1 The reaction was confirmed by the disappearance of the vinyl group peak (5.6-6.1 ppm) by 1H-NMR. The reaction mixture was then cooled to room temperature, and toluene was removed under reduced pressure using an evaporator. 140 g of methanol was added to the resulting solid, and the process of washing the solid at 50°C was repeated three times. Finally, the mixture was dried in a vacuum dryer at 40°C to obtain cyclic oligosaccharide-modified organopolysiloxane J (light brown solid, 64.3 g).

[0066] [ka]

[0067] [Comparative Example 1] A four-necked flask equipped with a stirrer, thermometer, reflux condenser, and dropping funnel was charged with 128.3 g of polyorganohydrogensiloxane represented by formula (2) below (hydrosilyl group amount: 0.052 mol), 45.0 g of the aforementioned vinyl-modified compound D (vinyl group amount: 0.016 mol), and 256.0 g of toluene. After purging the flask with nitrogen, the temperature was raised to 90°C, and 1.7 g of a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum concentration 0.5 wt%) was added to the flask and stirred at 90°C for 2 hours. 1The reaction was confirmed by the disappearance of the vinyl group peak (5.6-6.1 ppm) by 1H-NMR. Subsequently, 8.2 g (0.073 mol) of 1-octene and 0.9 g of a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum concentration 0.5 wt%) were added to the flask and stirred at 90°C for 4 hours. The reaction mixture was then cooled to room temperature, and toluene was removed under reduced pressure using an evaporator. Finally, the mixture was dried in a vacuum dryer at 40°C to obtain cyclic oligosaccharide-modified organopolysiloxane K (light brown solid, 159.7 g).

[0068] [ka]

[0069] [Comparative Example 2] A four-necked flask equipped with a stirrer, thermometer, reflux condenser, and dropping funnel contains 6.9 g of polyorganohydrogensiloxane represented by the following formula (3) (kinematic viscosity: 17 mm³). 2 A 45.0g solution of the aforementioned vinyl-modified compound D (number average molecular weight: 3,000, hydrosilyl group amount: 0.052 mol), a vinyl group amount: 0.016 mol, and 100.0g of toluene were charged. After purging the flask with nitrogen, the temperature was raised to 90°C, and 0.6g of a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum concentration 0.5 wt%) was added to the flask and stirred at 90°C for 2 hours. 1 The progress of the reaction was confirmed by the disappearance of the vinyl group peak (5.6-6.1 ppm) by 1H-NMR. Subsequently, 8.2 g (0.073 mol) of 1-octene and 0.3 g of a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum concentration 0.5 wt%) were added to the flask and stirred at 90°C for 4 hours. The reaction mixture was then cooled to room temperature, and toluene was removed under reduced pressure using an evaporator. 100 g of methanol was added to the resulting solid, and the washing of the solid at 50°C was repeated three times. Finally, the mixture was dried in a vacuum dryer at 40°C to obtain cyclic oligosaccharide-modified organopolysiloxane L (light brown solid, 44.6 g).

[0070] [ka]

[0071] [Comparative Example 3] A four-necked flask equipped with a stirrer, thermometer, reflux condenser, and dropping funnel was charged with 128.3 g of polyorganohydrogensiloxane represented by formula (2) below (hydrosilyl group amount: 0.052 mol), 45.0 g of the aforementioned vinyl-modified compound D (vinyl group amount: 0.016 mol), and 256.0 g of toluene. After purging the flask with nitrogen, the temperature was raised to 90°C, and 1.7 g of a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum concentration 0.5 wt%) was added to the flask and stirred at 90°C for 2 hours. 1 The reaction was confirmed to have progressed by the disappearance of the vinyl group peak (5.6-6.1 ppm) on 1H-NMR. Subsequently, 8.2 g (0.073 mol) of 1-octene and 0.9 g of a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum concentration 0.5 wt%) were added to the flask and stirred at 90°C for 4 hours. The reaction mixture was then cooled to room temperature, and toluene was removed under reduced pressure using an evaporator. When 300 g of acetone (dielectric constant 20.7) was added to the resulting solid and heated to 50°C, the product also dissolved, preventing further steps, and the evaluation was interrupted. The compounds obtained in the above examples and comparative examples were used to prepare coatings using the following methods, and various evaluations were performed.

[0072] [Coating preparation] Various cyclic oligosaccharide-modified organopolysiloxanes obtained in the above synthesis examples, examples, and comparative examples were dissolved in toluene to prepare a 30% solution. The above solution was poured onto a Teflon® coated plate cut to a shape of 5 cm long / 5 cm wide / 0.25 mm thick, left overnight at 25°C, and then dried in an 80°C oven for 1 hour to form a film. The appearance of the obtained film was observed visually, and the presence or absence of stickiness was checked by touch. Dynamic viscoelasticity measurements were also performed to determine the glass transition temperature.

[0073] [Table 1] The results in Table 1 show that the cyclic oligosaccharide-modified organopolysiloxane obtained by the production method of the present invention can form a transparent, non-sticky, flexible, and tough film. On the other hand, Comparative Example 1, in which step 2 was omitted, was cloudy and sticky. Comparative Example 2 had a low molecular weight and lacked flexibility and toughness.

[0074] This specification includes the following embodiments: [1]:[Step 1] A step to obtain an oligosaccharide-modified organopolysiloxane by hydrosilylation of a composition containing (A) to (D) below. (A) Kinematic viscosity at 25°C is 50 mm 2 Organohydrogenpolysiloxane having a molecular weight of 8,000 or more and containing one or more hydrosilyl groups per molecule. (B) Cyclic oligosaccharide derivatives having an unsaturated group represented by the following general formula (1) (C) Hydrosilylation catalyst (D) Organic solvents [Step 2] The cyclic oligosaccharide-modified organopolysiloxane obtained in Step 1 is washed with a washing organic solvent with a relative permittivity of 23 or higher at 25°C, or a mixture thereof, and then filtered. [Step 3] Step to remove the organic solvent used in Steps 1 and 2. A method for producing a cyclic oligosaccharide-modified organopolysiloxane, characterized by containing the following: [ka] (In the formula, A is an alkenyl group having 2 to 12 carbon atoms, R 1 R is independently selected from alkyl groups having 1 to 4 carbon atoms, aryl groups having 6 to 10 carbon atoms, and aralkyl groups having 7 to 10 carbon atoms. 2 R is an alkylene group having 1 to 4 carbon atoms. 3(The group is independently selected from an alkyl group having 1 to 4 carbon atoms, or an acyl group having 1 to 4 carbon atoms, where a is an integer from 0 to 8, b is an integer from 5 to 7, and x is 0 or 1.) [2] A method for producing a cyclic oligosaccharide-modified organopolysiloxane according to [1], characterized in that, in step 1, after the hydrosilylation reaction of (A) and (B), an α-olefin having 2 to 16 carbon atoms is further added by hydrosilylation. [3]: In the above general formula (1), R 1 is a methyl group, R 3 A method for producing a cyclic oligosaccharide-modified organopolysiloxane according to [1] or [2], wherein the group is an acetyl group. [4]: A method for producing a cyclic oligosaccharide-modified organopolysiloxane according to any of [1] to [3], wherein x is 1 in the general formula (1). [5]: A method for producing a cyclic oligosaccharide-modified organopolysiloxane according to any one of [1] to [4], wherein the glass transition temperature of the cyclic oligosaccharide-modified organopolysiloxane, as measured by dynamic viscoelasticity measurement, is 50 to 100°C. [6]: A method for producing a cyclic oligosaccharide-modified organopolysiloxane according to any one of [1] to [5], wherein the washing organic solvent used in step 2 is one or more selected from methanol, ethanol, and acetonitrile.

[0075] It should be noted that the present invention is not limited to the embodiments described above. The embodiments described above are illustrative, and any configuration that is substantially identical to the technical idea described in the claims of the present invention and achieves similar effects is included within the technical scope of the present invention.

Claims

1. [Step 1] A step to obtain an oligosaccharide-modified organopolysiloxane by hydrosilylation of a composition containing (A) to (D) below. (A) Kinematic viscosity at 25°C is 50 mm ２ Organohydrogenpolysiloxane having a molecular weight of 8,000 or more and containing one or more hydrosilyl groups per molecule. (B) Cyclic oligosaccharide derivatives having an unsaturated group represented by the following general formula (1) (C) Hydrosilylation catalyst (D) Organic solvents [Step 2] The cyclic oligosaccharide-modified organopolysiloxane obtained in Step 1 is washed with a washing organic solvent with a relative permittivity of 23 or higher at 25°C, or a mixture thereof, and then filtered. [Step 3] Step to remove the organic solvent used in Steps 1 and 2. A method for producing a cyclic oligosaccharide-modified organopolysiloxane, characterized by containing the following: 【Chemistry 1】 (In the formula, A is an alkenyl group having 2 to 12 carbon atoms, R １ R is a methyl group, ２ R is an alkylene group having 1 to 4 carbon atoms. ３ (where a is an acetyl group, a is an integer from 0 to 8, b is an integer from 5 to 7, and x is 0 or 1.)

2. A method for producing a cyclic oligosaccharide-modified organopolysiloxane according to claim 1, characterized in that, in step 1, after the hydrosilylation reaction of (A) and (B), an α-olefin having 2 to 16 carbon atoms is further added by hydrosilylation.

3. A method for producing a cyclic oligosaccharide-modified organopolysiloxane according to claim 1, wherein x is 1 in the general formula (1).

4. A method for producing a cyclic oligosaccharide-modified organopolysiloxane according to claim 1, wherein the glass transition temperature of the cyclic oligosaccharide-modified organopolysiloxane, as measured by dynamic viscoelasticity measurement, is 50 to 100°C.

5. A method for producing a cyclic oligosaccharide-modified organopolysiloxane according to claim 1, wherein the washing organic solvent used in step 2 is one or more selected from methanol, ethanol, and acetonitrile.

Images