Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/38—Polysiloxanes modified by chemical after-treatment

Definitions

• the present invention relates to an aldehyde-modified silicone and a method for producing the same.
• Aldehyde-modified silicone has the ability to react and bond with compounds having various polar functional groups such as hydroxy groups and amino groups. Therefore, it is attracting attention as a resin modifier and a feel improver for cosmetics.
• the synthetic routes for aldehyde-modified silicones are limited, and there are almost no examples of aldehyde-modified silicones being produced through large-scale industrial methods.
• Patent Documents 1 and 2 As a simple method for producing aldehyde-modified silicones, hydrosilylation of an aldehyde containing an unsaturated carbon-carbon bond with a hydrosilyl group-functional siloxane has been disclosed (Patent Documents 1 and 2). Although this method is desirable due to the high versatility of the hydrosilylation reaction, a competitive reaction of adding a hydrosilyl group to the carbonyl group of the aldehyde proceeds. This causes a decrease in the yield and purity of the desired aldehyde-modified silicone.
• an object of the present invention is to provide a highly pure aldehyde-modified silicone and a method for producing the aldehyde-modified silicone in which the competitive reaction of adding a hydrosilyl group to the carbonyl group of the aldehyde does not proceed.
• the present inventors have discovered that by using an oxidation reaction of a primary alcohol without using hydrosilylation, the competitive reaction of addition of a hydrosilyl group to a carbonyl group of an aldehyde group can be achieved.
• the present invention was completed by discovering a method for producing aldehyde-modified silicone without advancing the process.
• the present invention provides the following aldehyde-modified silicone and its manufacturing method.
• An aldehyde-modified silicone having one or two aldehyde groups in one molecule which has the following formula (1)
• A is a linear or branched alkylene group (-R-) having 2 to 20 carbon atoms, or an alkyleneoxyalkylene group (-R-O-R-), which has an aldehyde group at the end.
• R 1 is a group independently selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms.
• a is 0 ⁇ a ⁇ 3
• b is 0 ⁇ b ⁇ 200
• c is 0 ⁇ c ⁇ 1
• d is 0 ⁇ d ⁇ 1.
• the aldehyde-modified silicone (1) has the following formula (2):
• A is a linear or branched alkylene group (-R-) having 2 to 20 carbon atoms, or an alkyleneoxyalkylene group (-R-O-R-), which has an aldehyde group at the end.
• R 1 is a group independently selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms.
• [3] The above A is represented by the following formulas (3) to (6); (In the above formula, m is independently a number from 2 to 20, n1 is independently a number from 3 to 8, and n2 is independently a number from 1 to 6.)
• the following formula (1) In the formula, A is a linear or branched alkylene group (-R-) having 2 to 20 carbon atoms, or an alkyleneoxyalkylene group (-R-O-R-), which has an aldehyde group at the end.
• R 1 is a group independently selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms.
• a is 0 ⁇ a ⁇ 3
• b is 0 ⁇ b ⁇ 200
• c is 0 ⁇ c ⁇ 1
• d is 0 ⁇ d ⁇ 1.
• a method for producing an aldehyde-modified silicone represented by the following formula (7) (In the formula, A' is a linear or branched alkylene group (-R-) having 2 to 20 carbon atoms, or an alkyleneoxyalkylene group (-R-O-R-), with a hydroxyl group at the end. It is an organic group having one or two methyl groups.
• R 1 is a group independently selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms.
• a method for producing an aldehyde-modified silicone comprising producing an aldehyde-modified silicone by oxidizing the hydroxymethyl group of a carbinol-modified silicone.
• the aldehyde-modified silicone (1) has the following formula (2): (In the formula, A is a linear or branched alkylene group (-R-) having 2 to 20 carbon atoms, or an alkyleneoxyalkylene group (-R-O-R-), which has an aldehyde group at the end.
• R 1 is a group independently selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms. .e is a number from 1 to 150.
• the above A is represented by the following formulas (3) to (6); (In the above formula, m is independently a number from 2 to 20, n1 is independently a number from 3 to 8, and n2 is independently a number from 1 to 6.)
• the method for producing an aldehyde-modified silicone according to [4] or [5], which is a group selected from [7] The method for producing aldehyde-modified silicone according to any one of [4] to [6], characterized in that a nitroxyl radical compound is used as the oxidizing agent.
• the aldehyde-modified silicone of the present invention is produced using an oxidation reaction of a primary alcohol without using hydrosilylation, a competitive reaction of adding a hydrosilyl group to a carbonyl group of an aldehyde does not occur. Therefore, it is possible to produce high purity aldehyde-modified silicone in high yield, and it can be used as a material for resin modifiers and feel improvers for cosmetics.
• aldehyde-modified silicone The aldehyde-modified silicone of the present invention is represented by the following formula (1), and preferably is represented by the following formula (2).
• R 1 is a group independently selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms.
• alkyl group having 1 to 10 carbon atoms include alkyl groups such as methyl, ethyl, propyl and butyl; cycloalkyl groups such as cyclopentyl and cyclohexyl.
• the aryl group having 6 to 10 carbon atoms include phenyl group, tolyl group, xylyl group, and naphthyl group.
• Examples of the aralkyl group having 7 to 10 carbon atoms include benzyl group and phenethyl group. Among these, a methyl group, a butyl group, a phenyl group, or a benzyl group is preferable, and a methyl group or a butyl group is more preferable.
• a is 0 ⁇ a ⁇ 3, preferably 0 ⁇ a ⁇ 1, and b is 0 ⁇ b ⁇ 200, preferably 1 ⁇ b ⁇ 100, more preferably 5 ⁇ b ⁇ 60.
• c is 0 ⁇ c ⁇ 1, preferably 0, and d is 0 ⁇ d ⁇ 1, preferably 0.
• e is a number from 1 to 150, preferably from 1 to 100, and more preferably from 5 to 60.
• A is a linear or branched alkylene group (-R-) having 2 to 20 carbon atoms, or a linear or branched alkylene group having 2 to 20 carbon atoms.
• alkylene group having 2 to 20 carbon atoms include ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, and the like.
• n1 is independently a number of 3 to 8, preferably 3 to 4.
• the number n2 is independently a number from 1 to 6, preferably from 1 to 3. Note that the number of carbon atoms in A does not include the number of carbon atoms of the aldehyde group and the number of carbon atoms to which the aldehyde group is bonded.
• the method for producing an aldehyde-modified silicone of the present invention includes a step of oxidizing the hydroxyl group of the carbinol-modified silicone represented by the following formula (7). It is characterized by The production method of the present invention can produce the aldehyde-modified silicone of the present invention represented by the above formula (1) or formula (2).
• R 1 is independently a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms.
• alkyl group having 1 to 10 carbon atoms include alkyl groups such as methyl, ethyl, propyl and butyl; cycloalkyl groups such as cyclopentyl and cyclohexyl.
• the aryl group having 6 to 10 carbon atoms include phenyl group, tolyl group, xylyl group, and naphthyl group.
• Examples of the aralkyl group having 7 to 10 carbon atoms include benzyl group and phenethyl group. Among these, a methyl group, a butyl group, a phenyl group, or a benzyl group is preferable, and a methyl group or a butyl group is more preferable.
• a is 0 ⁇ a ⁇ 3, preferably 0 ⁇ a ⁇ 1, and b is 0 ⁇ b ⁇ 200, preferably 1 ⁇ b ⁇ 100, more preferably 5 ⁇ b ⁇ 60.
• c is 0 ⁇ c ⁇ 1, preferably 0, and d is 0 ⁇ d ⁇ 1, preferably 0.
• A' is a linear or branched alkylene group (-R-) having 2 to 20 carbon atoms, or an alkyleneoxyalkylene group (-R-OR-R-), It is an organic group having one or two hydroxymethyl groups at the end.
• alkylene group having 2 to 20 carbon atoms include ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, and the like. Note that the number of carbon atoms in A' does not include the number of carbon atoms of the hydroxymethyl group and the number of carbon atoms to which the hydroxymethyl group is bonded.
• a nitroxyl radical compound as the oxidizing agent.
• 2,2,6,6-tetramethylpiperidine N-oxyl, 1-methyl-2-azaadamantane N-oxyl, 2-azaadamantane N-oxyl, 9-azabicyclo[3.3.1]nonane N- Oxyl, 9-norazaadamantane N-oxyl, etc. are preferred.
• the amount of the oxidizing agent used is not particularly limited and is appropriately selected depending on the purpose.
• the amount is preferably 10 -6 mol to 1 mol, more preferably 1 x 10 -5 mol to 0.05 mol, and most preferably 1 x 10 -3 mol to 0.05 mol.
• Reoxidizing agents used include peroxyacids, hydrogen peroxide, hypohalous acids or salts thereof, perhalogen acids or salts thereof, persulfates, halides, halogenating agents such as N-bromosuccinimide, Trihalogenated isocyanuric acids such as trichloroisocyanuric acid and tribromoisocyanuric acid, diacetoxyiodoarenes such as (diacetoxyiodo)benzene, dialkyl azodicarboxylates such as diethyl azodicarboxylate, oxygen, air, or Mixtures may be mentioned. Further, when the oxidizing agent and the reoxidizing agent are used together, the ratio of the amounts used of each is preferably 10 to 200 mol, more preferably 20 to 150 mol, of the reoxidizing agent, or Mixtures may be mentioned. Further, when the oxidizing agent and the reoxidizing agent are used together, the ratio of the amounts used of each is preferably 10 to 200 mol,
• the reaction time is not particularly limited, but is preferably 1 to 24 hours, more preferably 2 to 12 hours, and most preferably 2 to 4 hours.
• the oxidation reaction in the production method of the present invention may be carried out either in the presence of a solvent or in the absence of a solvent, but when the oxidizing agent or reoxidizing agent is solid, it is preferably carried out using a solvent.
• a solvent the type of solvent is not particularly limited as long as it does not inhibit the reaction.
• solvents include aliphatic hydrocarbons such as hexane, heptane, and petroleum ether, aromatic hydrocarbons such as benzene, toluene, and xylene, nitriles such as acetonitrile, propionitrile, and benzonitrile, dichloromethane, and chloroform.
• 1,2-dichloroethane halogenated hydrocarbons such as carbon tetrachloride
• ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane, diethylene glycol dimethyl ether, formamide, dimethylformamide, dimethylacetamide, hexamethyl phosphoric acid
• Amides such as triamide, sulfoxides such as dimethyl sulfoxide, esters such as ethyl formate, ethyl acetate, propyl acetate, butyl acetate, diethyl carbonate, carboxylic acids such as acetic acid, formic acid, propionic acid, sulfolane, water, etc.
• aliphatic hydrocarbons, aromatic hydrocarbons, nitriles, halogenated hydrocarbons, esters, carboxylic acids, water, or mixtures thereof are preferred, including dichloromethane, acetonitrile, acetic acid, toluene, ethyl acetate, and acetic acid. Isopropyl, water, or a mixture thereof is more preferred, and dichloromethane, dichloromethane-water mixture, toluene-water mixture, ethyl acetate-water mixture, acetonitrile, or acetic acid is most preferred.
• the quenching step for deactivating the oxidizing agent and reoxidizing agent used in the oxidation reaction.
• the deactivating agent used in the quenching step is appropriately selected depending on the type of oxidizing agent, and an example is a method in which an aqueous sodium bicarbonate solution and an aqueous sodium thiosulfate solution are used together as the deactivating agent.
• the quenching step may be substituted by removing the oxidizing agent by column treatment filled with silica gel or the like.
• the number average molecular weight is a value determined by GPC (gel permeation chromatography) analysis using polystyrene as a standard material under the following conditions.
• GPC gel permeation chromatography
• the kinematic viscosity is a value measured at 25°C using a Cannon-Fenske viscometer described in JIS Z 8803:2011.
• the refractive index (nD) is a value measured at 25° C. using an Abbe refractometer described in JIS K 0062:1992.
• Example 1 In a 500 mL separable flask equipped with a thermometer, a stirring device, a reflux condenser, and a nitrogen gas inlet tube, 19.65 g (1.5 equivalents) of iodobenzene diacetate, 108.00 g of dichloromethane, and the following formula (8) were added. After charging 100.00 g (0.04 mol) of the carbinol-modified (containing primary alcohol group) silicone shown, 2,2,6,6-tetramethylpiperidine N-oxyl was added at 25°C under a nitrogen atmosphere with stirring. 0.32g (0.05 equivalent) was added, and the reaction was carried out at 23°C for 4 hours.
• Example 2 The above procedure was carried out except that the carbinol-modified (containing primary alcohol group) silicone (8) used in Example 1 was changed to carbinol-modified (containing primary alcohol group) silicone (10) (0.04 mol). The same operation as in Example 1 was carried out to obtain a colorless transparent liquid.
• This product was confirmed by 1 H-NMR to be an aldehyde-modified silicone represented by the following formula (11), yield: 90%, purity: 100%, kinematic viscosity: 54.3 mm 2 /s, refraction. ratio: 1.4083, number average molecular weight: 4,300.
• 1 H-NMR data of the compound represented by formula (11) is shown below. 0.00ppm (192H), 0.52ppm (4H), 0.89ppm (3H), 1.31ppm (12H), 1.62ppm (2H), 3.43ppm (2H), 4.06ppm (2H), 9 .76ppm (1H)
• Example 3 The above procedure was carried out except that the carbinol-modified (containing primary alcohol group) silicone (8) used in Example 1 was changed to carbinol-modified (containing primary alcohol group) silicone (12) (0.04 mol). The same operation as in Example 1 was carried out to obtain a colorless transparent liquid.
• This product was confirmed by 1 H-NMR to be an aldehyde-modified silicone represented by the following formula (13), yield: 88%, purity: 100%, kinematic viscosity: 87.2 mm 2 /s, refraction. ratio: 1.4077, number average molecular weight: 7,400.
• 1 H-NMR data of the compound represented by formula (13) is shown below. 0.00ppm (372H), 0.52ppm (4H), 0.89ppm (3H), 1.31ppm (4H), 1.62ppm (2H), 3.40ppm (4H), 3.80ppm (1H), 9 .80ppm (2H)

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• General Chemical & Material Sciences (AREA)

Priority Applications (3)

Applications Claiming Priority (2)

Publications (1)

Family

ID=88420059

Family Applications (1)

Country Status (4)

Citations (10)

• 2023
  • 2023-04-13 JP JP2024516229A patent/JPWO2023204136A1/ja active Pending
  • 2023-04-13 CN CN202380034832.2A patent/CN119053641A/zh active Pending
  • 2023-04-13 EP EP23791784.4A patent/EP4512847A1/en active Pending
  • 2023-04-13 WO PCT/JP2023/015014 patent/WO2023204136A1/ja not_active Ceased

Patent Citations (10)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events