Organopolysiloxane

Abstract

To provide an organosiloxane that has reactivity as a raw material for polyamides, polyurethanes, polyethers, polyesters and polycarbonates, and is sufficiently compatible with various solvents and water.SOLUTION: An organopolysiloxane is represented by the general formula (1) in the figure.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to organopolysiloxanes. [Background technology]

[0002] Organopolysiloxanes are used in a variety of fields, including plastics, fibers, paints, cosmetics, and resin coatings, due to their excellent chemical stability, heat resistance, weather resistance, mold releasability, water repellency, and physiological inertness.

[0003] Many of the organopolysiloxanes known to date are oils. To use these oily organopolysiloxanes as raw materials for general purposes, they must be compatible with other reaction substrates and solvents. However, because organopolysiloxanes are highly hydrophobic, they have poor compatibility with hydrophilic chemicals, especially water. For example, organopolysiloxanes are incompatible with alcoholic solvents and water. As a result, the applications of organopolysiloxanes have been limited.

[0004] Conventionally, methods for improving the compatibility of organopolysiloxanes have been known. For example, organopolysiloxanes whose main chain terminals are modified with polyoxyalkylene (Patent Document 1) and whose side chains are modified with polyoxyalkylene (Patent Documents 2 and 3) are known. Also known is one in which a dialkyldiol structure is introduced at one terminal (Patent Document 4).

[0005] However, when the organosiloxanes disclosed in Patent Documents 1 to 3 were used as raw materials for polyamide, polyurethane, polyether, polyester, and polycarbonate, they failed to react.Furthermore, when the organopolysiloxanes disclosed in Patent Documents 1 and 4 were mixed with various solvents, they were not compatible with the solvents.

[0006] Specifically, the polyoxyalkylene-modified diorganopolysiloxane compound A shown in Example 1 of Patent Document 1 is an organosiloxane modified with a terminally branched polyoxyalkylene. This organopolysiloxane has a small contribution of the terminal oxyalkylene moieties to the siloxane main chain, and does not exhibit sufficient solubility in polar solvents, particularly water.

[0007] Polyether-modified organopolysiloxane A shown in Example 1 of Patent Document 2 is an organopolysiloxane in which a portion of the siloxane side chain is modified with polyethylene glycol. This organopolysiloxane exhibits compatibility with alcoholic solvents to the extent that phase separation does not occur, but does not have reactive substituents that would allow it to react as a raw material for polyamide, polyurethane, polyether, polyester, or polycarbonate.

[0008] The polyether-modified silicone copolymer shown in Example 1 of Patent Document 3 is a polydimethylsiloxane in which some of the side chains have been modified with polyoxyalkylene. This organopolysiloxane has a low proportion of polyoxyalkylene in the entire molecule and does not have sufficient polarity to be fully compatible with alcohol-based solvents. Furthermore, it does not have reactive substituents that would allow it to react as a raw material for polyamide, polyurethane, polyether, polyester, or polycarbonate.

[0009] The organopolysiloxane shown in Example 1 of Patent Document 4 has a dialkyldiol structure branched at one end. This organopolysiloxane has reactive sites that allow it to be used as a raw material for polyurethane, polyether, and polyester, but it has poor compatibility with solvents and other raw materials, so the polymerization reaction does not proceed or proceeds extremely slowly. [Prior art documents] [Patent documents]

[0010] [Patent Document 1] Japanese Patent Application Laid-Open No. 2016-128538 [Patent Document 2] Japanese Patent Application Laid-Open No. 2012-224599 [Patent Document 3] Japanese Patent Application Laid-Open No. 2001-294753 [Patent Document 4] Japanese Patent Application Publication No. 2023-12918 Summary of the Invention [Problem to be solved by the invention]

[0011] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an organosiloxane that has the reactivity required for use as a raw material for polyamides, polyurethanes, polyethers, polyesters, and polycarbonates, and that is sufficiently compatible with various solvents and water. [Means for solving the problem]

[0012] The above-mentioned problems of the present invention have been solved by the means described below.

[0013] [1] An organopolysiloxane represented by the following general formula (1):

[0014] [ka]

[0015] (In the formula, R 1 ~R 5 are each independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, R 6 is a divalent group containing an oxyalkylene group, R 7 is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, X and Y each independently represent a monovalent hydrocarbon group having an organic group capable of forming an amide bond, a urethane bond, an ether bond, an ester bond, or a carbonate bond, and which may have a heteroatom; n is an integer between 1 and 50.)

[0016] [2] R6 The organopolysiloxane according to [1], which has a structure represented by the following formula (2):

[0017] [ka]

[0018] (In the formula, R 8 is an optionally branched divalent alkylene group having two or more carbon atoms, R 9 , R 10 and R 11 each independently represents an optionally branched divalent alkylene group having one or more carbon atoms, p and q are each independently an integer of 0 to 100.

[0019] [3] The organosiloxane according to [1] or [2], wherein X and Y in the formula (1) each independently have a structure represented by the following formula (3):

[0020] [ka]

[0021] (In the formula, R 12 and R 13 are each independently a divalent alkylene group, R 14 is a group selected from an amide group, a carboxy group, a carboxylic acid halide group, a carboxylic acid alkyl ester group, a carboxylic acid anhydride group, an isocyanate group, an alkanol group, a hydroxyphenyl group, a hydroxy group, an epoxy group, and a glycidyl group, E is a hetero element, r is an integer greater than or equal to 0.)

[0022] [4] The organopolysiloxane according to any one of [1] to [3], wherein X and Y in the formula (1) are the same group.

[0023] [5] R in the formula (3) 14The organopolysiloxane according to [3] or [4], wherein is a hydroxy group.

[0024] [6] R in the formula (3) 14 [3] The organopolysiloxane according to [4], wherein is an amide group.

[0025] [7] R in the formula (3) 14 The organopolysiloxane according to [3] or [4], wherein is a carboxy group.

[0026] [8] R in the formula (3) 14 [3] or [4], wherein is an epoxy group. [Effects of the Invention]

[0027] The present invention provides organosiloxanes that are reactive enough to be used as raw materials for polyamides, polyurethanes, polyethers, polyesters, and polycarbonates, and that are sufficiently compatible with various solvents and water. DETAILED DESCRIPTION OF THE INVENTION

[0028] The present invention will be described in detail below. However, the explanation of the constituent elements described below is a representative example of an embodiment of the present invention, and the present invention is not limited to these contents as long as it does not exceed the gist of the present invention.

[0029] The organopolysiloxane of the present invention is an organopolysiloxane represented by the following formula (1).

[0030] [ka] (In the formula, R 1 ~R 5 are each independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, R 6 is a divalent group containing an oxyalkylene group, R 7is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, X and Y each independently represent a monovalent hydrocarbon group having an organic group capable of forming an amide bond, a urethane bond, an ether bond, an ester bond, or a carbonate bond, and which may have a heteroatom; n is an integer between 1 and 50.)

[0031] (mechanism) The organopolysiloxane of the present invention has, at both ends, monovalent hydrocarbon groups X and Y, which may contain a heteroatom and have functional groups capable of forming an amide bond, a urethane bond, an ether bond, an ester bond, or a carbonate bond, and the side chains are modified with polyoxyalkylene, which gives the organopolysiloxane excellent reactivity as a raw material for polyamides, polyurethanes, polyethers, polyesters, and polycarbonates, and also has sufficient compatibility with various solvents and water.

[0032] (R 1 ~R 5 About R in formula (1) 1 , R 2 , R 3 , R 4 , R 5 are each independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms. The monovalent hydrocarbon group includes an alkyl group and an aryl group.

[0033] R 1 , R 2 , R 3 , R 4 , R 5 is preferably not substituted with a reactive substituent as described below.

[0034] R 1 , R 2 , R 3 , R 4 , R 5Examples of the alkyl group include linear or branched alkyl groups such as methyl, ethyl, propyl, n-butyl, i-butyl, s-butyl, t-butyl, pentyl, hexyl, ethylhexyl, octyl, decyl, and dodecyl. Examples of the cycloalkyl group include cyclopentyl and cyclohexyl. The aryl group includes phenyl, toluyl, xylyl, and the like. Of these, methyl, ethyl, n-butyl, t-butyl, hexyl, cyclohexyl, and phenyl are preferred, and methyl, ethyl, n-butyl, t-butyl, hexyl, and phenyl are more preferred. R 1 , R 2 , R 3 , R 4 , R 5 Among them, R 1 , R 2 , R 4 , R 5 is most preferably methyl, ethyl, hexyl, or phenyl, and R 3 is most preferably methyl or phenyl.

[0035] In addition, R 1 , R 2 , R 3 , R 4 , R 5 Introducing a bulky chemical species into the substituent of R is undesirable because it causes too much steric hindrance during synthesis, slowing down the reaction rate and lengthening the time required for production. 1 , R 2 , R 3 , R 4 , R 5 If a highly hydrophobic structure is introduced into the organosiloxane, the polarity of the organosiloxane as a whole decreases, resulting in a loss of compatibility with various solvents and water. Because the reagents used in synthesis are simplified, R 1 and R 4 , R 2 and R 5 Furthermore, it is preferable that R 1 , R 2 , R 4 , R5 are preferably all the same.

[0036] (R 6 About R in formula (1) 6 is a divalent group containing oxyalkylene, such as a group derived from polyethylene glycol, tetramethylene glycol, polypropylene glycol, etc. Specifically, it has a structure represented by the following formula (2).

[0037] [ka]

[0038] (In the formula, R 8 is an optionally branched divalent alkylene group having two or more carbon atoms, R 9 , R 10 and R 11 each independently represents an optionally branched divalent alkylene group having one or more carbon atoms, p and q are each independently an integer of 0 to 100.

[0039] R in equation (2) 8 is a divalent alkylene group having two or more carbon atoms which may be branched, and examples thereof include ethylene, propylene, n-butylene, methylethylene, hexylene, dodecylene, etc. Among these, propylene and n-butylene are preferred, and propylene is particularly preferred. R 9 , R 10 , R 11 are each independently a divalent alkylene group having one or more carbon atoms which may be branched, such as methylene, ethylene, propylene, n-butylene, and decylene. p and q are each independently an integer of 0 or more and 100 or less. One of p and q may be 0, or both may be 0. Both p and q may be 1 or more. The sum of p and q is preferably 1 or more and 70 or less, more preferably 2 or more and 50 or less, and most preferably 2 or more and 30 or less. If the sum of p and q is too small, it becomes difficult to ensure sufficient compatibility with various solvents and water, which is undesirable. If the sum of p and q is too large, the weight ratio of oxyalkylene to the entire molecule becomes too large, which is undesirable because the properties of organosiloxane are lost.

[0040] (R 7 About R in formula (1) 7 is a monovalent hydrocarbon group having 1 to 20 carbon atoms. Examples of the hydrocarbon group include linear, branched, or cyclic alkyl groups such as methyl, ethyl, propyl, n-butyl, s-butyl, t-butyl, hexyl, octyl, decyl, dodecyl, and ethylhexylcyclohexyl. Preferred are methyl, ethyl, propyl, n-butyl, s-butyl, t-butyl, hexyl, octyl, and decyl, particularly preferred are methyl, ethyl, propyl, n-butyl, s-butyl, and t-butyl, and most preferred are methyl and ethyl.

[0041] R 7 When is a hydrogen atom, the oxyalkylene ends in an alkanol. If the end is an alkanol, it becomes a reaction point for polyurethane, polyester, polyether, etc., which undesirably causes high viscosity and hardening.

[0042] (About X and Y) In formula (1), X and Y each independently represent a monovalent hydrocarbon group having a functional group capable of forming an amide bond, a urethane bond, an ether bond, an ester bond, or a carbonate bond, and which may contain a heteroatom.

[0043] Examples of X and Y include those having a structure represented by the following formula (3).

[0044] [ka]

[0045] (In the formula, R 12 and R 13 are each independently a divalent alkylene group, R 14 is a group selected from an amide group, a carboxy group, a carboxylic acid halide group, a carboxylic acid alkyl ester group, a carboxylic acid anhydride group, an isocyanate group, an alkanol group, a hydroxyphenyl group, a hydroxy group, an epoxy group, and a glycidyl group, E is a hetero element, r is an integer greater than or equal to 0.)

[0046] R in equation (3) 12 , R 13 is a divalent alkylene group, such as ethylene, propylene, n-butylene, pentylene, hexylene, decenylene, and ethylhexylene. E is a hetero element, and examples thereof include O, S, amide N, imide N, B, and Si. E is preferably O, S, amide N, or imide N, more preferably O or S, and most preferably O.

[0047] R 14 is a group selected from an amide group, a carboxy group, a carboxylic acid halide group, a carboxylic acid alkyl ester group, a carboxylic acid anhydride group, an isocyanate group, an alkanol group, a hydroxyphenyl group, a hydroxy group, an epoxy group, and a glycidyl group, preferably an amide group, a carboxy group, a carboxylic acid halide group, a carboxylic acid alkyl ester group, a carboxylic acid anhydride group, an alkanol group, a hydroxyphenyl group, a hydroxy group, an epoxy group, or a glycidyl group, more preferably an amide group, a carboxy group, an alkanol group, a hydroxy group, an epoxy group, or a glycidyl group, and still more preferably an amide group, a carboxy group, a hydroxy group, or an epoxy group.

[0048] r is an integer of 0 to 100, preferably 0 to 50, more preferably 0 to 20, and most preferably 0 to 15. If r is too large, the molecular weight of the organopolysiloxane itself becomes too large, which is undesirable as it reduces fluidity.

[0049] Preferred structures of X and Y include the following: In the following, "*" indicates the bonding position with the Si atom in formula (1).

[0050] [ka]

[0051] X and Y may be the same or different, but are preferably the same in order to simplify the reagents used in synthesis.

[0052] (About n) In formula (1), n ​​is an integer of 1 or more and 50 or less. A larger n is preferable from the viewpoint of reducing the proportion of unreacted by-products contained in the product and from the viewpoint of the obtained organopolysiloxane easily exhibiting the properties of organosiloxane. A smaller n is preferable from the viewpoint of preventing the viscosity from becoming too high and making it easy to handle. n is preferably an integer of 1 or more and 50 or less, more preferably an integer of 3 or more and 30 or less, even more preferably an integer of 5 or more and 30 or less, and most preferably an integer of 5 or more and 20 or less.

[0053] When the organopolysiloxane of the present invention is provided as a mixture of organopolysiloxanes in which n in formula (1), p and q in formula (2), and r in formula (3) are different, n, p, q, and r as organopolysiloxanes are expressed as average values ​​and therefore include decimal points and cannot necessarily be called "integers." However, in a single compound as organopolysiloxane, n in formula (1), p and q in formula (2), and a in formula (3) are expressed as integers.

[0054] (What is a polar group?) The polar group measured in the examples below is a substituent having a dipole moment in an atomic group. Examples of the polar group used in the present invention include a hydroxyl group, a carboxyl group, an amino group, a glycidyl group, an ether group, a nitro group, a nitroso group, a carbonyl group, an aldehyde group, an amide group, an imide group, a sulfo group, a sulfonyl group, a thiol group, a thioether group, a cyano group, a fluoro group, a chloro group, a bromo group, and an iodo group.

[0055] To ensure that the organosiloxane of the present invention has sufficient compatibility and solubility in various organic solvents and water, the "number of polar groups / number of Si atoms" of the organosiloxane of the present invention, as measured by the method described in the Examples section below, is preferably 0.5 or more, more preferably 0.8 or more, and most preferably 1.0 or more. However, because the number of sites in the organopolysiloxane that can be modified with polar groups is limited, the "number of polar groups / number of Si atoms" of the organosiloxane of the present invention is usually 2.4 or less.

[0056] (What is a reactive substituent?) The reactive substituents measured in the examples below refer to functional groups capable of forming amide bonds, urethane bonds, ester bonds, ether bonds, and carbonate bonds. Specific examples include amide groups, carboxy groups, carboxylic acid halide groups, carboxylic acid alkyl ester groups, carboxylic acid anhydride groups, isocyanate groups, alkanol groups, hydroxyphenyl groups, hydroxy groups, epoxy groups, and glycidyl groups.

[0057] (Regarding purity) The organopolysiloxane of the present invention preferably has a purity of 98% as calculated by NMR measurement using an internal standard. Lower purity is undesirable because the impurities are insoluble in organic solvents, making the organopolysiloxane appear to be insoluble.

[0058] (Regarding the manufacturing method of organopolysiloxane) The organopolysiloxane of the present invention is represented by the formula (1) R 1 ~R7 It can be produced by using starting materials capable of introducing X and Y by the method shown in the section of Examples described below.

[0059] (Regarding the catalyst) In Reference Examples 1 to 8, Reference Example 10, Reference Example 12, and Reference Example 14 described below, which are steps for obtaining the organopolysiloxane in the present invention, a catalyst known as a hydrosilylation catalyst can be used. For example, Karstedt catalyst (Pt(O)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex), Speier catalyst (hexachloroplatinic(IV) acid), Wilkinson catalyst (tris(triphenylphosphine)rhodium(I) chloride), Trost catalyst (pentamethylcyclopentadienyltris(acetonitrile)ruthenium(II) hexafluorophosphate), etc. can be mentioned.

[0060] (Regarding purification) The purification step used in the step of obtaining the organopolysiloxane in the present invention can be carried out by a known method. For example, liquid-liquid separation operation, distillation operation, thin-film distillation operation, preparative chromatography, etc., can be mentioned.

Examples

[0061] Hereinafter, the present invention will be described in more detail with reference to Examples. However, the present invention is not limited to the following Examples in any way as long as it does not exceed the gist thereof.

[0062] <Measurement of NMR> For nuclear magnetic resonance (NMR) measurement, as a deuterated chloroform solution of organopolysiloxane, using a "ADVANCE600 spectrometer" manufactured by Bruker, the resonance frequency was 600 MHz, the flip angle was 45°, the data acquisition time was 3 seconds, the pulse repetition time was 10 seconds, the number of integrations was 16, and the temperature was 25°C. 1 1H NMR was measured.

[0063] <Number of reactive functional groups> The reactive substituents contained and their number were calculated from the peak areas of the NMR spectrum. The reactive substituents referred to here are as described above, and examples include alkanol groups, amino groups, carboxyl groups, hydroxyl groups, epoxy groups, and glycidyl groups. In the case of alkanol groups, an NMR peak of H bonded to the same carbon atom as OH can be observed at 3.8 ppm, and the number of alkanol groups contained in one molecule can be estimated from the relative peak area of ​​this peak.

[0064] <Number of polar groups / Number of Si atoms> The number of polar groups introduced, calculated by NMR, was defined as a, and the number of Si atoms contained in the molecule, calculated by adding 2 for the terminal Si atoms to the degree of polymerization calculated by NMR, was defined as b. By dividing a by b, the formula (number of polar groups) / (number of Si atoms) = a / b was calculated. When polar groups are bonded consecutively, the atomic group is considered to be one polar group. Specifically, polyethylene glycol has multiple consecutive ether bonds, but the entire polyethylene glycol group is counted as one polar group. Hydroxy ether groups are also counted as one polar group for the same reason.

[0065] <Solubility test> A solubility test was performed on synthesized or purchased organopolysiloxanes using the following procedure. 3 g of organosiloxane and 7 g of an organic solvent (toluene or ethanol) or water were added to a 10 mL vial and shaken thoroughly. After shaking, the condition inside the vial was visually observed and rated on a four-point scale (S to C) as follows: S: Overall uniform and clear. A: There is a slight cloudiness, but overall it is highly transparent. B: The suspension remains suspended even after standing for 10 minutes. C: Suspended, and the silicone layer and solvent layer separate after standing for 10 minutes.

[0066] [Reference example 1] Dimethylethoxysilane (3.13 g, 30 mmol), ethylene glycol monoallyl ether (3.06 g, 30 mmol), and dehydrated toluene (50 mL) were placed in a 200 mL two-necked flask. Under a nitrogen atmosphere, Karstedt catalyst (2% Pt(O)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex in xylene solution) (0.05 g) was added and the mixture was stirred at room temperature for 18 hours. The solvent was removed by evaporation, and the mixture was purified by vacuum distillation to obtain intermediate compound 1 (4.46 g, 22 mmol, 72% yield). The obtained intermediate compound 1 was dissolved in CDCl3. 1 When H-NMR measurement was carried out, peaks at around 0.6 ppm and 1.6 ppm were confirmed that were derived from Si-CH2-CH2 formed by the progress of the addition reaction to the allyl group, confirming the production of the target product.

[0067] [Reference example 2] Intermediate compound 2 was obtained in the same manner as in Reference Example 1, except that allyl alcohol (1.74 g, 30 mmol) was used instead of ethylene glycol monoallyl ether. The obtained intermediate compound 2 was dissolved in CDCl3. 1 When H-NMR measurement was carried out, peaks at around 0.6 ppm and 1.6 ppm were confirmed that were derived from Si-CH2-CH2 formed by the progress of the addition reaction to the allyl group, confirming the production of the target product.

[0068] [Reference example 3] Intermediate compound 3 was obtained in the same manner as in Reference Example 1, except that allylamine (1.71 g, 30 mmol) was used instead of ethylene glycol monoallyl ether. The obtained intermediate compound 3 was dissolved in CDCl3. 1 When H-NMR measurement was carried out, peaks at around 0.6 ppm and 1.6 ppm were confirmed that were derived from Si-CH2-CH2 formed by the progress of the addition reaction to the allyl group, confirming the production of the target product.

[0069] [Reference example 4] Intermediate compound 4 was obtained in the same manner as in Reference Example 1, except that 4-pentenoic acid (3.00 g, 30 mmol) was used instead of ethylene glycol monoallyl ether. The obtained intermediate compound 4 was dissolved in CDCl3. 1 When H-NMR measurement was carried out, peaks at around 0.6 ppm and 1.6 ppm were confirmed that were derived from Si-CH2-CH2 formed by the progress of the addition reaction to the allyl group, confirming the production of the target product.

[0070] [Reference example 5] Intermediate compound 5 was obtained in the same manner as in Reference Example 1, except that 1,2-epoxy-5-hexane (2.94 g, 30 mmol) was used instead of ethylene glycol monoallyl ether. The obtained intermediate compound 5 was dissolved in CDCl3. 1 When H-NMR measurement was carried out, peaks at around 0.6 ppm and 1.6 ppm were confirmed that were derived from Si-CH2-CH2 formed by the progress of the addition reaction to the allyl group, confirming the production of the target product.

[0071] [Reference example 6] Intermediate compound 6 was obtained in the same manner as in Reference Example 1, except that diphenylethoxysilane (6.85 g, 30 mmol) (synthesized with reference to https: / / doi.org / 10.1016 / j.jorganchem.2004.07.048) was used instead of dimethylethoxysilane. The obtained intermediate compound 6 was dissolved in CDCl3. 1 When H-NMR measurement was carried out, peaks at around 0.6 ppm and 1.6 ppm were confirmed that were derived from Si-CH2-CH2 formed by the progress of the addition reaction to the allyl group, confirming the production of the target product.

[0072] [Reference example 7] Intermediate compound 7 was obtained in the same manner as in Reference Example 1, except that dihexylethoxysilane (7.34 g, 30 mmol) (synthesized with reference to https: / / doi.org / 10.1016 / j.jorganchem.2004.07.048) was used instead of dimethylethoxysilane. The obtained intermediate compound 7 was dissolved in CDCl3. 1 When H-NMR measurement was carried out, peaks at around 0.6 ppm and 1.6 ppm were confirmed that were derived from Si-CH2-CH2 formed by the progress of the addition reaction to the allyl group, confirming the production of the target product.

[0073] [Reference example 8] A 200 mL two-necked eggplant flask was charged with methyldiethoxysilane (8.06 g, 60 mmol), 2,5,8,11-tetraoxatetradec-13-ene (12.26 g, 60 mmol), and dehydrated toluene (100 mL). Under a nitrogen atmosphere, Karstedt catalyst (2% Pt(O)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex in ethylene) (0.10 g) was added and the mixture was stirred at room temperature for 4 hours. The solvent was removed by evaporation, and the mixture was purified by vacuum distillation to obtain intermediate compound 8 (16.45 g, 49 mmol, 81% yield). The obtained intermediate compound 8 was dissolved in CDCl3. 1 When H-NMR measurement was carried out, peaks at around 0.6 ppm and 1.6 ppm were confirmed that were derived from Si-CH2-CH2 formed by the progress of the addition reaction to the allyl group, confirming the production of the target product.

[0074] [Reference example 9] NaH (1.80 g, 75 mmol) and tetrahydrofuran (50 mL) were added to a 200 mL two-necked recovery flask and stirred at 0 °C under a nitrogen atmosphere. Polyethylene glycol monomethyl ether 400 (24.00 g, 60 mmol) dissolved in 20 mL of tetrahydrofuran was added dropwise over 30 minutes. After the dropwise addition, the mixture was stirred for 30 minutes, and then allyl bromide (8.71 g, 72 mmol) dissolved in 20 mL of tetrahydrofuran was added dropwise over 30 minutes. The mixture was warmed to room temperature and stirred for 2 hours. The reaction solution was filtered through filter paper to remove salts, and the solvent was removed by evaporation to obtain intermediate compound 9 (22.57 g, 51 mmol, 85% yield). The intermediate compound 9 obtained was dissolved in CDCl3. 1 H-NMR measurement confirmed that the peak derived from the allyl group shifted from 6.1 ppm (allyl bromide) to 5.9 ppm, confirming the production of the target product.

[0075] [Reference example 10] Intermediate compound 9 (9.85 g, 22 mmol) prepared in Reference Example 9 and dehydrated toluene (80 mL) were added to a 200 mL two-necked recovery flask and refluxed for 3 hours. After cooling to room temperature, phenyldiethoxysilane (4.48 g, 22 mmol) and Karstedt catalyst (2% Pt(O)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex in ethylene) (0.05 g) were added under a nitrogen atmosphere and stirred at room temperature for 4 hours. The solvent was removed by evaporation to obtain intermediate compound 10 (12.50 g, 20 mmol, 89% yield). The obtained intermediate compound 10 was dissolved in CDCl3. 1 When H-NMR measurement was carried out, peaks at around 0.9 ppm and 1.6 ppm were confirmed that were derived from Si-CH2-CH2 formed by the progress of the addition reaction to the allyl group, confirming the production of the target product.

[0076] [Reference example 11] Intermediate compound 11 was obtained in the same manner as in Reference Example 9, except that polytetramethylene ether glycol monomethyl ether 250 (15.00 g, 60 mmol) was used instead of polyethylene glycol monomethyl ether 400 (24.00 g, 60 mmol). The intermediate compound 11 obtained was dissolved in CDCl3. 1 H-NMR measurement confirmed that the peak derived from the allyl group shifted from 6.1 ppm (allyl bromide) to 5.9 ppm, confirming the production of the target product.

[0077] [Reference example 12] Intermediate compound 12 was obtained in the same manner as in Reference Example 8, except that intermediate compound 11 (15.00 g, 60 mmol) prepared in Reference Example 11 was used instead of 2,5,8,11-tetraoxatetradec-13-ene (12.26 g, 60 mmol). The intermediate compound 11 obtained was dissolved in CDCl3. 1 When H-NMR measurement was carried out, peaks at around 0.6 ppm and 1.6 ppm were confirmed that were derived from Si-CH2-CH2 formed by the progress of the addition reaction to the allyl group, confirming the production of the target product.

[0078] [Reference example 13] Intermediate compound 13 was obtained in the same manner as in Reference Example 9, except that polypropylene glycol monomethyl ether 400 (24.00 g, 60 mmol) was used instead of polyethylene glycol monomethyl ether 400 (24.00 g, 60 mmol). The intermediate compound 13 obtained was dissolved in CDCl3. 1 H-NMR measurement confirmed that the peak derived from the allyl group shifted from 6.1 ppm (allyl bromide) to 5.9 ppm, confirming the production of the target product.

[0079] [Reference example 14] Intermediate compound 14 was obtained in the same manner as in Reference Example 8, except that intermediate compound 13 (24.00 g, 60 mmol) prepared in Reference Example 13 was used instead of 2,5,8,11-tetraoxatetradec-13-ene (12.26 g, 60 mmol). The intermediate compound 14 obtained was dissolved in CDCl3. 1 When H-NMR measurement was carried out, peaks at around 0.6 ppm and 1.6 ppm were confirmed that were derived from Si-CH2-CH2 formed by the progress of the addition reaction to the allyl group, confirming the production of the target product.

[0080] [Example 1] Intermediate compound 1 (4.44 g, 22 mmol) obtained in Reference Example 1, intermediate compound 8 (18.20 g, 54 mmol) obtained in Reference Example 8, and tetrahydrofuran (50 mL) were added to an eggplant-shaped flask equipped with a magnetic stirrer, a distillation tube, and a receiver. The eggplant-shaped flask was placed on a stirrer, and the magnetic stirrer was rotated to stir, yielding a homogeneous solution. Water (4 mL) and formic acid (2 mL) were added to the resulting homogeneous solution to obtain a mixed solution. The resulting mixed solution was stirred at room temperature under a nitrogen atmosphere for 30 minutes. The eggplant-shaped flask containing the mixed solution was then immersed in an oil bath at 90°C and reacted under a nitrogen atmosphere for 2 hours, at which point it was confirmed that the distillation of a distillate containing tetrahydrofuran into the receiver had stopped. To further advance the dehydration reaction, the temperature of the oil bath was raised to 130°C, and the reaction was continued for 4 hours under a nitrogen atmosphere until the distillation stopped, yielding a reaction solution. The mixture was then stirred under a vacuum (8 × 10 -3 Volatiles were removed at 120°C under a pressure of 1000 torr. After returning to room temperature, toluene (20 mL) and an aqueous solution of sodium bicarbonate (20 mL) were added and the mixture was separated. The organic layer was further washed with saturated brine (20 mL), dehydrated over magnesium sulfate, and the solvent was removed to obtain a visually colorless, transparent oil.

[0081] The resulting oil was dissolved in CDCl3. 1 When H-NMR was measured, the peaks of the ethoxy groups derived from intermediate compound 1 and intermediate compound 8 disappeared, confirming that the target organopolysiloxane 1 (15.91 g) had been obtained. 1 The degree of polymerization was determined from the integral ratio of the peak of Me on Si around 0.1 ppm and the peak of OMe at the oxyalkylene terminal around 3.4 ppm in 1 H NMR to be 5, which agreed with the value calculated from the feed ratio. Since the degree of polymerization is 5, this organosiloxane 1 has 7 Si atoms. In addition, the repeating unit has five polar groups on its five Si atoms: triethylene glycol groups capped with methoxy groups at the ends, and two polar groups, hydroxy ether groups, at the ends of the main chain, for a total of 7 polar groups. The ratio (number of polar groups) / (number of silicon atoms) of this organosiloxane 1 is 1.0. The obtained organosiloxane 1 1 The integral ratio of the peaks assigned to H next to the terminal OH in H NMR indicates that this molecule contains two alkanol groups. In other words, the number of reactive groups in this organosiloxane 1 is two. When the above-mentioned solubility test was carried out on this organosiloxane 1, the liquid became entirely clear after adding toluene, ethanol, and water and shaking, and therefore the liquid was rated as S. Table 1 shows the number of reactive groups and (number of polar groups) / (number of silicon atoms) of the obtained organosiloxane 1, as well as the results of the solubility test.

[0082] [Example 2] Organopolysiloxane 2 was obtained in the same manner as in Example 1, except that intermediate compound 10 (28.78 g, 54 mmol) obtained in Reference Example 10 was used instead of intermediate compound 8 (18.20 g, 54 mmol) obtained in Reference Example 8. About this organopolysiloxane 2 1 The degree of polymerization was calculated to be 5 from 1 H NMR. When this organosiloxane 2 was subjected to the above-mentioned solubility test, the content liquid became entirely clear after adding toluene, ethanol, and water and shaking, and therefore was given an S rating. Table 1 shows the number of reactive groups and (number of polar groups) / (number of silicon atoms) of the obtained organosiloxane 2, as well as the results of the solubility test.

[0083] [Example 3] Organopolysiloxane 3 was obtained in the same manner as in Example 1, except that intermediate compound 2 (3.57 g, 22 mmol) obtained in Reference Example 2 was used instead of intermediate compound 1 (4.44 g, 22 mmol) obtained in Reference Example 1. About this organopolysiloxane 3 1 The degree of polymerization was calculated to be 5 from 1 H NMR. When this organosiloxane 3 was subjected to the above-mentioned solubility test, the liquid became entirely clear after adding toluene, ethanol, and water and shaking, and was therefore rated S. Table 1 shows the number of reactive groups and (number of polar groups) / (number of silicon atoms) of the obtained organosiloxane 3, as well as the results of the solubility test.

[0084] [Example 4] Organopolysiloxane 4 was obtained in the same manner as in Example 1, except that intermediate compound 3 (3.55 g, 22 mmol) obtained in Reference Example 3 was used instead of intermediate compound 1 (4.44 g, 22 mmol) obtained in Reference Example 1. About this organopolysiloxane 4 1 The degree of polymerization was calculated to be 5 from 1 H NMR. When organosiloxane 4 was subjected to the above-mentioned solubility test, the liquid contents became entirely clear after adding toluene, ethanol, and water and shaking, and was therefore rated S. Table 1 shows the number of reactive groups and (number of polar groups) / (number of silicon atoms) of the obtained organosiloxane 4, as well as the results of the solubility test.

[0085] [Example 5] Organopolysiloxane 5 was obtained in the same manner as in Example 1, except that intermediate compound 4 (4.50 g, 22 mmol) obtained in Reference Example 4 was used instead of intermediate compound 1 (4.44 g, 22 mmol) obtained in Reference Example 1. About this organopolysiloxane 5 1The degree of polymerization was calculated to be 5 from 1 H NMR. When this organosiloxane 5 was subjected to the above-mentioned solubility test, the liquid contents became entirely clear after adding toluene, ethanol, and water and shaking, and was therefore rated S. Table 1 shows the number of reactive groups and (number of polar groups) / (number of silicon atoms) of the obtained organosiloxane 5, as well as the results of the solubility test.

[0086] [Example 6] Organopolysiloxane 6 was obtained in the same manner as in Example 1, except that intermediate compound 5 (4.45 g, 22 mmol) obtained in Reference Example 5 was used instead of intermediate compound 1 (4.44 g, 22 mmol) obtained in Reference Example 1. About this organopolysiloxane 6 1 The degree of polymerization was calculated to be 5 from 1 H NMR. When this organosiloxane 6 was subjected to the above-mentioned solubility test, the content liquid became entirely clear after adding toluene, ethanol, and water and shaking, and therefore was given an S rating. Table 1 shows the number of reactive groups and (number of polar groups) / (number of silicon atoms) of the obtained organosiloxane 6, as well as the results of the solubility test.

[0087] [Example 7] Organopolysiloxane 7 was obtained in the same manner as in Example 1, except that intermediate compound 6 (7.27 g, 22 mmol) obtained in Reference Example 6 was used instead of intermediate compound 1 (4.44 g, 22 mmol) obtained in Reference Example 1. About this organopolysiloxane 7 1 The degree of polymerization was calculated to be 5 from 1 H NMR. When organosiloxane 7 was subjected to the above-mentioned solubility test, the liquid contents became entirely clear after adding toluene, ethanol, and water and shaking, and was therefore rated S. Table 1 shows the number of reactive groups and (number of polar groups) / (number of silicon atoms) of the obtained organosiloxane 7, as well as the results of the solubility test.

[0088] [Example 8] Organopolysiloxane 8 was obtained in the same manner as in Example 1, except that intermediate compound 7 (7.63 g, 22 mmol) obtained in Reference Example 7 was used instead of intermediate compound 1 (4.44 g, 22 mmol) obtained in Reference Example 1. About this organopolysiloxane 8 1 The degree of polymerization was calculated to be 5 from 1 H NMR. When this organosiloxane 8 was subjected to the above-mentioned solubility test, the liquid became entirely clear after adding toluene, ethanol, and water and shaking, and was therefore given an S rating. Table 1 shows the number of reactive groups and (number of polar groups) / (number of silicon atoms) of the obtained organosiloxane 8, as well as the results of the solubility test.

[0089] [Example 9] Organopolysiloxane 9 was obtained in the same manner as in Example 1, except that intermediate compound 12 (20.68 g, 54 mmol) obtained in Reference Example 12 was used instead of intermediate compound 8 (18.20 g, 54 mmol) obtained in Reference Example 8. About this organopolysiloxane 9 1 The degree of polymerization was calculated to be 5 from 1 H NMR. When organosiloxane 9 was subjected to the above-mentioned solubility test, the liquid became entirely clear after adding toluene, ethanol, and water and shaking, and was therefore given an S rating. Table 1 shows the number of reactive groups and (number of polar groups) / (number of silicon atoms) of the obtained organosiloxane 9, as well as the results of the solubility test.

[0090] [Example 10] Organopolysiloxane 10 was obtained in the same manner as in Example 1, except that intermediate compound 14 (28.78 g, 54 mmol) obtained in Reference Example 14 was used instead of intermediate compound 8 (18.20 g, 54 mmol) obtained in Reference Example 8. About this organopolysiloxane 10 1 The degree of polymerization was calculated to be 5 from 1 H NMR. When this organosiloxane 10 was subjected to the above-mentioned solubility test, the liquid contents became entirely clear after adding toluene, ethanol, and water and shaking, and was therefore rated S. Table 1 shows the number of reactive groups and (number of polar groups) / (number of silicon atoms) of the obtained organosiloxane 10, as well as the results of the solubility test.

[0091] [Comparative Example 1] The organopolysiloxane "FM-4411" manufactured by JNC Corporation was evaluated. This organopolysiloxane has all dimethyl side chains and both ends are symmetrically modified with monohydric alcohols. 1 H-NMR measurements revealed that one molecule of this organopolysiloxane contained 13 Si atoms. When this organopolysiloxane was subjected to the solubility test described above, the contents became entirely clear after adding toluene and ethanol and shaking, and therefore were rated S. On the other hand, the contents were suspended immediately after adding water and shaking, and separated into a silicone layer and a water layer after being left to stand for 30 minutes, and therefore were rated C. Table 1 shows the number of reactive groups and (number of polar groups) / (number of silicon atoms) of this organopolysiloxane, as well as the results of the solubility test.

[0092] Comparative Example 2 The organopolysiloxane "KF-6011" manufactured by Shin-Etsu Chemical Co., Ltd. was evaluated. This organopolysiloxane has a portion of its side chains modified with polyether, and both ends are symmetrically modified with trimethylsilyl groups. 1 H-NMR measurements revealed that one molecule of this organopolysiloxane contained 42 Si atoms, of which 14 were modified with PEG chains. When this organopolysiloxane was subjected to the solubility test described above, the contents became entirely clear after adding toluene and ethanol and shaking, and therefore were rated S. On the other hand, the contents were suspended immediately after adding water and shaking, and separated into a silicone layer and a water layer after being left to stand for 30 minutes, and therefore were rated C. Table 1 shows the number of reactive groups and (number of polar groups) / (number of silicon atoms) of this organopolysiloxane, as well as the results of the solubility test.

[0093] [Table 1]

[0094] Table 1 shows that the organopolysiloxane of the present invention has reactive functional groups and also exhibits good solubility in various solvents and water. Therefore, it can be seen that the organopolysiloxane of the present invention not only exhibits good reactivity as a raw material for polyamides, polyurethanes, polyethers, polyesters, and polycarbonates, but also has excellent polymerization reaction efficiency because it is compatible with various solvents and water.

Claims

1. An organopolysiloxane represented by the following general formula (1): 【Chemical 1】 (In the formula, R １ ~R ５ are each independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, R ６ is a divalent group containing an oxyalkylene group, R ７ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, X and Y each independently represent a monovalent hydrocarbon group having an organic group capable of forming an amide bond, a urethane bond, an ether bond, an ester bond, or a carbonate bond, and which may have a heteroatom; n is an integer of 1 or more and 50 or less.

2. The R ６ 2. The organopolysiloxane according to claim 1, wherein the organopolysiloxane has a structure represented by the following formula (2): 【Chemistry 2】 (In the formula, R ８ represents an optionally branched divalent alkylene group having two or more carbon atoms, R ９ , R １０ and R １１ each independently represents an optionally branched divalent alkylene group having one or more carbon atoms, p and q each independently represent an integer of 0 to 100.

3. 3. The organosiloxane according to claim 1, wherein X and Y in formula (1) each independently have a structure represented by formula (3): 【Chemistry 3】 (In the formula, R １２ and R １３ are each independently a divalent alkylene group, R １４ is a group selected from an amide group, a carboxy group, a carboxylic acid halide group, a carboxylic acid alkyl ester group, a carboxylic acid anhydride group, an isocyanate group, an alkanol group, a hydroxyphenyl group, a hydroxy group, an epoxy group, and a glycidyl group, E is a heteroatom; r is an integer equal to or greater than 0.

4. 3. The organopolysiloxane according to claim 1, wherein X and Y in formula (1) are the same group.

5. R in the formula (3) １４ The organopolysiloxane according to claim 3, wherein is a hydroxy group.

6. R in the formula (3) １４ The organopolysiloxane according to claim 3, wherein is an amide group.

7. R in the formula (3) １４ The organopolysiloxane according to claim 3, wherein is a carboxy group.

8. R in the formula (3) １４ The organopolysiloxane according to claim 3, wherein is an epoxy group.

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