Low-residue siloxane compounds, lubricating oil compositions and lubricants using the same

Abstract

The present invention relates to the siloxane compound represented by formula (1).　

Description

Technical Field

[0001] The present invention relates to a low-residue siloxane compound, a lubricating oil composition, and a lubricant using the same.

Background Art

[0002] Lubricating oils and lubricating oil compositions are used to reduce friction and wear between moving parts and moving surfaces of various mechanical devices.

[0003] Recently, due to the expansion and severity of the usage environment of transportation equipment, the sophistication and miniaturization of mechanical devices have been progressing. Along with the sophistication and miniaturization of mechanical devices, there is a demand for lubricating oils with a high viscosity index (VI) that can be used in a wide temperature range (with a small viscosity change with respect to temperature change). Lubricating oils with a high VI have a low viscosity at low temperatures and are excellent in terms of energy saving because the energy loss due to the viscous resistance of the lubricating oil itself is small. Also, in a high-temperature environment, compared with lubricating oils with a low VI, they do not overly decrease in viscosity, so they can maintain an oil film necessary for lubrication on the lubricating surface, and because they maintain an appropriate viscosity, the scattering of the lubricating oil is suppressed and the surrounding area is less contaminated.

[0004] Hitherto, as a method for generally increasing the viscosity index of hydrocarbon-based lubricating oils, high molecular compounds such as polymethacrylate esters and polybutene have been used as VI improvers (Patent Documents 1 and 2).

[0005] In recent years, lubricating oil compositions using siloxane compounds such as silicone oil (hereinafter also referred to as Si oil), which are known as lubricating oils with a high VI, as a lubricating oil base material have been proposed (Patent Documents 3 and 4).

[0006] However, siloxane compounds have a problem that sludge (SiO2) remains as a residue after oxidative degradation, which causes pipe blockage and filter clogging. Therefore, lubricants mainly composed of existing siloxane compounds have limitations in their applications. Thus, in order to further expand into a wider field, further improvement in lubricity and reduction of residues, which are bottlenecks in the lubricant field, are required.

[0007] So far, as a copolymer that can be used in a lubricating oil having excellent heat resistance, a polysiloxane-polyether block copolymer composed of a polysiloxane and a polyether containing a bisphenol structure has been reported (Patent Document 5). In addition, a lubricating oil composition having a polyalkylene glycol and a polyol ester having low residue properties (high sludge suppression effect) as base oils and consisting of phosphorus-based and amine-based antioxidants has also been reported (Patent Document 6).

[0008] However, since the copolymer described in Patent Document 5 has a structure containing polysiloxane, thickening due to deterioration and generation of sludge are problems.

[0009] Further, in the technique described in Patent Document 6, polyalkylene glycol and ester oil are synthetic oils with little thickening and sludge generation after deterioration, respectively. Therefore, it is considered that thickening and sludge generation after deterioration are also minor as a lubricant composition. However, in order to obtain a composition that can be used in a wide temperature range (high viscosity index) which is a current trend of lubricants, the VI of these mixed base oils is insufficient, and it is necessary to add a VI improver (a high molecular weight additive). The VI improver not only causes an increase in low-temperature viscosity, but also has a problem of being affected by shear force in the lubricating oil usage environment and impairing the initial lubricating oil characteristics (viscosity decrease occurs).

[0010] An object of the present invention is to solve the above-described problems. That is, an object is to provide a siloxane compound having excellent lubricity and a high viscosity index (VI) and having low residue properties, and a lubricating oil composition using the same.

Prior Art Documents

Patent Documents

[0011]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Summary of the Invention

[0012] As a result of intensive research to solve the above problems, the present inventor has found that the above object can be achieved by the following configuration, and has completed the present invention by further repeating studies based on this finding.

[0013] That is, the siloxane compound according to one aspect of the present invention is characterized by being represented by the following formula (1).

[0014]

Chemical formula

[0015] [In formula (1), X 1 is the same or different and is hydrogen, an alkyl group having 1 to 12 carbon atoms, or a polyoxyalkyl group represented by the following formula (2), Y is an alkylene group having 2 to 12 carbon atoms, Z 1 represents a divalent organic group bonded to an adjacent silicon atom by a carbon-silicon bond and to a polyoxyalkylene block by an oxygen atom, p is an integer from 0 to 13, q and r are each an integer from 0 to 16, n is an integer from 2 to 4, and a is an integer from 0 to 11.

Chemical formula

Brief Description of the Drawings

[0016]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Modes for Carrying Out the Invention

[0017] Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited thereto.

[0018] ((A) Siloxane Compound) The siloxane compound of this embodiment is characterized by being represented by the following formula (1).

[0019]

Chemical Formula

[0020] Such a siloxane compound of the present embodiment has a high viscosity index and low residue properties, and thus can be used as a lubricant or the like in a wide range of fields.

[0021] That is, according to the above configuration, it is possible to provide a siloxane compound having extremely excellent lubricity and low residue properties, and a lubricating oil composition using the same.

[0022] In the above formula (1), X 1 is the same or different and is hydrogen, an alkyl group having 1 to 12 carbon atoms, or a polyoxyalkyl group represented by the following formula (2).

Chemical formula

[0023] In the above formula (1) and formula (2), the structure of the alkyl group having 1 to 12 carbon atoms in X 1 and X 2 is not particularly limited, and may be linear, branched, or cyclic. Specifically, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an octyl group, a nonyl group, a dodecyl group, etc. can be mentioned. These functional groups may be contained alone in the structure, or in combination of two or more in X 1 .

[0024] X 1 and X 2 Preferably have 1 to 12 carbon atoms from the viewpoint of maintaining low viscosity at low temperatures, more preferably 1 to 10, and particularly preferably 1 to 8. If the carbon number of X 1 and X 2 exceeds 12, the low-temperature characteristics deteriorate significantly, making it difficult to use in the low-temperature range when used as a lubricating oil composition.

[0025] Also, in the above formula (1) and formula (2), Z 1 and Z2 represents a divalent organic group that is bonded to adjacent silicon atoms by a carbon-silicon bond and to a polyoxyalkylene block by an oxygen atom. Z 1 and Z 2 There are no particular limitations on the structure of the divalent organic group in, for example, -R-, -R-CO-, -R-NHCO-, -R-NHCONH-R 2 -NHCO-, -R-OOCNH-R 2 -NHCO- (wherein R is a divalent alkylene group such as ethylene, propylene, butylene, etc., and R 2 is a divalent arylene group such as, for example, -C6H4-, -C6H4-C6H4-, -C6H4-CH(CH3)2-C6H4-. Preferably, R 2 is a phenylene group). Examples thereof include. More preferably, Z 1 and Z 2 are divalent alkylene groups, particularly ethylene and propylene.

[0026] In the above formula (1), Y is an alkylene group having 2 to 12 carbon atoms. The structure of Y is not particularly limited and may be linear, branched, or cyclic.

[0027] Specifically, for example, alkylene groups such as an ethylene group, a propylene group, a butylene group, and a hexylene group can be mentioned. These functional groups may be contained singly or in combination of two or more in the structure.

[0028] From the viewpoint of maintaining low viscosity at low temperatures, the number of carbon atoms of the alkylene group in Y is preferably 2 to 12, more preferably 2 to 10, and particularly preferably 2 to 8. If the number of carbon atoms of the alkylene group in Y exceeds 12, the low-temperature characteristics may be significantly deteriorated.

[0029] Also, from the viewpoint of obtaining the viscosity required as a lubricating oil, the number of repeating units of the polyoxyalkylene group is preferably 1 to 11. If the number of repeating units exceeds 11, the proportion of the siloxane part in the molecular structure may become small and the viscosity index may decrease.

[0030] Also, in the above formula (1), p is an integer from 0 to 13. If p exceeds 13, the amount of residue after thermal degradation may increase.

[0031] In the above formula (1), q and r are each the same or different and are integers from 0 to 16. However, if these values exceed 16, the viscosity may become too high as a lubricating oil, and there is a risk of lacking energy-saving performance.

[0032] Furthermore, in the above formula (1), since the polyoxyalkylene compound is polyoxyethylene, polyoxypropylene, polyoxybutylene, mixed polyoxyethylene-oxypropylene, etc., n is an integer from 2 to 4.

[0033] Also, in the above formula (2), since the polyoxyalkylene compound is polyoxyethylene, polyoxypropylene, polyoxybutylene, mixed polyoxyethylene-oxypropylene, etc., m is an integer from 2 to 4.

[0034] Furthermore, in the above formula (2), b is an integer from 1 to 10. If b exceeds 10, the proportion of the siloxane part in the molecular structure may decrease, and the viscosity index may decrease.

[0035] The mass average molecular weight of the siloxane compound of this embodiment is not particularly limited, but it is preferably 500 to 11000. If the mass average molecular weight is less than 500, the evaporation amount may increase. Also, if the mass average molecular weight exceeds 11000, the viscosity becomes too high as a lubricating oil, lacking energy-saving performance, so it is not preferable.

[0036] Note that the mass average molecular weight of the siloxane compound in this embodiment is, as shown in the examples described later, 1 a value measured using H-NMR. Hereinafter, the mass average molecular weight is also simply referred to as the "average molecular weight".

[0037] Specifically, the siloxane compound of the present embodiment preferably has a viscosity index of 200 or more, and the residue amount after heating at 140°C for 100 hours and then at 250°C for 700 hours is 20% or less.

[0038] The viscosity index (VI) of the siloxane compound in the present embodiment is preferably 200 or more in order to obtain a lubricating oil composition having a high VI. More preferably, it is preferably 240 or more. In this specification, VI is a value measured and calculated based on JIS K 2283 (2000).

[0039] The method for synthesizing the siloxane compound as described above is not particularly limited. However, to show some production examples, for example, by subjecting a dimethylsiloxane blocked with hydrodimethoxysilyl groups at both ends of the molecular chain and a divinyl ether of a polyalkylene glycol to a hydrosilylation reaction in the presence of a platinum catalyst, the siloxane compound (silicone oil) of the present embodiment can be obtained. Alternatively, after subjecting a dimethylsiloxane blocked with hydrodimethoxysilyl groups at both ends of the molecular chain and a divinyl ether of a polyalkylene glycol to a hydrosilylation reaction in the presence of a platinum catalyst, a siloxane compound (silicone oil) can be obtained by subjecting it to a hydrosilylation reaction with an olefin compound in the presence of a platinum catalyst.

[0040] The siloxane compound of the present embodiment can be used alone as various lubricants as it is, but it may also be used as a lubricating oil composition in combination with a hydrocarbon-based lubricating oil as described later and at least one of an antioxidant and an extreme pressure agent.

[0041] That is, the lubricating oil composition of the present embodiment is characterized by containing at least (A) the above-mentioned siloxane compound, (B) a hydrocarbon-based lubricating oil, and at least one of (C) an extreme pressure agent and (D) an antioxidant.

[0042] The viscosity index (VI) of the lubricating oil composition of the present embodiment is preferably 180 or more. More preferably, it is preferably 200 or more, and further preferably 250 or more.

[0043] In the lubricating oil composition of the present embodiment, the content of the (A) siloxane compound with respect to the whole composition is 30 to 95% by mass from the viewpoints of viscosity index and lubricity. Particularly, it is preferably 50 to 90% by mass, and more preferably 60 to 90% by mass. Even when the content of the component (A) is less than 30% by mass, it is possible to improve the viscosity index when a lubricating oil composition is formed, but the effect of improving the viscosity index is poor. Also, there is no particular limitation on the upper limit, and as described above, 100% by mass may be a siloxane compound.

[0044] Hereinafter, components other than the siloxane compound in the lubricating oil composition of the present embodiment will be described.

[0045] ((B) Hydrocarbon-based lubricating oil) The lubricating oil composition of the present embodiment contains a hydrocarbon-based lubricating oil. The hydrocarbon-based lubricating oil that can be used is not particularly limited as long as it is compatible with the above-described (A) siloxane compound (silicone oil). Specifically, for example, ester oil, ether oil, polyalphaolefin (PAO) oil, mineral oil, etc. can be mentioned.

[0046] Specific examples of the ester oil include esters of monohydric alcohols or polyhydric alcohols and monobasic acids or polybasic acids.

[0047] Examples of the monohydric alcohol or polyhydric alcohol include monohydric alcohols or polyhydric alcohols having a hydrocarbon group with 1 to 30 carbon atoms, preferably 4 to 20 carbon atoms, and more preferably 6 to 18 carbon atoms. Specific examples of the polyhydric alcohols include trimethylolpropane, pentaerythritol, dipentaerythritol, etc.

[0048] Examples of the monobasic acid or polybasic acid include monobasic acids or polybasic acids having a hydrocarbon group with 1 to 30 carbon atoms, preferably 4 to 20 carbon atoms, and more preferably 6 to 18 carbon atoms.

[0049] The hydrocarbon group mentioned here may be linear or branched, and examples thereof include hydrocarbon groups such as an alkyl group, an alkenyl group, a cycloalkyl group, an alkylcycloalkyl group, an aryl group, an alkylaryl group, and an arylalkyl group.

[0050] In the present embodiment, when an ester oil is used as the component (B), the above-described ester oil may be used alone or in combination of two or more.

[0051] In a preferred embodiment, as the ester oil, a dibasic acid ester or a polyhydric alcohol fatty acid ester having a flash point of 200 °C or higher and a pour point of -40 °C or lower can be used. In particular, from the viewpoint of low volatility, a polyhydric alcohol fatty acid ester such as a fatty acid ester of trimethylolpropane or a fatty acid ester of pentaerythritol is more preferable.

[0052] Specific examples of the ether oil include polyoxyethers, dialkyl ethers, and aromatic ethers.

[0053] In addition, examples of the poly-α-olefin oil include polymers of α-olefins having 2 to 15 carbon atoms such as polybutene, 1-octene oligomer, and 1-decene oligomer, or hydrogenated products thereof.

[0054] Examples of the mineral oil include atmospheric residue obtained by atmospheric distillation of crude oil such as paraffinic, naphthenic, and intermediate-base crude oils; distillate oil obtained by vacuum distillation of the atmospheric residue; mineral oil refined by performing one or more treatments such as solvent dewaxing, solvent extraction, hydrocracking, solvent deasphalting, catalytic deasphalting, and hydrorefining, for example, light neutral oil, medium neutral oil, heavy neutral oil, bright stock, etc., and mineral oil obtained by isomerizing wax (GTL wax (Gas To Liquids WAX)) produced by the Fischer-Tropsch method or the like.

[0055] In this embodiment, as the component (B), the hydrocarbon-based lubricating oil as described above can be used alone, or two or more thereof can be used in combination.

[0056] In the lubricating oil composition of this embodiment, the content of the (B) hydrocarbon-based lubricating oil is 0 to 70% by mass with respect to the whole composition from the viewpoints of lubricity and viscosity index. In particular, it is preferably 10 to 50% by mass, and more preferably 10 to 20% by mass. When the content of the hydrocarbon-based lubricating oil is less than 10% by mass, it becomes difficult to obtain sufficient lubricity. Also, when it exceeds 70% by mass, the content of the (A) siloxane compound in the lubricating oil composition decreases, and the viscosity index of the lubricating oil composition becomes low, which is not preferable.

[0057] Furthermore, the lubricating oil composition of this embodiment further improves the lubricity of the lubricating oil composition by containing 10% by mass or more of an ester oil as the (B) hydrocarbon-based lubricating oil. That is, as a preferred embodiment, it is desirable that the (B) hydrocarbon-based lubricating oil contains 10 to 50% by mass of an ester oil.

[0058] ((C) Extreme pressure agent) The lubricating oil composition of this embodiment contains at least one of a (C) extreme pressure agent or a (D) antioxidant described later.

[0059] When the lubricating oil composition of this embodiment contains a (C) extreme pressure agent, the lubricating oil composition of this embodiment has an advantage that the lubricity and anti-wear property can be further improved.

[0060] As the (C) extreme pressure agent that can be used in this embodiment, sulfur-based extreme pressure agents such as thiadiazole-based compounds, polysulfides, thiocarbamate-based compounds, sulfurized fats and oils, sulfurized olefins, sulfurized esters, sulfurized fatty acids, thiophosphoric acid esters, thiophosphates, thiophosphites, molybdenum dialkyldithiocarbamate, molybdenum dialkyldithiophosphate, zinc dialkyldithiocarbamate, and zinc dialkyldithiophosphate can be preferably used. These can be used alone or in combination of two or more.

[0061] Among them, it is preferable to use at least one selected from thiophosphates, dithiocarbamates, sulfurized olefins, and dimercaptothiadiazole compounds as the (C) extreme pressure agent.

[0062] When the lubricating oil composition of the present embodiment contains the (C) extreme pressure agent, its content is about 0.5 to 10.0% by mass with respect to the whole composition from the viewpoint of obtaining sufficient wear resistance. By containing the (C) extreme pressure agent in such a content, there is an advantage that both the extreme pressure effect and the increase in the evaporation amount of the lubricating oil composition due to the evaporation of the extreme pressure agent itself can be achieved.

[0063] ((D) antioxidant) When the lubricating oil composition of the present embodiment contains the (D) antioxidant, there is an advantage that the life of the lubricating oil composition can be extended.

[0064] As the (D) antioxidant used in the present embodiment, antioxidants generally used in lubricating oils can be used without particular limitation. For example, phenolic compounds, amine compounds, phosphorus compounds, etc. can be mentioned.

[0065] More specifically, for example, alkylphenols such as 2,6-di-tert-butyl-4-methylphenol, bisphenols such as methylene-4,4-bis(2,6-di-tert-butyl-4-methylphenol), naphthylamines such as phenyl-α-naphthylamine, dialkyldiphenylamines, phosphite esters, etc. can be mentioned.

[0066] Among these, from the viewpoint of further improving lubricity, it is preferable to contain phosphorus compounds such as phosphate esters, phosphite esters, acidic phosphate esters, phosphonate esters, etc.

[0067] Furthermore, it is preferable to use two or more kinds of antioxidant (D) in the lubricating oil composition of the present embodiment in combination. For example, it is particularly preferable to use in combination a phenolic compound or an amine compound that functions as a primary antioxidant and a secondary antioxidant such as a phosphorus compound.

[0068] When the lubricating oil composition of the present embodiment contains antioxidant (D), the content of the antioxidant (D) with respect to the whole composition is 0.5 to 10.0% by mass from the viewpoints of oxidation suppression and evaporation reduction. More preferably, it is 2.0 to 7.0% by mass. By containing antioxidant (D) in such a content, there is an advantage that both the antioxidant effect and the increase in the evaporation amount of the lubricating oil composition due to the evaporation of the antioxidant itself can be achieved.

[0069] From the viewpoint of further enhancing lubricity, it is preferable to contain both the extreme pressure agent (C) and the antioxidant (D). In that case, the total amount thereof is preferably about 0.5 to 10.0% by mass with respect to the whole composition.

[0070] (Other additives) In the lubricating oil composition of the present embodiment, for the purpose of further improving its performance or for imparting further performance as necessary, various additives such as a metal deactivator, an antifoaming agent, a thickener, and a colorant may be blended alone or in combination within a range that does not impair the effects of the present invention.

[0071] Examples of the metal deactivator include benzotriazole-based, tolyltriazole-based, and imidazole-based compounds.

[0072] Examples of the antifoaming agent include polysiloxane, polyacrylate, and styrene ester polymer.

[0073] Examples of the thickener include metal soaps (e.g., lithium soap), silica, expanded graphite, polyurea, and clays (e.g., hectorite or bentonite).

[0074] When formulating the lubricating oil composition of the present embodiment with the additives as described above, the addition amount can be 0.0 to 10.0% by mass, or about 0.1 to 5% by mass, based on the total mass of the lubricant composition. The thickener for producing grease using the lubricating oil composition of the present embodiment can be used in an amount of 5 to 25% by mass based on the total mass of the lubricant grease composition.

[0075] (Preparation Method) The method for preparing the lubricating oil composition of the present embodiment is not particularly limited. For example, it can be adjusted by heating and mixing at least one of (A) a siloxane compound, (B) a hydrocarbon oil, (C) an extreme pressure agent, and (D) an antioxidant, and other additives to 100 °C.

[0076] (Applications) Since the lubricating oil composition of the present embodiment can be stably used at a wide range of temperatures for a long period of time, it can be used as various lubricants. For example, it is preferably used as a lubricant for turbo machinery, a lubricant for compressors, a lubricant for hydraulic equipment, a lubricant for machine tools, a grease base oil, a refrigeration oil, a plasticizer, etc. In particular, since there is less residue when heated and burned than in the past, it is less likely to cause pipe blockage and filter clogging due to the residue, and is suitable for applications where the lubricant is used in a circulation system.

[0077] This specification discloses technologies in various aspects as described above, and the main technologies are summarized below.

[0078] The siloxane compound according to one aspect of the present invention is characterized by being represented by the following formula (1).

[0079] [Chemical Formula]

[0080] [In formula (1), X 1 is the same or different and is hydrogen, an alkyl group having 1 to 12 carbon atoms, or a polyoxyalkyl group represented by the following formula (2). Y is an alkylene group having 2 to 12 carbon atoms, Z 1 represents a divalent organic group bonded to an adjacent silicon atom by a carbon-silicon bond and to a polyoxyalkylene block by an oxygen atom, p is an integer from 0 to 13, q and r are each an integer from 0 to 16, n is an integer from 2 to 4, and a is an integer from 0 to 11. [Chemical formula] (In formula (2), Z 2 represents a divalent organic group bonded to an adjacent silicon atom by a carbon-silicon bond and to a polyoxyalkylene block by an oxygen atom, X 2 is hydrogen or an alkyl group having 1 to 12 carbon atoms, m is an integer from 2 to 4 and b is an integer from 1 to 10. )]

[0081] With such a configuration, a siloxane compound having extremely excellent lubricity and low residue properties can be provided.

[0082] Further, it is preferable that the viscosity index of the siloxane compound is 200 or more, and the residue amount after heating at 140 °C for 100 hours and after heating at 250 °C for 700 hours is 20% or less. Thereby, it is considered that the above-described effects can be obtained more reliably.

[0083] Furthermore, a lubricating oil composition according to another aspect of the present invention is characterized by containing at least (A) the siloxane compound according to claim 1 or 2, (B) a hydrocarbon-based lubricating oil, (C) an extreme pressure agent, and (D) an antioxidant. With such a configuration, a lubricating oil composition having extremely excellent lubricity and low residue properties can be provided.

[0084] The lubricant according to still another aspect of the present invention is characterized by using the above-mentioned siloxane compound or lubricating oil composition. The present invention also includes the above-mentioned siloxane compound, a lubricating composition and a lubricant using the same, a grease and an emulsion using them, and a lubricating method using them.

Examples

[0085] Hereinafter, examples of the present invention will be described, but the present invention is not limited thereto. First, each raw material used in this example is shown below.

[0086] 〔Synthesis of (A) siloxane compound (silicone oil)〕 ·Silicone A-1 Silicone A-1 is 1,1,3,3-tetramethyldisiloxane (average molecular weight 134, average number of dimethyl units (p in the above formula (1)): 0) manufactured by Tokyo Chemical Industry Co., Ltd.

[0087] (Synthesis Example 1: Silicones A-2 and A-3) Into a 500 mL separable flask, 150 g (1.1 mol) of the above-mentioned silicone A-1, 416 g (0.9 mol) of decamethylcyclopentasiloxane (trade name: KF-995) manufactured by Shin-Etsu Chemical Co., Ltd., and 3 g of activated clay were added, and the mixture was stirred at 65 ° C for 7 hours. After cooling to room temperature, the activated clay was removed by filtration. Subsequently, the filtrate was placed in a 500 mL separable flask, heated and depressurized, and 191 g of low molecular weight dimethylsiloxane blocked with hydrogen dimethylsiloxy groups at both ends of the molecular chain (silicone A-2) and 343 g of high molecular weight dimethylsiloxane blocked with hydrogen dimethylsiloxy groups at both ends of the molecular chain (silicone A-3) remaining in the kettle were obtained as distillates.

[0088] 1As a result of analyzing silicone A-2 and silicone A-3 obtained using H-NMR, it was found that silicone A-2 had an average molecular weight of 529 and an average number of dimethyl units (p in the above formula (1)) of 5.3, and silicone A-3 had an average molecular weight of 1154 and an average number of dimethyl units (p in the above formula (1)) of 13.8.

[0089] Figure 1 shows the NMR data of silicone A-2.

[0090] Note that for the molecular chain at both ends of silicones A-2 to A-3, the hydrogen dimethylsiloxy group-blocked dimethylsiloxane 1 The H-NMR analysis method is as follows. a (chemical shift 0.05 to 0.10 ppm) indicates the peak of hydrogen derived from the methyl group of the repeating unit of dimethylsiloxane. b (chemical shift 0.17 to 0.22 ppm) indicates the peak of hydrogen derived from the methyl group of the hydrogendimethylsiloxy group at both ends of the molecular chain.

[0091] And the average molecular weight and the average number of dimethyl units (p in the above formula (1)) were calculated from the following calculation formulas based on the integration values (ratios) of the peaks of a and b above, respectively. Average number of dimethyl units = 2a ÷ b Average molecular weight = Average number of dimethyl units × Molecular weight of dimethyl unit + Molecular weight of hydrogendimethylsiloxy group at both ends of molecular chain

[0092] The NMR data of silicone A-2 was as follows. 1 H-NMR (solvent: deuterated chloroform, reference substance: TMS) When the integration value of δ = 0.05 to 0.10 ppm is set to 10.0, The integration value of δ = 0.17 to 0.22 ppm is 3.8.

[0093] (Synthesis Example 2: Silicone A-4) Into a 200 mL separable flask, 40 g (77 mmol) of dimethylsiloxane blocked with hydrogendimethylsiloxy groups at both ends of the molecular chain (average molecular weight 522, average number of dimethyl units (p in the above formula (1)) 5.2) obtained in the same manner as in Synthesis Example 1 and 25 mg of Pt alumina powder (Pt conversion: 21 ppm), which is a platinum catalyst manufactured by N.E. Chemcat Corporation, were placed. 19 g (38 mmol) of polyethylene glycol diallyl ether (trade name: Unionox AA-480R) manufactured by NOF Corporation was placed in a dropping funnel, and nitrogen substitution was performed. The mixed solution of dimethylsiloxane blocked with hydrogendimethylsiloxy groups at both ends of the molecular chain and the platinum catalyst was heated. After the liquid temperature reached 85°C, the dropping of polyethylene glycol diallyl ether was started. After all of the polyethylene glycol diallyl ether was dropped, it was aged at 125°C for 6 hours. After completion of the aging, 1 The disappearance of the peak of the unsaturated double bond was confirmed using 1 H-NMR. After cooling to room temperature, the platinum catalyst was removed by filtration. Subsequently, the filtrate was placed in a 200 mL separable flask, heated and depressurized to remove the dimethylsiloxane blocked with hydrogendimethylsiloxy groups at both ends of the molecular chain remaining from the reaction product, and 51 g of a dimethylsiloxane·polyether copolymer blocked with hydrogendimethylsiloxy groups at both ends of the molecule (Silicone A-4) was obtained.

[0094] 1 As a result of analyzing the obtained Silicone A-4 using 1 H-NMR, it was found that Silicone A-4 had an average molecular weight of 3546, an average number of dimethyl units (p in the above formula (1)) of 4.6, 3.1 repeating units of dimethylsiloxane·polyether (r in the above formula (1)), and 10.1 repeating numbers of oxyethylene (a in the above formula (1)).

[0095] The NMR data of Silicone A-4 are shown in Figure 2.

[0096] In addition, for the dimethylsiloxane·polyether copolymers blocked with hydrogendimethylsiloxy groups at both ends of the molecule shown in Silicone A-4 and the later-described Silicone A-7, A-8, and A-12 1The H-NMR analysis method is as follows. a (chemical shift 0.01 - 0.10 ppm) indicates the peak of hydrogen derived from the methyl group of the repeating unit of dimethylsiloxane and the methyl group of the dimethylsiloxane unit bonded to the polyether. b (chemical shift 0.16 - 0.21 ppm) indicates the peak of hydrogen derived from the methyl group of the hydridodimethylsiloxy groups at both ends of the molecular chain. c (chemical shift 0.40 - 1.10 ppm) indicates the peak of hydrogen derived from CH2 adjacent to silicon in the polyether part bonded to silicon. d (chemical shift 3.30 - 3.70 ppm) indicates the peak of hydrogen derived from CH2 bonded to oxygen in the hydrocarbon part connecting the repeating part of oxyethylene in the polyether part and the repeating part of oxyethylene to silicon.

[0097] The average molecular weight, the average number of dimethyl units, as well as the average number of repeating units of dimethylsiloxane - polyether and the average number of repeating units of oxyethylene were calculated respectively from the following calculation formulas based on the integral values (ratios) of the peaks a, b, c, and d above. Average number of dimethyl units = (2a - 6b - c) ÷ 3b Average number of repeating units of dimethylsiloxane - polyether = 3b ÷ c Number of repeating units of oxyethylene = d ÷ b - 1 Average molecular weight = (Number of repeating units of oxyethylene × Molecular weight of oxyethylene + Average number of dimethyl units × Molecular weight of dimethyl unit + Molecular weight of the hydrocarbon part connecting the polyether part and silicon + Molecular weight of the silicon part connected through the polyether part and the hydrocarbon part) × Average number of repeating units of dimethylsiloxane - polyether + Average number of dimethyl units × Molecular weight of dimethyl unit + Molecular weight of the hydridodimethylsiloxy groups at both ends of the molecular chain

[0098] The NMR data of silicone A - 4 was as follows. 1 H-NMR (solvent: deuterated chloroform, reference substance: TMS) When the integrated value of δ = 0.01 to 0.10 ppm is set to 10.0, the integrated value of δ = 0.16 to 0.21 ppm is 1.0 the integrated value of δ = 0.40 to 1.10 ppm is 0.9 the integrated value of δ = 3.30 to 3.70 ppm is 10.6.

[0099] (Synthesis Example 3: Silicone A-5) Into a 200 mL separable flask, 20 g (36 mmol) of dimethylsiloxane blocked with hydridodimethylsiloxy groups at both ends of the molecular chain (average molecular weight 558, average number of dimethyl units (p in the above formula (1)) 5.7) obtained by the same method as in Synthesis Example 1 and 70 g of toluene were placed. 24 g (214 mmol) of diisobutylene manufactured by Idemitsu Kosan Co., Ltd. and 3 μL of a Pt-CTS-toluene solution (Pt conversion: 2 ppm), which is a platinum catalyst manufactured by N.E. Chemcat Corporation, were placed in a dropping funnel, and nitrogen substitution was performed. The mixed solution of dimethylsiloxane blocked with hydridodimethylsiloxy groups at both ends of the molecular chain and toluene was heated. After the liquid temperature reached 60 °C, the dropping of the mixed solution of diisobutylene and the platinum catalyst was started. After all of the mixed solution of diisobutylene and the platinum catalyst was dropped, it was aged at 95 °C for 4.5 hours. After completion of the aging, 1 The disappearance of the peak of the SiH group was confirmed using 1H-NMR. Subsequently, it was heated and depressurized to remove the remaining diisobutylene and toluene used as a solvent from the reaction product, and 28 g of dimethylsiloxane blocked with isooctyldimethylsiloxy groups at both ends of the molecule (Silicone A-5) was obtained.

[0100] 1 As a result of analyzing the obtained Silicone A-5 using 1H-NMR, it was found that Silicone A-5 has an average molecular weight of 739 and an average number of dimethyl units (p in the above formula (1)) of 5.1.

[0101] Figure 3 shows the NMR data of Silicone A-5.

[0102] Note that for the dimethylsiloxane blocked with alkyldimethylsiloxy groups at both ends of the molecule shown in Silicone A-5 and Silicone A-6 described later1 The H-NMR analysis method is as follows. a (chemical shift 0.06 to 0.12 ppm) indicates the peak of hydrogen derived from the methyl group of the repeating unit of dimethylsiloxane. b (chemical shift 0.45 to 0.72 ppm) indicates the peak of hydrogen derived from CH2 adjacent to silicon of the alkyl group bonded to silicon.

[0103] Then, the average molecular weight and the average number of dimethyl units were calculated from the following calculation formulas based on the integral values (ratio) of the peaks of a and b above. Average number of dimethyl units = 2a ÷ 3b Average molecular weight = Average number of dimethyl units × Molecular weight of dimethyl unit + Molecular weight of alkyldimethylsiloxy groups at both ends of the molecular chain

[0104] The NMR data of silicone A-5 was as follows. 1 H-NMR (solvent: deuterated chloroform, reference substance: TMS) When the integral value of δ = 0.06 to 0.12 ppm is taken as 10.0, The integral value of δ = 0.45 to 0.72 ppm is 1.3.

[0105] (Synthesis Example 4: Silicone A-6) Into a 200 mL separable flask, 23 g (41 mmol) of dimethylsiloxane blocked with hydrodimethysiloxy groups at both ends of the molecular chain (average molecular weight 558, average number of dimethyl units (p) 5.7) obtained by the same method as in Synthesis Example 1 above and 71 g of toluene were placed. In a dropping funnel, 18 g (214 mol) of 1-hexene (trade name: Linearene 6) manufactured by Idemitsu Kosan Co., Ltd. and 3 μL of a Pt-CTS-toluene solution which is a platinum catalyst manufactured by N.E. Chemcat Corporation (Pt conversion: 2 ppm) were placed, and nitrogen substitution was carried out. The mixed solution of dimethylsiloxane blocked with hydrodimethysiloxy groups at both ends of the molecular chain and toluene was heated, and after the liquid temperature reached 60 °C, the dropping of the mixed solution of 1-hexene and platinum catalyst was started. After all of the mixed solution of 1-hexene and platinum catalyst was dropped, it was aged at 80 °C for 6 hours. After the aging was completed,1 The disappearance of the peak of the SiH group was confirmed using H-NMR. Subsequently, heating and decompression were carried out to remove the residual 1-hexene and toluene used as a solvent from the reaction product, and 30 g of dimethylsiloxane blocked with hexyl dimethylsiloxy groups at both molecular ends (silicone A-6) was obtained.

[0106] 1 As a result of analyzing silicone A-6 obtained using H-NMR, it was found that silicone A-6 had an average molecular weight of 677 and an average number of dimethyl units (p in the above formula (1)) of 5.1.

[0107] (Synthesis Example 5: Silicone A-7) Into a 200 mL separable flask, 25 g (48 mmol) of dimethylsiloxane blocked with hydrodimethylsiloxy groups at both molecular chains obtained by the same method as in Synthesis Example 1 above (average molecular weight 522, average number of dimethyl units (p in the above formula (1)) 5.2), 31 g of toluene, 5 g (25 mmol) of triethylene glycol divinyl ether manufactured by Tokyo Chemical Industry Co., Ltd., and 12 mg of Pt alumina powder (Pt conversion: 20 ppm), which is a platinum catalyst manufactured by N.E. Chemcat Corporation, were placed, and nitrogen substitution was carried out. The mixed solution was heated and aged at 60 °C for 5 hours. After completion of the aging, 1 The disappearance of the peak of the unsaturated double bond was confirmed using H-NMR. Subsequently, after cooling to room temperature, the platinum catalyst was removed by filtration.

[0108] Subsequently, the filtrate was placed in a 200 mL eggplant flask, heated and decompressed to remove the residual dimethylsiloxane blocked with hydrodimethylsiloxy groups at both molecular chains and toluene used as a solvent from the reaction product, and 20 g of a dimethylsiloxane·polyether copolymer blocked with hydrodimethylsiloxy groups at both molecular ends (silicone A-7) was obtained.

[0109] 1As a result of analyzing silicone A-7 obtained using H-NMR, it was found that silicone A-7 had an average molecular weight of 1470, an average number of 4.9 dimethyl units (p in the above formula (1)), 1.4 repeating units of dimethylsiloxane-polyether (r in the above formula (1)), and a repeating number of oxyethylene (a in the above formula (1)) of 3.1 units.

[0110] (Synthesis Example 6: Silicone A-8) Into a 500 mL separable flask, 150 g (287 mmol) of silicone A-2 obtained in the above Synthesis Example 1, 150 g of toluene, 45 g (22 mmol) of triethylene glycol divinyl ether manufactured by Tokyo Chemical Industry Co., Ltd., and 81 mg of Pt alumina powder (Pt conversion: 20 ppm), which is a platinum catalyst manufactured by N.E. Chemcat Corporation, were placed, and nitrogen substitution was performed. The mixed solution was heated and aged at 75 °C for 4.5 hours. After completion of the aging, 1 The disappearance of the peak of the unsaturated double bond was confirmed using H-NMR. Subsequently, after cooling to room temperature, the platinum catalyst was removed by filtration.

[0111] Subsequently, the filtrate was placed in a 500 mL eggplant flask, heated under reduced pressure, and the dimethylsiloxane blocked with hydridodimethylsiloxy groups at both ends of the molecular chain remaining in the reaction product and toluene used as a solvent were removed to obtain 160 g of a dimethylsiloxane-polyether copolymer (silicone A-8) blocked with hydridodimethylsiloxy groups at both ends of the molecule.

[0112] 1 As a result of analyzing silicone A-8 obtained using H-NMR, it was found that silicone A-8 had an average molecular weight of 2760, an average number of 4.6 dimethyl units (p in the above formula (1)), 3.5 repeating units of dimethylsiloxane-polyether (r in the above formula (1)), and a repeating number of oxyethylene (a in the above formula (1)) of 3.0 units.

[0113] (Synthesis Example 7: Silicone A-9) Into a 200 mL separable flask, 50 g (18 mmol) of silicone A-8 obtained in Synthesis Example 7 was placed. In a dropping funnel, 32 g (0.4 mol) of 1-hexene (trade name: Linearene 6) manufactured by Idemitsu Kosan Co., Ltd. and 10 μL of a Pt-CTS-toluene solution (Pt equivalent: 3 ppm), which is a platinum catalyst manufactured by N.E. Chemcat Corporation, were placed, and nitrogen substitution was performed. Silicone A-8 was heated, and after the liquid temperature reached 30°C, the dropping of the mixed solution of 1-hexene and the platinum catalyst was started. At this time, the dropping rate was adjusted so that the liquid temperature was maintained at 65 to 75°C. After all of the mixed solution of 1-hexene and the platinum catalyst was dropped, it was aged at 65°C for 5.5 hours. After the aging was completed, 1 The disappearance of the peak of the SiH group was confirmed using 1H-NMR. Subsequently, it was heated and depressurized to remove the remaining 1-hexene and toluene from the reaction product, and 52 g of a dimethylsiloxane-polyether copolymer (silicone A-9) blocked with hexyl dimethylsiloxy groups at both molecular ends was obtained.

[0114] 1 As a result of analyzing silicone A-9 obtained using 1H-NMR, it was found that silicone A-9 had an average molecular weight of 2772, an average number of 4.4 dimethyl units (p in the above formula (1)), 3.3 repeating units of dimethylsiloxane-polyether (r in the above formula (1)), and 3.1 repeating numbers of oxyethylene (a in the above formula (1)).

[0115] Fig. 4 shows the NMR data of silicone A-9.

[0116] In addition, for the dimethylsiloxane-polyether copolymer blocked with alkyldimethylsiloxy groups at both molecular ends shown in silicone A-9 and silicone A-11 described later, 1 The 1H-NMR analysis method is as follows. a (chemical shift 0.01 to 0.15 ppm) indicates the peak of hydrogen derived from the methyl group of the repeating unit of dimethylsiloxane, the methyl group of the dimethylsiloxane unit bonded to the polyether, and the methyl group of the dimethylsiloxane unit bonded to the alkyl group. b (chemical shift 0.80 - 0.95 ppm) indicates the peak of the hydrogen from the terminal CH3 of the alkyl group bonded to silicon. c (chemical shift 0.95 - 1.10 ppm) indicates the peak of the hydrogen from the CH2 adjacent to the silicon in the polyether part bonded to silicon and then the CH2 adjacent to that. d (chemical shift 3.30 - 3.75 ppm) indicates the peak of the hydrogen from the CH2 that binds to the oxygen in the hydrocarbon part connecting the repeating part of oxyethylene in the polyether part, the repeating part of oxyethylene, and silicon.

[0117] And the average molecular weight, the average number of dimethyl units, the average number of repeating units of dimethylsiloxane - polyether, and the average number of repeats of oxyethylene were calculated respectively from the following calculation formulas based on the integral values (ratios) of the peaks a, b, c, and d above. Average number of dimethyl units = (2a - 8b - 6c) ÷ 3c Average number of repeating units of dimethylsiloxane - polyether = 3c ÷ 2b Number of repeats of oxyethylene = d ÷ c - 1 Average molecular weight = (number of repeats of oxyethylene × molecular weight of oxyethylene + average number of dimethyl units × molecular weight of dimethyl unit + molecular weight of the hydrocarbon part connecting the polyether part and silicon + molecular weight of the silicon part connected through the polyether part and the hydrocarbon part) × average number of repeating units of dimethylsiloxane - polyether + average number of dimethyl units × molecular weight of dimethyl unit + molecular weight of the alkyldimethylsiloxy groups at both ends of the molecular chain

[0118] The NMR data of silicone A - 9 was as follows. 1 H - NMR (solvent: deuterated chloroform, reference substance: TMS) When the integral value of δ = 0.05 - 0.15 ppm is taken as 10.0, The integral value of δ = 0.80 - 0.95 ppm is 0.4 The integral value of δ = 0.95 - 1.10 ppm is 0.9 The integral value of δ = 3.50 to 3.75 ppm is 3.6.

[0119] (Synthesis Example 8: Silicone A-10) Into a 200 mL separable flask, 25 g (9 mmol) of the silicone A-8 obtained in the above Synthesis Example 7 and 53 g of toluene were placed. In a dropping funnel, 5 g (42 mmol) of α-methylstyrene (AMS) manufactured by Mitsui Chemicals, Inc., 11 g of toluene, and 55 μL of a Pt-CTS-toluene solution (Pt conversion: 47 ppm), which is a platinum catalyst manufactured by N.E. Chemcat Corporation, were placed, and nitrogen substitution was performed. The silicone A-8 was heated, and after the liquid temperature reached 30°C, the dropping of the mixed solution in the dropping funnel was started. After all of the mixed solution in the dropping funnel was dropped, it was aged at 80°C for 22 hours. After completion of the aging, 1 The disappearance of the peak of the SiH group was confirmed using 1H-NMR. Subsequently, it was heated and depressurized to remove the residual α-methylstyrene (AMS) and toluene used as the solvent from the reaction product, and 24 g of a dimethylsiloxane-polyether copolymer (silicone A-10) blocked with 2-phenylpropyldimethylsiloxy groups at both molecular ends was obtained.

[0120] 1 As a result of analyzing the obtained silicone A-10 using 1H-NMR, it was found that silicone A-10 has an average molecular weight of 3933, an average number of 4.7 dimethyl units (p in the above formula (1)), 4.8 repeating units of dimethylsiloxane-polyether (r in the above formula (1)), and 2.9 repeating numbers of oxyethylene (a in the above formula (1)).

[0121] Fig. 5 shows the NMR data of silicone A-10.

[0122] Note that for the dimethylsiloxane-polyether copolymer blocked with 2-phenylpropyldimethylsiloxy groups at both molecular ends shown in silicone A-10 1 The 1H-NMR analysis method is as follows. a (chemical shift 0.01 - 0.15 ppm) indicates the peak of hydrogen derived from the methyl group of the repeating unit of dimethylsiloxane and the methyl group of the dimethylsiloxane unit bonded to the polyether. b (chemical shift 0.99 - 1.05 ppm) indicates the peak of hydrogen derived from CH2 adjacent to silicon in the polyether moiety bonded to silicon. c (chemical shift 2.85 - 3.00 ppm) indicates the peak of hydrogen derived from CH of the aralkyl group bonded to silicon. d (chemical shift 3.30 - 3.75 ppm) indicates the peak of hydrogen derived from CH2 that binds to oxygen in the hydrocarbon moiety connecting the repeating part of oxyethylene in the polyether moiety, the repeating part of oxyethylene, and silicon.

[0123] And the average molecular weight, the average number of dimethyl units, the average number of repeating units of dimethylsiloxane - polyether, and the average number of repeating units of oxyethylene were calculated respectively from the following calculation formulas based on the integral values (ratios) of the peaks a, b, c, and d above. Average number of dimethyl units = (2a - 6b) ÷ 3b Average number of repeating units of dimethylsiloxane - polyether = b ÷ 2c Number of repeating units of oxyethylene = d ÷ b - 1 Average molecular weight = (Number of repeating units of oxyethylene × Molecular weight of oxyethylene + Average number of dimethyl units × Molecular weight of dimethyl unit + Molecular weight of the hydrocarbon moiety connecting the polyether moiety and silicon + Molecular weight of the silicon moiety connected through the polyether moiety and the hydrocarbon moiety) × Average number of repeating units of dimethylsiloxane - polyether + Average number of dimethyl units × Molecular weight of dimethyl unit + Molecular weight of the 2 - phenylpropyldimethylsiloxy group at both ends of the molecule

[0124] The NMR data of silicone A - 10 was as follows. 1 H - NMR (solvent: deuterated chloroform, reference substance: TMS) When the integral value of δ = 0.01 - 0.15 ppm is taken as 10.0, The integral value at δ = 0.99 - 1.05 ppm is 0.1 The integral value at δ = 2.85 - 3.00 ppm is 1.0 The integral value at δ = 3.30 - 3.75 ppm is 3.8

[0125] (Synthesis Example 9: Silicone A-11) Into a 200 mL separable flask, 25 g (9 mmol) of the silicone A-8 obtained in the above Synthesis Example 7 and 50 g of toluene were placed. In a dropping funnel, 6 g (36 mmol) of 1-dodecene (trade name: Linearene 12) manufactured by Idemitsu Kosan Co., Ltd., 10 g of toluene, and 59 μL of a Pt-CTS-toluene solution (Pt conversion: 49 ppm), which is a platinum catalyst manufactured by N.E. Chemcat Corporation, were placed, and nitrogen substitution was performed. The mixed solution was heated, and after the liquid temperature reached 30°C, the dropping of the mixed solution in the dropping funnel was started. After all of the mixed solution in the dropping funnel was dropped, it was aged at 85°C for 16 hours. After the aging was completed, 1 The disappearance of the peak of the SiH group was confirmed using 1H-NMR. Subsequently, it was heated and depressurized to remove the residual 1-dodecene and toluene used as the solvent from the reaction product, and 27 g of a dimethylsiloxane-polyether copolymer (silicone A-11) blocked with dodecyldimethylsiloxy groups at both molecular ends was obtained.

[0126] 1 As a result of analyzing the obtained silicone A-11 using 1H-NMR, it was found that silicone A-11 has an average molecular weight of 2865, an average number of 4.4 dimethyl units (p in the above formula (1)), 3.2 repeating units of dimethylsiloxane-polyether (r in the above formula (1)), and 3.0 repeating numbers of oxyethylene (a in the above formula (1)).

[0127] (Synthesis Example 10: Silicone A-12) In a 200 mL separable flask, 35 g (66 mmol) of silicone A-2 obtained in Synthesis Example 1, 13 g (64 mmol) of triethylene glycol divinyl ether manufactured by Tokyo Chemical Industry Co., Ltd., and 22 mg (Pt equivalent: 23 ppm) of Pt alumina powder, which is a platinum catalyst manufactured by N.E. Chemcat Corporation, were placed, and nitrogen substitution was carried out. The mixed solution was heated and aged at 75 °C for 3 hours. After completion of aging, 1 The disappearance of the peak of the unsaturated double bond was confirmed using 1H-NMR. Subsequently, after cooling to room temperature, the platinum catalyst was removed by filtration.

[0128] Subsequently, the filtrate was placed in a 100 mL eggplant flask, heated and depressurized to remove residual silicone A-2 from the reaction product, and 32 g of a dimethylsiloxane-polyether copolymer (silicone A-12) blocked with hydrogenodimethylsiloxy groups at both molecular ends was obtained.

[0129] 1 As a result of analyzing silicone A-12 obtained using 1H-NMR, it was found that silicone A-12 had an average molecular weight of 10572, an average number of 4.1 dimethyl units (p in the above formula (1)), 16.2 repeating units of dimethylsiloxane-polyether (r in the above formula (1)), and a repeating number of oxyethylene (a in the above formula (1)) of 3.0.

[0130] (Synthesis Example 11: Silicone A-13) In a 200 mL separable flask, 25 g (48 mmol) of dimethylsiloxane blocked with hydrogenodimethylsiloxy groups at both molecular chains (average molecular weight 522, average number of dimethyl units (p in the above formula (1)) 5.2) obtained in the same manner as in Synthesis Example 1, 58 g of toluene, 2 g (24 mmol) of 1,5-hexadiene manufactured by Tokyo Chemical Industry Co., Ltd., and 10 mg (Pt equivalent: 19 ppm) of Pt alumina powder, which is a platinum catalyst manufactured by N.E. Chemcat Corporation, were placed, and nitrogen substitution was carried out. The mixed solution was heated and aged at 80 °C for 5 hours. After completion of aging, 1The disappearance of the unsaturated double bond peak was confirmed using H-NMR. Subsequently, after cooling to room temperature, the platinum catalyst was removed by filtration.

[0131] Subsequently, the filtrate was placed in a 100 mL eggplant flask, heated under reduced pressure to remove the molecular chain terminal hydrogen dimethylsiloxy group-blocked dimethylsiloxane remaining from the reaction and toluene used as a solvent, and 14 g of the molecular chain terminal hydrogen dimethylsiloxy group-blocked dimethylsiloxane / hexylene copolymer was obtained. 1 As a result of analyzing the copolymer obtained using H-NMR, it was found that the copolymer had an average molecular weight of 1201, an average number of 5.3 dimethyl units (p in the above formula (1)), and 1.1 repeating units of dimethylsiloxane / hexylene (q in the above formula (1)).

[0132] Figure 6 shows the NMR data of the molecular chain terminal hydrogen dimethylsiloxy group-blocked dimethylsiloxane / hexylene copolymer.

[0133] Note that for the molecular chain terminal hydrogen dimethylsiloxy group-blocked dimethylsiloxane / hexylene copolymer 1 The H-NMR analysis method is as follows. a (chemical shift 0.01 - 0.11 ppm) shows the peak of hydrogen derived from the methyl group of the dimethylsiloxane unit bonded to the hexylene group and the methyl group of the repeating unit of dimethylsiloxane. b (chemical shift 0.17 - 0.21 ppm) shows the peak of hydrogen derived from the methyl group of the hydrogen dimethylsiloxy group at both ends of the molecular chain. c (chemical shift 0.45 - 0.60 ppm) shows the peak of hydrogen derived from CH2 adjacent to silicon of the hexylene group bonded to silicon.

[0134] And the average molecular weight, the average number of dimethyl units, and the average number of repeating units of dimethylsiloxane / hexylene were calculated respectively by the following calculation formulas based on the integral values (ratios) of the peaks of a, b, and c above. Average number of dimethyl units = (2a - b - 6c) ÷ 3c Average number of repeating units of dimethylsiloxane - hexylene = 3c ÷ b Average molecular weight = (Average number of dimethyl units × Molecular weight of dimethyl unit + Molecular weight of hexylene + Molecular weight of silicon part connected to hexylene part) × Average number of repeating units of dimethylsiloxane - hexylene + Average number of dimethyl units × Molecular weight of dimethyl unit + Molecular weight of hydridodimethylsiloxy groups at both ends of molecular chain

[0135] The NMR data of the dimethylsiloxane - hexylene copolymer blocked with hydridodimethylsiloxy groups at both ends of the molecule were as follows. 1 H - NMR (Solvent: deuterated chloroform, Reference substance: TMS) When the integral value of δ = 0.01 - 0.11 ppm is set to 10.0, The integral value of δ = 0.17 - 0.21 ppm is 2.2 The integral value of δ = 0.45 - 0.60 ppm is 0.8.

[0136] Next, 9 g (7 mmol) of the dimethylsiloxane - hexylene copolymer blocked with hydridodimethylsiloxy groups at both ends of the molecule obtained above and 72 g of toluene were placed in a 200 mL separable flask. 24 g (60 mmol) of methoxypolyethylene glycol allyl ether (trade name: Unionox PKA - 5007) manufactured by NOF Corporation and 63 μL (Pt conversion: 49 ppm) of a Pt - CTS - toluene solution, which is a platinum catalyst manufactured by N - E - Chemcat Corporation, were placed in a dropping funnel, and nitrogen substitution was performed. The mixed solution was heated, and after the liquid temperature reached 35°C, the dropping of the mixed solution in the dropping funnel was started. After all of the mixed solution in the dropping funnel was dropped, it was aged at 75°C for 23 hours. After the aging was completed, 1 The disappearance of the peak of the SiH group was confirmed using H - NMR. Subsequently, distilled water and hexane were added to the obtained reaction solution, the hexane layer was recovered, and the hexane and toluene used as solvents were removed to obtain 4 g of the dimethylsiloxane - hexylene copolymer blocked with polyoxyalkyldimethylsiloxy groups at both ends of the molecule (Silicone A - 13).

[0137] 1 As a result of analyzing silicone A-13 obtained using H-NMR, it was found that silicone A-13 has an average molecular weight of 1897, an average number of 4.6 dimethyl units (p in the above formula (1)), 1.4 repeating units of dimethylsiloxane·xylene (q in the above formula (1)), and a repeating number of oxyethylene at the molecular terminals (b in the above formula (2)) of 6.0.

[0138] Fig. 7 shows the NMR data of silicone A-13.

[0139] Note that for the dimethylsiloxane·alkylene copolymer blocked with polyoxyalkyl dimethylsiloxy groups at both molecular terminals shown in silicone A-13 1 The H-NMR analysis method is as follows. a (chemical shift 0.01 to 0.15 ppm) shows the peak of hydrogen derived from the methyl group of the repeating unit of dimethylsiloxane, the methyl group of the dimethylsiloxane unit bonded to polyether, and the methyl group of the dimethylsiloxane unit bonded to the hexylene group. b (chemical shift 1.20 to 1.40 ppm) shows the peak of hydrogen derived from CH2 of the hexylene group not bonded to silicon. c (chemical shift 1.50 to 1.70 ppm) shows the peak of hydrogen derived from the CH2 adjacent to the CH2 adjacent to silicon of the polyoxyalkyl group bonded to silicon. d (chemical shift 3.50 to 3.70 ppm) shows the peak of hydrogen derived from the repeating portion of ethylene in the polyoxyalkyl part.

[0140] And the average molecular weight, the average number of dimethyl units, the average number of repeating units of dimethylsiloxane·polyether, and the average number of repeating units of oxyethylene were calculated from the following calculation formulas based on the integral values (ratios) of the peaks of a, b, c, and d above, respectively. Average number of dimethyl units = (4a - 6b - 18c) ÷ 3b Average number of repeating units of dimethylsiloxane - hexylene = b÷2c Degree of polymerization of oxyethylene = d÷2c Average molecular weight = (Average number of dimethyl units × Molecular weight of dimethyl unit + Molecular weight of hexylene + Molecular weight of silicon part connected to hexylene part) × Average number of repeating units of dimethylsiloxane - hexylene + Average number of dimethyl units × Molecular weight of dimethyl unit + Molecular weight of polyoxyalkyldimethylsiloxy groups at both ends of molecular chain

[0141] The NMR data of silicone A - 13 was as follows. 1 H - NMR (Solvent: deuterated chloroform, Reference substance: TMS) When the integral value of δ = 0.05 - 0.15 ppm is set to 10.0, the integral value of δ = 1.20 - 1.40 ppm is 1.5 the integral value of δ = 1.50 - 1.70 ppm is 0.6 the integral value of δ = 3.50 - 3.70 ppm is 6.7.

[0142] The data of the above (A) siloxane compound (silicone oil) are summarized in Table 1. In Table 1, X represents X in the above formulas (1) and (2), 1 and X 2 and Y, Z 1 and p, q, r, a, n, Z 2 and b and m have the same meanings as those in the above formulas (1) and (2), respectively.

[0143] Also, the residue amount (wt%) in the table was measured by the method described below. Among the silicone oils shown in Table 1, for silicone A - 3, since the value of p in formula (1) exceeds 13, it is considered that the residue amount has increased.

[0144]

Table 1

[0145] ((B) Hydrocarbon-based lubricating oil) · Ester oil: Pentaerythritol fatty acid ester manufactured by NOF CORPORATION, product name: Unister HR-32 (kinematic viscosity at 40°C: 33.5 mm 2 / s, kinematic viscosity at 100°C: 5.8 mm 2 / s, VI: 115, flash point: 274°C, pour point: -50°C) · Ester oil: Trimethylolpropane fatty acid ester (C6-C12) manufactured by NOF CORPORATION, product name: Unister H-334R (kinematic viscosity at 40°C: 19.6 mm 2 / s, kinematic viscosity at 100°C: 4.4 mm 2 / s, VI: 138, pour point -40°C) · PAG (polybutylene glycol): "UCON OSP-32" manufactured by DOW CORNING Toray Co., Ltd. (kinematic viscosity at 40°C: 32.0 mm 2 / s, kinematic viscosity at 100°C: 6.5 mm 2 / s, VI: 146) · PAO oil: Polyalphaolefin manufactured by Chevron Phillips, product name: Synfluid PAO 6 cSt (kinematic viscosity at 40°C: 30.5 mm 2 / s, kinematic viscosity at 100°C: 5.9 mm 2 / s, VI: 137) · Ether oil: Alkyl diphenyl ether "Moresco Hi-Lube LB-100" manufactured by MORESCO CORPORATION (kinematic viscosity at 40°C: 102.6 mm 2 / s, kinematic viscosity at 100°C: 12.6 mm 2 / s, VI: 117) · Mineral oil: Mineral oil manufactured by Cosmo Oil Lubricants Co., Ltd., product name: Cosmo Pure Spin TK (kinematic viscosity at 40°C: 9.3 mm 2 / s, kinematic viscosity at 100°C: 2.5 mm 2 / s, VI: 94) · Liquid paraffin: "Moresco White P-70" manufactured by MORESCO CORPORATION (kinematic viscosity at 40°C: 12.6 mm 2 / s, kinematic viscosity at 100°C: 2.9 mm 2 / s, VI: 56) · PAG (polyalkylene glycol): "Newpol HB50-660" manufactured by Sanyo Chemical Industries, Ltd. (kinematic viscosity at 40°C: 130.1 mm 2 / s, kinematic viscosity at 100 °C: 20.1 mm 2 / s, VI: 178)

[0146] ((C) Extreme Pressure Additive) · Sulfur-based extreme pressure additive: Isobutene sulfide, manufactured by RheinChemie, "RC 2545" · Sulfur-phosphorus-based extreme pressure additive: Thiol phosphate ester, "LUBRIZOL IC9AW31" manufactured by LUBRIZOL · Phosphorus-based extreme pressure additive: Amine salt of fatty acid phosphate ester, "NA-LUBE AW-6400FG" manufactured by Kingindustries

[0147] ((D) Antioxidant) · Primary antioxidant: Aromatic amine-based compound manufactured by BASF, "IRGANOX L-57" · Primary antioxidant: Phenol-based compound manufactured by BASF, "IRGANOX L-135" · Secondary antioxidant: Phosphite-based compound manufactured by Johoku Chemical Industry Co., Ltd., "JP-310"

[0148] (Others) · Metal deactivator: Benzotriazole compound "CUVAN303" manufactured by VANDERBILT · Silicone 1 used in comparative test: Methylphenyl silicone, "SH-550" manufactured by Toray Dow Corning Co., Ltd. (kinematic viscosity at 40 °C: 75.3 mm 2 / s, kinematic viscosity at 100 °C: 20.1 mm 2 / s, VI: 291) · Silicone 2 used in comparative test: Alkyl silicone, "KF-4917" manufactured by Shin-Etsu Chemical Co., Ltd. (kinematic viscosity at 40 °C: 13.8 mm 2 / s, kinematic viscosity at 100 °C: 4.6 mm 2 / s, VI: 292)

[0149] [Examples 1 to 22 and Comparative Examples 1 to 6] For Examples 1 to 10, various siloxane compounds (silicone oils) obtained in the above Synthesis Examples shown in Table 2 were used as they were. For Examples 11 to 22 and Comparative Examples 1 to 6, the respective components were blended so as to have the ratios (mass %) shown in Tables 2 and 3 below, and each lubricating oil composition was prepared by heating (A) silicone oil, (B) hydrocarbon oil, (C) extreme pressure agent, and (D) antioxidant and other additives to 100 °C and mixing them.

[0150] [Evaluation Method] For the siloxane compounds and lubricating oil compositions obtained in each of the Examples and Comparative Examples, the lubricity was evaluated by the following test methods.

[0151] (Viscosity Index) The viscosity index (VI) was measured and calculated according to JIS K 2283 (2000). The evaluation criteria were as follows.

[0152] Viscosity index (VI) 250 or more ◎ Viscosity index (VI) 180 - 250 ○ Viscosity index (VI) less than 180 ×

[0153] (Measurement of Residue Amount) 0.2 g of each sample was weighed into a glass petri dish with an inner diameter of 3 cm, heated in a constant temperature bath at 140 °C for 100 hours, and then heated in a constant temperature bath at 250 °C for 700 hours. Thereafter, the residue amount of each was measured. The evaluation criteria were as follows.

[0154] Ratio of residue (weight %) 10% or less ◎ Ratio of residue (weight %) more than 10% to 20% or less ○ Ratio of residue (weight %) more than 20% × The above results are shown in Tables 2 and 3.

[0155]

Table 2

[0156]

Table 3

[0157] Investigation From the results of Examples 1 to 10, it was shown that the siloxane compound of the present invention can achieve both a high viscosity index and low residue properties even when used alone.

[0158] Also, in Examples 11 to 22, it was shown that even when the siloxane compound of the present invention is used as a composition together with other components, it can also achieve both a high viscosity index and low residue properties. In particular, from the results of Examples 2 to 3 and 11 to 15, it was shown that the greater the blending amount of the siloxane compound, the less the residue after heating. Furthermore, from the results of Examples 16 to 17, it was found that the greater the blending amount of the siloxane compound, the more excellent it is in terms of viscosity index.

[0159] On the other hand, in Comparative Examples 1 to 6 where the siloxane compound of the present invention was not used, it was inferior to the results of the Examples in at least one of the viscosity index and low residue properties.

[0160] In particular, from the results of Comparative Examples 1 to 2, it was found that although the conventional silicone oil has a high viscosity index, it has a large amount of residue. Also, for the ester oil and PAG oil, which are synthetic oils used in Comparative Examples 3 to 5, although the amount of residue was small, they did not show a sufficient viscosity index. Even the PAG oil, which is known as a synthetic oil with a relatively high viscosity index, had a viscosity index of less than 180. In Comparative Example 6, although an attempt was made to combine a conventional silicone oil and an ester oil with a small amount of residue, the result was that the viscosity index decreased while the amount of residue could be suppressed.

[0161] This application is based on Japanese Patent Application No. 2019-229833 filed on December 20, 2019, the content of which is incorporated herein.

[0162] In order to describe the present invention, the present invention has been appropriately and fully described through embodiments with reference to specific examples and the like above. However, it should be recognized by those skilled in the art that it may be easy to make changes and / or improvements to the above-described embodiments. Therefore, as long as the modified or improved forms implemented by those skilled in the art do not depart from the scope of the claims described in the claims, the modified or improved forms are construed to be included in the scope of the claims of the claims.

Industrial Applicability

[0163] The siloxane compound and the lubricating oil composition of the present invention can be used as a lubricating oil having excellent lubricity, and thus can be suitably used as lubricants for various applications, for example, lubricants for turbo machines, lubricants for compressors, lubricants for hydraulic equipment, lubricants for machine tools, grease base oils, refrigeration oils, plasticizers, and the like. It is particularly suitable for applications with high loads.

Claims

1. A lubricant using a siloxane compound represented by the following formula (1). [Chemical Formula 1] [In formula (1), X １ is, independently or identically, hydrogen or an alkyl group having 1 to 12 carbon atoms, Y is an alkylene group having 2 to 12 carbon atoms, Z １ represents an alkylene group that is bonded to an adjacent silicon atom by a carbon-silicon bond and to a polyoxyalkylene block by an oxygen atom, p is an integer from 0 to 13, r is an integer from 0 to 16, q is 0, n is an integer from 2 to 4, a is an integer from 1 to 11, and r has an average number of 1.4 or more.

2. A lubricant using a siloxane compound represented by the following formula (1). 【Chemical 2】 [In formula (1), X １ is, the same or different, hydrogen, an alkyl group having 1 to 12 carbon atoms or a polyoxyalkyl group represented by the following formula (2), and X １ at least one of which is a polyoxyalkyl group represented by the following formula (2). Y is an alkylene group having 2 to 12 carbon atoms, Z １ represents an alkylene group that is bonded to an adjacent silicon atom by a carbon-silicon bond and to a polyoxyalkylene block by an oxygen atom, p is an integer from 0 to 13, q is an integer from 0 to 16, r is 0, n is an integer from 2 to 4, a is an integer from 0 to 11, and q has an average number of 1.

4. [Chemical Formula 3] (In formula (2), Z ２ represents an alkylene group that is bonded to an adjacent silicon atom by a carbon-silicon bond and to a polyoxyalkylene block by an oxygen atom, X ２ is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, m is an integer from 2 to 4, and b is an integer from 1 to 10.)]

3. The lubricant according to claim 1 or 2, wherein the siloxane compound has a mass average molecular weight of 500 to 11,000.

4. The lubricant according to any one of claims 1 to 3, wherein the siloxane compound has a viscosity index of 200 or more, and the residue amount after heating at 140 °C for 100 hours and then at 250 °C for 700 hours is 20% or less.

5. (A) A siloxane compound according to any one of claims 1 to 4, (B) A hydrocarbon-based lubricating oil, (C) At least one of an extreme pressure agent and (D) an antioxidant, and a lubricant containing at least these.

6. A grease using the lubricant according to any one of claims 1 to 5.

7. An emulsion using the lubricant according to any one of claims 1 to 5.

8. A lubrication method using the lubricant according to any one of claims 1 to 5.

9. A siloxane compound represented by the following formula (1) and having a mass average molecular weight of 500 to 11,000. 【Chemical Formula 4】 [In formula (1), X １ is, independently or identically, hydrogen or an alkyl group having 1 to 12 carbon atoms, Y is an alkylene group having 2 to 12 carbon atoms, Z １ represents an alkylene group that is bonded to an adjacent silicon atom by a carbon-silicon bond and to a polyoxyalkylene block by an oxygen atom, p is an integer from 0 to 13, r is an integer from 0 to 16, q is 0, n is an integer from 2 to 4, a is an integer from 1 to 11, and r has an average number of 1.4 or more.

10. The siloxane compound according to claim 9, having a viscosity index of 200 or more, and the residue amount after heating at 140 °C for 100 hours and then at 250 °C for 700 hours is 20% or less.

11. (A) A siloxane compound according to claim 9 or 10, (B) A hydrocarbon-based lubricating oil, (C) At least one of an extreme pressure agent and (D) an antioxidant, and a lubricating oil composition containing at least these.

12. A grease using the siloxane compound according to claim 9 or 10 or the lubricating oil composition according to claim 11.

13. An emulsion using the siloxane compound according to claim 9 or 10 or the lubricating oil composition according to claim 11.

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