JP7709919B2 - Low-residue siloxane compound, and lubricating oil composition and lubricant using same - Google Patents

Description

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

Lubricants and lubricating oil compositions are used to reduce friction and wear between moving parts or surfaces in a variety of mechanical devices.

Recently, the use environment of transportation equipment has become more extensive and harsh, leading to the sophistication and miniaturization of machinery and equipment. As machinery and equipment become more sophisticated and miniaturized, there is a demand for lubricants with a high viscosity index (VI) (small change in viscosity with respect to temperature changes) that can be used over a wide temperature range. Lubricants with a high VI have low viscosity at low temperatures and are excellent in terms of energy saving (energy conservation) because the energy loss due to the viscous resistance of the lubricant itself is small. In addition, in high temperature environments, compared to lubricants with a low VI, the viscosity does not become excessively low, so the oil film necessary for lubrication can be maintained on the lubricating surface, and because the appropriate viscosity is maintained, the lubricant is less likely to splash and contaminate the surroundings.

Until now, polymeric compounds such as polymethacrylates and polybutenes have generally been used as VI improvers to increase the viscosity index of hydrocarbon lubricating oils (Patent Documents 1 and 2).

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

However, siloxane compounds have a problem of leaving sludge (SiO ₂ ) as a residue after oxidative degradation, which can cause pipe blockage and filter clogging, so existing lubricants that contain siloxane compounds as the main ingredient have limited applications. Therefore, in order to expand into a wider range of fields, there is a demand for further improvement in lubricity and reduction of the residue, which is a bottleneck in the field of lubricants.

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

However, since the copolymer described in Patent Document 5 has a structure containing polysiloxane, problems of thickening and sludge formation due to deterioration arise.

In addition, in the technology described in Patent Document 6, polyalkylene glycol and ester oil are synthetic oils that do not increase in viscosity or produce much sludge after degradation. Therefore, it is considered that the lubricant composition also does not increase in viscosity or produce much sludge after degradation. However, in order to make a composition that can be used in a wide temperature range (having a high viscosity index), which is the trend of recent lubricants, the VI of these mixed base oils is insufficient, and it is necessary to add a VI improver (a polymer additive). VI improvers not only cause an increase in low-temperature viscosity, but also have the problem of impairing the initial lubricant properties (causing a decrease in viscosity) due to the effect of shear force in the lubricant's operating environment.

The object of the present invention is to solve the problems described above. That is, the object is to provide a siloxane compound and a lubricating oil composition using the same that have excellent lubricity, a high viscosity index (VI), and low residue.

JP 2015-172165 A JP 2017-155193 A JP 2012-207082 A JP 2003-261892 A Japanese Patent Application Publication No. 9-286230 JP 2018-28024 A

As a result of intensive research into solving the above problems, the inventors discovered that the above objective could be achieved by the following configuration, and further research based on this knowledge led to the completion of the present invention.

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

[In formula (1),
X ¹ may be the same or different and is a hydrogen atom, 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;
^Z1 represents a divalent organic group bonded to an adjacent silicon atom by a carbon-silicon bond and to the 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.
(In formula (2),
^Z2 represents a divalent organic group bonded to an adjacent silicon atom by a carbon-silicon bond and to the polyoxyalkylene block by an oxygen atom;
^X2 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.

FIG. 1 shows the NMR data of the silicone A-2 synthesized in the example. FIG. 2 shows NMR data for the silicone A-4 synthesized in the example. FIG. 3 shows NMR data for the silicone A-5 synthesized in the example. FIG. 4 shows NMR data for the silicone A-9 synthesized in the example. FIG. 5 shows NMR data for the silicone A-10 synthesized in the example. FIG. 6 shows NMR data for a dimethylsiloxane-hexylene copolymer in which both ends of the silicone molecule are blocked with hydrodimethylsiloxy groups, which was synthesized in the examples. FIG. 7 shows NMR data for the silicone A-13 synthesized in the example.

The following describes in detail the embodiments of the present invention, but the present invention is not limited to these.

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

The siloxane compound of this embodiment has a high viscosity index and low residue, making it possible to use it as a lubricant in a wide range of fields.

In other words, according to the above configuration, it is possible to provide a siloxane compound having excellent lubricity and low residue, as well as a lubricating oil composition using the same.

In the above formula (1), X ^{1 s} may be the same or different and each is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a polyoxyalkyl group represented by the following formula (2).
In the above formula (2), ^X2 represents hydrogen or an alkyl group having 1 to 12 carbon atoms.

In the above formula (1) and formula (2), the structure of the alkyl group having 1 to 12 carbon atoms in ^X1 and ^X2 is not particularly limited, and may be linear, branched, or cyclic. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an octyl group, a nonyl group, and a dodecyl group. ^X1 may contain one type of these functional groups alone in the structure, or two or more types in combination.

From the viewpoint of maintaining a low viscosity at low temperatures, the carbon number of ^X1 and ^X2 is preferably 1 to 12, more preferably 1 to 10, and particularly preferably 1 to 8. If the carbon number of ^X1 and ^X2 exceeds 12, the low temperature properties are significantly deteriorated, and it becomes difficult to use the lubricating oil composition in a low temperature range.

In the above formulas (1) and (2), Z ¹ and Z ² each represent a divalent organic group bonded to an adjacent silicon atom by a carbon-silicon bond and to a polyoxyalkylene block by an oxygen atom. The structure of the divalent organic group in ^Z1 and ^Z2 is not particularly limited, and examples thereof include -R-, -R-CO-, -R-NHCO-, -R-NHCONH- ^R2 -NHCO-, -R-OOCNH- ^R2 -NHCO- (wherein R is a divalent alkylene group such as ethylene, propylene, butylene, and ^R2 is _a divalent arylene group such as _-C6H4- , _{-C6H4 -C6H4- , -C6H4 - CH} ( _CH3 ) ₂ - _C6H4- . Suitably, ^R2 is a phenylene group). More suitably, ^Z1 and ^Z2 are divalent alkylene groups, particularly ethylene and _propylene .

In the above formula (1), Y is an alkylene group having 2 to 12 carbon atoms. There are no particular limitations on the structure of Y, and it may be linear, branched, or cyclic.

Specific examples include alkylene groups such as ethylene, propylene, butylene, and hexylene. These functional groups may be contained in the structure alone or in combination of two or more.

From the viewpoint of maintaining a low viscosity at low temperatures, the number of carbon atoms in 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 in the alkylene group in Y exceeds 12, the low-temperature properties may be significantly deteriorated.

From the viewpoint of obtaining the viscosity required for 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 portion in the molecular structure decreases, and there is a risk of the viscosity index decreasing.

In addition, in the above formula (1), p is an integer from 0 to 13. If p exceeds 13, there is a risk that the amount of residue after thermal degradation will be large.

In the above formula (1), q and r are the same or different and are integers from 0 to 16. If these values exceed 16, the viscosity of the lubricating oil may become too high, which may result in a lack of energy saving properties.

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.

In addition, 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.

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

The mass average molecular weight of the siloxane compound of this embodiment is not particularly limited, but is preferably 500 to 11,000. If the mass average molecular weight is below 500, there is a risk of a large amount of evaporation. Also, if the mass average molecular weight exceeds 11,000, the viscosity becomes too high as a lubricant, and energy saving properties are lacking, which is not preferable.

The mass average molecular weight of the siloxane compound in this embodiment is a value measured by ¹ H-NMR as shown in the examples described later. Hereinafter, the mass average molecular weight will also be simply referred to as "average molecular weight".

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

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

The method for synthesizing the siloxane compound as described above is not particularly limited, but some manufacturing examples are as follows: for example, the siloxane compound (silicone oil) of this embodiment can be obtained by hydrosilylation reaction of dimethylsiloxane blocked at both ends of the molecular chain with hydrodimethylsiloxy groups and divinyl ether of polyalkylene glycol in the presence of a platinum catalyst. Alternatively, the siloxane compound (silicone oil) can be obtained by hydrosilylation reaction of dimethylsiloxane blocked at both ends of the molecular chain with hydrodimethylsiloxy groups and divinyl ether of polyalkylene glycol in the presence of a platinum catalyst, and then hydrosilylation reaction of the dimethylsiloxane with an olefin compound in the presence of a platinum catalyst.

The siloxane compound of this embodiment can be used alone as various lubricants, but it may also be used as a lubricating oil composition in combination with a hydrocarbon lubricating oil as described below and at least one of an antioxidant and an extreme pressure agent.

That is, the lubricating oil composition of this 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.

The viscosity index (VI) of the lubricating oil composition of this embodiment is preferably 180 or more. More preferably, it is 200 or more, and even more preferably, it is 250 or more.

In the lubricating oil composition of this embodiment, the content of the siloxane compound (A) relative to the entire composition is 30 to 95 mass% from the viewpoint of viscosity index and lubricity. In particular, 50 to 90 mass% is preferable, and 60 to 90 mass% is even more preferable. Even if the content of component (A) is less than 30 mass%, it is possible to improve the viscosity index when the lubricating oil composition is made, but the effect of improving the viscosity index is poor, and there is no particular upper limit, and as described above, 100 mass% may be the siloxane compound.

Below, we will explain the components other than the siloxane compound in the lubricating oil composition of this embodiment.

((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-mentioned (A) siloxane compound (silicone oil), but specific examples include ester oil, ether oil, poly-alpha-olefin (PAO) oil, mineral oil, etc.

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

The monohydric alcohol or polyhydric alcohol may be a monohydric alcohol or polyhydric alcohol having a hydrocarbon group having 1 to 30 carbon atoms, preferably 4 to 20 carbon atoms, and more preferably 6 to 18 carbon atoms. Specific examples of the polyhydric alcohol include trimethylolpropane, pentaerythritol, and dipentaerythritol.

Furthermore, the monobasic acid or polybasic acid may be a monobasic acid or polybasic acid having a hydrocarbon group having 1 to 30 carbon atoms, preferably 4 to 20 carbon atoms, and more preferably 6 to 18 carbon atoms.

The hydrocarbon group referred to here may be linear or branched, and examples include hydrocarbon groups such as alkyl groups, alkenyl groups, cycloalkyl groups, alkylcycloalkyl groups, aryl groups, alkylaryl groups, and arylalkyl groups.

When an ester oil is used as component (B) in this embodiment, the above-mentioned ester oils may be used alone or in a mixture of two or more types.

In a preferred embodiment, the ester oil may be 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. In particular, from the viewpoint of low volatility, polyhydric alcohol fatty acid esters such as fatty acid esters of trimethylolpropane and fatty acid esters of pentaerythritol are more preferable.

Specific examples of the ether oil include polyoxyethers, dialkyl ethers, aromatic ethers, etc.

Examples of the poly-alpha-olefin oil include polymers of alpha-olefins having 2 to 15 carbon atoms, such as polybutene, 1-octene oligomer, and 1-decene oligomer, or hydrogenated products thereof.

Examples of the mineral oil include atmospheric residual oil obtained by atmospheric distillation of crude oils such as paraffinic, naphthenic, and intermediate base oils; distillate oil obtained by vacuum distillation of the atmospheric residual oil; mineral oil refined by subjecting the distillate oil to one or more of the following processes: solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining, etc., such as light neutral oil, medium neutral oil, heavy neutral oil, bright stock, etc.; and mineral oil obtained by isomerizing wax produced by the Fischer-Tropsch process (GTL wax (Gas To Liquids WAX)).

In this embodiment, the hydrocarbon-based lubricating oils described above can be used alone as component (B), or two or more types can be used in combination.

The content of (B) hydrocarbon-based lubricating oil in the lubricating oil composition of this embodiment is 0 to 70 mass% of the entire composition from the viewpoints of lubricity and viscosity index. In particular, 10 to 50 mass% is preferable, and 10 to 20 mass% is even more preferable. If the content of the hydrocarbon-based lubricating oil is less than 10 mass%, it becomes difficult to obtain sufficient lubricity, and if it exceeds 70 mass%, the content of (A) siloxane compound in the lubricating oil composition becomes small, and the viscosity index of the lubricating oil composition becomes low, which is not preferable.

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

((C) Extreme Pressure Agent)
The lubricating oil composition of the present embodiment contains at least one of (C) an extreme pressure agent or (D) an antioxidant, which will be described later.

When the lubricating oil composition of this embodiment contains (C) an extreme pressure agent, the lubricating oil composition of this embodiment has the advantage of being able to further improve lubricity and wear resistance.

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

In particular, it is preferable to use at least one selected from thiophosphate esters, dithiocarbamates, sulfurized olefins, and dimercaptothiadiazole-based compounds as the extreme pressure agent (C).

When the lubricating oil composition of this embodiment contains an extreme pressure agent (C), the content is about 0.5 to 10.0 mass% of the entire composition from the viewpoint of obtaining sufficient wear resistance. By containing the extreme pressure agent (C) at such a content, there is an advantage that it is possible to achieve both an extreme pressure effect and an increase in the evaporation amount of the lubricating oil composition due to the evaporation of the extreme pressure agent itself.

((D) Antioxidants)
When the lubricating oil composition of this embodiment contains an antioxidant (D), there is an advantage in that the life of the lubricating oil composition can be extended.

The antioxidant (D) used in this embodiment may be any antioxidant commonly used in lubricating oils, without any particular limitations. Examples include phenolic compounds, amine compounds, phosphorus compounds, etc.

More specifically, examples of such compounds include alkylphenols such as 2,6-di-tert-butyl-4-methylphenol, bisphenols such as methylene-4,4-bisphenol (2,6-di-tert-butyl-4-methylphenol), naphthylamines such as phenyl-α-naphthylamine, dialkyldiphenylamines, and phosphites.

Among these, from the viewpoint of further improving lubricity, it is preferable to include phosphorus-based compounds such as phosphate esters, phosphites, acid phosphate esters, and phosphonate esters.

In addition, the lubricating oil composition of this embodiment preferably uses two or more types of (D) antioxidants in combination. For example, it is particularly preferable to use a phenolic compound or an amine compound that functions as a primary antioxidant in combination with a secondary antioxidant such as a phosphorus compound.

When the lubricating oil composition of this embodiment contains an antioxidant (D), the content of the antioxidant (D) relative to the entire composition is 0.5 to 10.0 mass % from the viewpoint of inhibiting oxidation and reducing the amount of evaporation. More preferably, it is 2.0 to 7.0 mass %. By containing the antioxidant (D) at such a content, there is an advantage that it is possible to achieve both an antioxidant effect and an increase in the amount of evaporation of the lubricating oil composition due to the evaporation of the antioxidant itself.

From the viewpoint of further enhancing lubricity, it is preferable to contain both the extreme pressure agent (C) and the antioxidant (D), and in that case, it is preferable that the total amount of these is approximately 0.5 to 10.0 mass% of the entire composition.

(Other additives)
For the purpose of further improving the performance of the lubricating oil composition of this embodiment, or for the purpose of imparting further performance as necessary, various additives such as metal deactivators, antifoaming agents, thickeners, colorants, etc. may be blended alone or in combination, within a range that does not impair the effects of the present invention.

Examples of metal deactivators include benzotriazole-based, tolyltriazole-based, and imidazole-based compounds.

Examples of antifoaming agents include polysiloxanes, polyacrylates, and styrene ester polymers.

Examples of thickening agents include metal soaps (e.g., lithium soaps), silica, expanded graphite, polyurea, clays (e.g., hectorite or bentonite), etc.

When the additives described above are blended in the lubricating oil composition of this embodiment, the additives may be added in an amount of about 0.0 to 10.0 mass %, or about 0.1 to 5 mass %, based on the entire lubricant composition (total mass). A thickener for producing a grease using the lubricating oil composition of this embodiment may be used in an amount of 5 to 25 mass % based on the entire lubricant grease composition (total mass).

(Preparation method)
The method for preparing the lubricating oil composition of this embodiment is not particularly limited, and the composition can be prepared, for example, by heating (A) the siloxane compound, (B) the hydrocarbon oil, and at least one of (C) the extreme pressure agent and (D) the antioxidant, and other additives, to 100° C. and mixing them.

(Application)
The lubricating oil composition of the present embodiment can be used for a long time with stability at a wide range of temperatures, and therefore can be used as various lubricants.For example, it can be suitably used as a lubricant for turbomachinery, 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 the residue generated when heated and burned is smaller than that of the conventional lubricating oil composition, pipe blockage and filter clogging caused by the residue are unlikely to occur, and it is suitable for applications in which lubricants are used in a circulation system.

As described above, this specification discloses various aspects of the technology, the main technologies of which are summarized below.

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

[In formula (1),
X ¹ is the same or different and is a hydrogen atom, 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;
^Z1 represents a divalent organic group bonded to an adjacent silicon atom by a carbon-silicon bond and to the 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.
(In formula (2),
^Z2 represents a divalent organic group bonded to an adjacent silicon atom by a carbon-silicon bond and to the polyoxyalkylene block by an oxygen atom;
^X2 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.

This configuration makes it possible to provide a siloxane compound that has excellent lubricity and low residue.

In addition, it is preferable that the siloxane compound has a viscosity index of 200 or more and has a residue amount of 20% or less after heating at 140°C for 100 hours and then at 250°C for 700 hours. This is believed to make it possible to more reliably obtain the above-mentioned effects.

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, and at least one of (C) an extreme pressure agent and (D) an antioxidant. With this configuration, it is possible to provide a lubricating oil composition having excellent lubricity and low residue.

A lubricant according to yet 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 or lubricant using the same, a grease or emulsion using them, and a lubricating method using them.

Examples of the present invention will be described below, but the present invention is not limited to these.
First, the raw materials used in this example are shown below.

[(A) Synthesis of 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.

(Synthesis Example 1: Silicones A-2 and A-3)
In a 500 mL separable flask, 150 g (1.1 mol) of the 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 placed and stirred at 65° C. for 7 hours. After cooling to room temperature, the activated clay was removed by filtration. The filtrate was then placed in a 500 mL separable flask, heated and decompressed to obtain, as a distillate, 191 g of a low molecular weight dimethylsiloxane terminated at both ends of the molecular chain by hydrodimethylsiloxy groups (silicone A-2) and 343 g of a high molecular weight dimethylsiloxane terminated at both ends of the molecular chain by hydrodimethylsiloxy groups (silicone A-3) remaining in the kettle.

Analysis of the obtained Silicone A-2 and Silicone A-3 using ¹ H-NMR revealed 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, while 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.

Figure 1 shows NMR data for Silicone A-2.

^{The 1} H-NMR analysis method for the dimethylsiloxanes capped at both molecular chain terminals with hydrodimethylsiloxy groups shown in Silicones A-2 to A-3 is as follows.
A (chemical shift of 0.05 to 0.10 ppm) indicates a peak of hydrogen derived from the methyl group of the repeating unit of dimethylsiloxane.
b (chemical shift 0.17 to 0.22 ppm) indicates a peak of hydrogen derived from the methyl groups of the hydrodimethylsiloxy groups at both ends of the molecular chain.

The average molecular weight and the average number of dimethyl units (p in the above formula (1)) were calculated from the integral values (ratio) of the peaks a and b using the following formulas.
Average number of dimethyl units = 2a ÷ b
Average molecular weight = average number of dimethyl units x molecular weight of dimethyl units + molecular weight of hydrodimethylsiloxy groups at both ends of molecular chain

The NMR data of Silicone A-2 was as follows:
¹ H-NMR (solvent: deuterated chloroform, standard substance: TMS)
If the integral value of δ=0.05 to 0.10 ppm is 10.0,
The integral value for δ=0.17 to 0.22 ppm is 3.8.

(Synthesis Example 2: Silicone A-4)
A 200 mL separable flask was charged with 40 g (77 mmol) of dimethylsiloxane capped at both molecular chain terminals with hydrodimethylsiloxy groups (average molecular weight 522, average number of dimethyl units (p in the above formula (1)) 5.2) obtained by the same method as in Synthesis Example 1, and 25 mg of Pt alumina powder (Pt equivalent: 21 ppm) which is a platinum catalyst manufactured by N.E. Chemcat Corporation. 19 g (38 mmol) of polyethylene glycol diallyl ether (product name: Uniox AA-480R) manufactured by NOF Corporation was charged into the dropping funnel, and nitrogen substitution was performed. The mixture of dimethylsiloxane capped at both molecular chain terminals with hydrodimethylsiloxy groups and the platinum catalyst was heated, and after the temperature of the mixture reached 85° C., the dropping of polyethylene glycol diallyl ether was started. After all the polyethylene glycol diallyl ether had been dropped, the mixture was aged at 125° C. for 6 hours. After completion of the aging, 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. The filtrate was then placed in a 200 mL separable flask and heated and decompressed to remove the remaining dimethylsiloxane capped at both molecular chain ends with hydrodimethylsiloxy groups from the reaction product, yielding 51 g of a dimethylsiloxane-polyether copolymer capped at both molecular chain ends with hydrodimethylsiloxy groups (Silicone A-4).

Analysis of the obtained Silicone A-4 using ¹ H-NMR revealed that Silicone A-4 had an average molecular weight of 3,546, 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 units of oxyethylene (a in the above formula (1)).

Figure 2 shows NMR data for Silicone A-4.

The ¹ H-NMR analysis method for Silicone A-4, and dimethylsiloxane-polyether copolymers terminated at both molecular ends with hydrodimethylsiloxy groups, shown as Silicone A-7, A-8, and A-12 described below, is as follows.
The peak a (chemical shift 0.01 to 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 polyether.
b (chemical shift 0.16 to 0.21 ppm) indicates a peak of hydrogen derived from the methyl groups of the hydrodimethylsiloxy groups at both ends of the molecular chain.
c (chemical shift 0.40 to 1.10 ppm) indicates the peak of hydrogen derived from _CH2 next to the silicon of the polyether moiety bonded to silicon.
d (chemical shift 3.30 to 3.70 ppm) indicates the peak of hydrogen derived from _CH2 bonded to the repeating portion of oxyethylene in the polyether portion and to oxygen in the hydrocarbon portion connecting the repeating portion of oxyethylene and silicon.

The average molecular weight, the average number of dimethyl units, the average number of dimethylsiloxane polyether repeating units, and the average number of oxyethylene repeating units were each calculated from the integral values (ratios) of the peaks a, b, c, and d using the following formulas.
Average number of dimethyl units = (2a - 6b - c) ÷ 3b
Average number of repeating units of dimethylsiloxane polyether =
3b÷c
Number of repeats of oxyethylene = d ÷ b - 1
Average molecular weight = (number of oxyethylene repeats x molecular weight of oxyethylene + average number of dimethyl units x molecular weight of dimethyl units + molecular weight of hydrocarbon units connecting polyether units and silicon + molecular weight of silicon units connected via polyether units and hydrocarbon units) x average number of dimethylsiloxane/polyether repeat units + average number of dimethyl units x molecular weight of dimethyl units + molecular weight of hydrodimethylsiloxy groups at both ends of molecular chain

The NMR data of Silicone A-4 was as follows:
¹ H-NMR (solvent: deuterated chloroform, standard substance: TMS)
If the integral value of δ=0.01 to 0.10 ppm is 10.0,
The integral value for δ=0.16 to 0.21 ppm is 1.0
The integral value for δ=0.40 to 1.10 ppm is 0.9
The integral value for δ=3.30 to 3.70 ppm is 10.6.

(Synthesis Example 3: Silicone A-5)
A 200 mL separable flask was charged with 20 g (36 mmol) of dimethylsiloxane capped with hydrodimethylsiloxy groups at both molecular chain ends (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. 24 g (214 mmol) of diisobutylene manufactured by Idemitsu Kosan Co., Ltd. and 3 μL of Pt-CTS-toluene solution (Pt equivalent: 2 ppm), which is a platinum catalyst manufactured by N.E. Chemcat Corporation, were charged into the dropping funnel, and nitrogen substitution was performed. The mixed solution of dimethylsiloxane capped with hydrodimethylsiloxy groups at both molecular chain ends and toluene was heated, and after the liquid temperature reached 60° C., the dropwise addition of the mixed solution of diisobutylene and platinum catalyst was started. After the mixed solution of diisobutylene and platinum catalyst was all dropped, the mixture was aged at 95° C. for 4.5 hours. After completion of the aging, disappearance of the peak of the SiH group was confirmed using ¹ H-NMR. Subsequently, the reaction mixture was heated and depressurized to remove the remaining diisobutylene and the toluene used as the solvent from the reaction mixture, yielding 28 g of dimethylsiloxane capped at both molecular ends with isooctyldimethylsiloxane groups (Silicone A-5).

Analysis of the obtained Silicone A-5 using ¹ H-NMR revealed that Silicone A-5 had an average molecular weight of 739 and an average number of dimethyl units (p in the above formula (1)) of 5.1.

Figure 3 shows NMR data for Silicone A-5.

The ¹ H-NMR analysis method for Silicone A-5 and the dimethylsiloxane terminated at both molecular ends with alkyldimethylsiloxy groups shown in Silicone A-6 described below is as follows.
A (chemical shift 0.06 to 0.12 ppm) indicates a 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 next to the silicon of the alkyl group bonded to the silicon.

The average molecular weight and the average number of dimethyl units were calculated from the integral values (ratio) of the peaks a and b using the following formulas.
Average number of dimethyl units = 2a ÷ 3b
Average molecular weight = average number of dimethyl units x molecular weight of dimethyl units + molecular weight of alkyldimethylsiloxy groups at both ends of molecular chain

The NMR data of Silicone A-5 was as follows:
¹ H-NMR (solvent: deuterated chloroform, standard substance: TMS)
If the integral value of δ=0.06 to 0.12 ppm is 10.0,
The integral value for δ=0.45 to 0.72 ppm is 1.3.

(Synthesis Example 4: Silicone A-6)
In a 200 mL separable flask, 23 g (41 mmol) of dimethylsiloxane capped with hydrodimethylsiloxy groups at both molecular chain ends (average molecular weight 558, average number of dimethyl units (p) 5.7) obtained by the same method as in Synthesis Example 1 and 71 g of toluene were placed, and 18 g (214 mol) of 1-hexene (trade name: Linearene 6) manufactured by Idemitsu Kosan Co., Ltd. and 3 μL of Pt-CTS-toluene solution (Pt equivalent: 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 capped with hydrodimethylsiloxy groups at both molecular chain ends and toluene was heated, and after the liquid temperature reached 60° C., the dropwise addition of the mixed solution of 1-hexene and platinum catalyst was started. After the mixed solution of 1-hexene and platinum catalyst was all dropped, it was aged at 80° C. for 6 hours. After aging, the disappearance of the SiH group peak was confirmed using ¹ H-NMR. The reaction mixture was then heated and depressurized to remove the remaining 1-hexene and the toluene used as the solvent, yielding 30 g of dimethylsiloxane capped at both molecular terminals with hexyldimethylsiloxane groups (Silicone A-6).

Analysis of the obtained Silicone A-6 using ¹ H-NMR revealed 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.

(Synthesis Example 5: Silicone A-7)
Into a 200 mL separable flask were placed 25 g (48 mmol) of dimethylsiloxane capped with hydrodimethylsiloxy groups at both molecular chain ends (average molecular weight 522, average number of dimethyl units (p in the above formula (1)) 5.2) obtained by the same method as in Synthesis Example 1, 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 equivalent: 20 ppm) which is a platinum catalyst manufactured by N.E. Chemcat Corporation, and nitrogen substitution was performed. The mixed solution was heated and aged at 60° C. for 5 hours. After the aging was completed, the disappearance of the peak of the unsaturated double bond was confirmed using ¹ H-NMR. Subsequently, the mixture was cooled to room temperature, and the platinum catalyst was removed by filtration.

The filtrate was then placed in a 200 mL recovery flask, heated and depressurized to remove the remaining dimethylsiloxane terminated at both ends of the molecular chain with hydrodimethylsiloxy groups and the toluene used as the solvent from the reaction product, yielding 20 g of dimethylsiloxane-polyether copolymer terminated at both ends with hydrodimethylsiloxy groups (Silicone A-7).

Analysis of the obtained Silicone A-7 using ¹ H-NMR revealed that Silicone A-7 had an average molecular weight of 1,470, an average number of dimethyl units (p in the above formula (1)) of 4.9, an average number of dimethylsiloxane polyether repeating units (r in the above formula (1)) of 1.4, and an average number of oxyethylene repeating units (a in the above formula (1)) of 3.1.

(Synthesis Example 6: Silicone A-8)
In a 500 mL separable flask, 150 g (287 mmol) of the silicone A-2 obtained in 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 (Pt equivalent: 20 ppm) of Pt alumina powder, which is a platinum catalyst manufactured by N.E. Chemcat Co., Ltd., were placed, and nitrogen substitution was performed. The mixed solution was heated and aged at 75° C. for 4.5 hours. After the aging was completed, the disappearance of the peak of the unsaturated double bond was confirmed using ¹ H-NMR. Subsequently, after cooling to room temperature, the platinum catalyst was removed by filtration.

The filtrate was then placed in a 500 mL recovery flask, heated and depressurized to remove the remaining dimethylsiloxane terminated at both ends of the molecular chain with hydrodimethylsiloxy groups and the toluene used as the solvent from the reaction product, yielding 160 g of dimethylsiloxane-polyether copolymer terminated at both ends with hydrodimethylsiloxy groups (Silicone A-8).

Analysis of the obtained Silicone A-8 using ¹ H-NMR revealed that Silicone A-8 had an average molecular weight of 2760, an average number of dimethyl units (p in the above formula (1)) of 4.6, an average number of dimethylsiloxane polyether repeating units (r in the above formula (1)) of 3.5, and an average number of oxyethylene repeating units (a in the above formula (1)) of 3.0.

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

Analysis of the obtained Silicone A-9 using ¹ H-NMR revealed that Silicone A-9 had an average molecular weight of 2772, an average number of dimethyl units (p in the above formula (1)) of 4.4, an average number of dimethylsiloxane polyether repeating units (r in the above formula (1)) of 3.3, and an average number of oxyethylene repeating units (a in the above formula (1)) of 3.1.

Figure 4 shows NMR data for Silicone A-9.

The ¹ H-NMR analysis method for the dimethylsiloxane-polyether copolymer capped at both ends of the molecule with alkyldimethylsiloxy groups shown in Silicone A-9 and Silicone A-11 described below is as follows.
The peak 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 a polyether, and the methyl group of the dimethylsiloxane unit bonded to an alkyl group.
b (chemical shift 0.80 to 0.95 ppm) indicates the peak of hydrogen derived from _CH3 at the end of the alkyl group bonded to silicon.
c (chemical shift 0.95 to 1.10 ppm) indicates the peak of hydrogen derived from the CH _{2 next to the CH 2 next} to the silicon of the polyether moiety bonded to silicon.
d (chemical shift 3.30 to 3.75 ppm) indicates the peak of hydrogen derived from _CH2 bonded to the repeating portion of oxyethylene in the polyether portion and to oxygen in the hydrocarbon portion connecting the repeating portion of oxyethylene and silicon.

The average molecular weight, the average number of dimethyl units, the average number of dimethylsiloxane polyether repeating units, and the average number of oxyethylene repeating units were each calculated from the integral values (ratios) of the peaks a, b, c, and d using the following formulas.
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 oxyethylene repeats x molecular weight of oxyethylene + average number of dimethyl units x molecular weight of dimethyl units + molecular weight of hydrocarbon units connecting polyether units and silicon + molecular weight of silicon units connected via polyether units and hydrocarbon units) x average number of dimethylsiloxane/polyether repeat units + average number of dimethyl units x molecular weight of dimethyl units + molecular weight of alkyldimethylsiloxy groups at both ends of molecular chain

The NMR data of Silicone A-9 was as follows:
¹ H-NMR (solvent: deuterated chloroform, standard substance: TMS)
If the integral value of δ=0.05 to 0.15 ppm is 10.0,
The integral value for δ=0.80 to 0.95 ppm is 0.4
The integral value for δ=0.95 to 1.10 ppm is 0.9
The integral value for δ=3.50 to 3.75 ppm is 3.6.

(Synthesis Example 8: Silicone A-10)
In a 200 mL separable flask, 25 g (9 mmol) of the silicone A-8 obtained in Synthesis Example 7 and 53 g of toluene were placed, and 5 g (42 mmol) of alpha methylstyrene (AMS) manufactured by Mitsui Chemicals, Inc., 11 g of toluene, and 55 μL (Pt equivalent: 47 ppm) of a platinum catalyst Pt-CTS-toluene solution manufactured by N.E. Chemcat Corporation were placed in a dropping funnel, and nitrogen substitution was performed. 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 the entire mixed solution in the dropping funnel was dropped, the mixture was aged at 80° C. for 22 hours. After the aging was completed, the disappearance of the peak of the SiH group was confirmed using ¹ H-NMR. Subsequently, the reaction mixture was heated and depressurized to remove the remaining alpha-methylstyrene (AMS) and the toluene used as the solvent, yielding 24 g of a dimethylsiloxane-polyether copolymer (silicone A-10) terminated at both molecular ends with 2-phenylpropyldimethylsiloxy groups.

Analysis of the obtained Silicone A-10 using ¹ H-NMR revealed that Silicone A-10 had an average molecular weight of 3,933, an average number of dimethyl units (p in the above formula (1)) of 4.7, an average number of dimethylsiloxane polyether repeating units (r in the above formula (1)) of 4.8, and an average number of oxyethylene repeating units (a in the above formula (1)) of 2.9.

Figure 5 shows NMR data for Silicone A-10.

The ¹ H-NMR analysis method for the dimethylsiloxane-polyether copolymer terminally blocked with 2-phenylpropyldimethylsiloxane groups shown as Silicone A-10 is as follows.
The peak 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 and the methyl group of the dimethylsiloxane unit bonded to polyether.
b (chemical shift 0.99 to 1.05 ppm) indicates the peak of hydrogen derived from _CH2 next to the silicon of the polyether moiety bonded to silicon.
The peak c (chemical shift 2.85 to 3.00 ppm) indicates a peak of hydrogen derived from CH of an aralkyl group bonded to silicon.
d (chemical shift 3.30 to 3.75 ppm) indicates the peak of hydrogen derived from _CH2 bonded to the repeating portion of oxyethylene in the polyether portion and to oxygen in the hydrocarbon portion connecting the repeating portion of oxyethylene and silicon.

The average molecular weight, the average number of dimethyl units, the average number of dimethylsiloxane polyether repeating units, and the average number of oxyethylene repeating units were each calculated from the integral values (ratios) of the peaks a, b, c, and d using the following formulas.
Average number of dimethyl units = (2a - 6b) ÷ 3b
Average number of repeating units of dimethylsiloxane polyether = b ÷ 2c
Number of repeats of oxyethylene = d ÷ b - 1
Average molecular weight = (number of oxyethylene repeats x molecular weight of oxyethylene + average number of dimethyl units x molecular weight of dimethyl units + molecular weight of hydrocarbon units connecting polyether units and silicon + molecular weight of silicon units connected via polyether units and hydrocarbon units) x average number of dimethylsiloxane/polyether repeat units + average number of dimethyl units x molecular weight of dimethyl units + molecular weight of 2-phenylpropyldimethylsiloxy groups at both ends of the molecule

The NMR data of Silicone A-10 was as follows:
¹ H-NMR (solvent: deuterated chloroform, standard substance: TMS)
If the integral value of δ=0.01 to 0.15 ppm is 10.0,
The integral value for δ=0.99 to 1.05 ppm is 0.1
The integral value for δ=2.85 to 3.00 ppm is 1.0
The integral value for δ=3.30 to 3.75 ppm is 3.8.

(Synthesis Example 9: Silicone A-11)
In a 200 mL separable flask, 25 g (9 mmol) of the silicone A-8 obtained in Synthesis Example 7 and 50 g of toluene were placed, and 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 Pt-CTS-toluene solution (Pt equivalent: 49 ppm) which is a platinum catalyst manufactured by N.E. Chemcat Co., Ltd. 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 from the dropping funnel was started. After the entire mixed solution from the dropping funnel was dropped, the mixture was aged at 85° C. for 16 hours. After the aging was completed, the disappearance of the peak of the SiH group was confirmed using ¹ H-NMR. The reaction mixture was then heated and depressurized to remove the remaining 1-dodecene and the toluene used as the solvent, yielding 27 g of a dimethylsiloxane-polyether copolymer (silicone A-11) terminated at both molecular ends with dodecyldimethylsiloxy groups.

Analysis of the obtained Silicone A-11 using ¹ H-NMR revealed that Silicone A-11 had an average molecular weight of 2,865, an average number of dimethyl units (p in the above formula (1)) of 4.4, an average number of dimethylsiloxane polyether repeating units (r in the above formula (1)) of 3.2, and an average number of oxyethylene repeating units (a in the above formula (1)) of 3.0.

(Synthesis Example 10: Silicone A-12)
In a 200 mL separable flask, 35 g (66 mmol) of the 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 performed. The mixed solution was heated and aged at 75° C. for 3 hours. After the aging was completed, the disappearance of the peak of the unsaturated double bond was confirmed using ¹ H-NMR. Then, after cooling to room temperature, the platinum catalyst was removed by filtration.

The filtrate was then placed in a 100 mL recovery flask, heated and depressurized to remove any remaining Silicone A-2 from the reaction mixture, yielding 32 g of dimethylsiloxane-polyether copolymer (Silicone A-12) blocked at both ends with hydrodimethylsiloxy groups.

Analysis of the obtained Silicone A-12 using ¹ H-NMR revealed that Silicone A-12 had an average molecular weight of 10,572, an average number of dimethyl units (p in the above formula (1)) of 4.1, 16.2 repeating units of dimethylsiloxane polyether (r in the above formula (1)), and 3.0 repeating units of oxyethylene (a in the above formula (1)).

(Synthesis Example 11: Silicone A-13)
Into a 200 mL separable flask were placed 25 g (48 mmol) of dimethylsiloxane capped with hydrodimethylsiloxy groups at both molecular chain terminals (average molecular weight 522, average number of dimethyl units (p in the above formula (1)) 5.2) obtained by the same method 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 of Pt alumina powder (Pt equivalent: 19 ppm) which is a platinum catalyst manufactured by N.E. Chemcat Corporation, and the atmosphere was replaced with nitrogen. The mixed solution was heated and aged at 80° C. for 5 hours. After aging, the disappearance of the unsaturated double bond peak was confirmed using ¹ H-NMR. Subsequently, the solution was cooled to room temperature, and the platinum catalyst was removed by filtration.

The filtrate was then placed in a 100 mL recovery flask and heated and decompressed to remove the remaining dimethylsiloxane terminated at both molecular chain ends with hydrodimethylsiloxy groups and the toluene used as the solvent from the reaction product, yielding 14 g of a dimethylsiloxane-hexylene copolymer terminated at both molecular chain ends with hydrodimethylsiloxy groups. Analysis of the resulting copolymer using ¹ H-NMR revealed that the copolymer had an average molecular weight of 1201, an average number of dimethyl units (p in the above formula (1)) of 5.3, and a repeating unit of dimethylsiloxane-hexylene (q in the above formula (1)) of 1.1.

Figure 6 shows NMR data for a dimethylsiloxane-hexylene copolymer capped at both ends with hydrodimethylsiloxy groups.

The ¹ H-NMR analysis method for the dimethylsiloxane-hexylene copolymer terminated at both molecular ends with hydrodimethylsiloxy groups is as follows.
The peak a (chemical shift 0.01 to 0.11 ppm) indicates 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 to 0.21 ppm) indicates a peak of hydrogen derived from the methyl groups of the hydrodimethylsiloxy groups at both ends of the molecular chain.
c (chemical shift 0.45 to 0.60 ppm) indicates the peak of hydrogen derived from _CH2 next to the silicon of the hexylene group bonded to silicon.

The average molecular weight, the average number of dimethyl units, and the average number of dimethylsiloxane-hexylene repeating units were calculated from the integrals (ratios) of the peaks a, b, and c using the following formulas.
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 x molecular weight of dimethyl units + molecular weight of hexylene + molecular weight of silicon parts connected to hexylene parts) x average number of repeating units of dimethylsiloxane/hexylene + average number of dimethyl units x molecular weight of dimethyl units + molecular weight of hydrodimethylsiloxy groups at both ends of molecular chain

The NMR data for the dimethylsiloxane-hexylene copolymer terminated at both molecular ends with hydrodimethylsiloxy groups was as follows:
¹ H-NMR (solvent: deuterated chloroform, standard substance: TMS)
If the integral value of δ=0.01 to 0.11 ppm is 10.0,
The integral value for δ=0.17 to 0.21 ppm is 2.2
The integral value for δ=0.45 to 0.60 ppm is 0.8.

Next, 9 g (7 mmol) of the dimethylsiloxane-hexylene copolymer capped with hydrodimethylsiloxy groups at both ends of the molecule obtained above and 72 g of toluene were placed in a 200 mL separable flask, and 24 g (60 mmol) of methoxypolyethylene glycol allyl ether (trade name: Uniox PKA-5007) manufactured by NOF Corp. and 63 μL of Pt-CTS-toluene solution (Pt equivalent: 49 ppm) which is a platinum catalyst manufactured by N.E. Chemcat Corp. 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 from the dropping funnel was started. After the mixed solution from the dropping funnel was all dropped, the mixture was aged at 75° C. for 23 hours. After the aging was completed, the disappearance of the peak of the SiH group was confirmed using ¹ H-NMR. Distilled water and hexane were then added to the resulting reaction liquid, the hexane layer was recovered, and the hexane and toluene used as the solvent were removed, yielding 4 g of a dimethylsiloxane-hexylene copolymer capped at both molecular terminals with polyoxyalkyldimethylsiloxy groups (silicone A-13).

Analysis of the obtained Silicone A-13 using ¹ H-NMR revealed that Silicone A-13 had an average molecular weight of 1,897, an average number of dimethyl units (p in the above formula (1)) of 4.6, 1.4 dimethylsiloxane-hexylene repeating units (q in the above formula (1)), and 6.0 oxyethylene repeating units at the molecular terminals (b in the above formula (2)).

Figure 7 shows NMR data for silicone A-13.

The ¹ H-NMR analysis method for the dimethylsiloxane/alkylene copolymer capped at both ends of the molecule with polyoxyalkyldimethylsiloxy groups shown as Silicone A-13 is as follows.
The peak a (chemical shift 0.01 to 0.15 ppm) indicates the peaks of hydrogen derived from the methyl group of the repeating unit of dimethylsiloxane, the methyl group of the dimethylsiloxane unit bonded to a polyether, and the methyl group of the dimethylsiloxane unit bonded to a hexylene group.
b (chemical shift 1.20 to 1.40 ppm) indicates the peak of hydrogen derived from _CH2 of the hexylene group not bonded to silicon.
c (chemical shift 1.50 to 1.70 ppm) indicates the peak of hydrogen derived from the _CH2 next to the _CH2 next to the silicon of the polyoxyalkyl group bonded to the silicon.
d (chemical shift 3.50 to 3.70 ppm) indicates a peak of hydrogen derived from the repeating ethylene moiety of the polyoxyalkyl portion.

The average molecular weight, the average number of dimethyl units, the average number of dimethylsiloxane polyether repeating units, and the average number of oxyethylene repeating units were each calculated from the integral values (ratios) of the peaks a, b, c, and d using the following formulas.
Average number of dimethyl units = (4a - 6b - 18c) ÷ 3b
Average number of repeating units of dimethylsiloxane-hexylene = b ÷ 2c
Number of repeats of oxyethylene = d ÷ 2c
Average molecular weight = (average number of dimethyl units x molecular weight of dimethyl units + molecular weight of hexylene + molecular weight of silicon parts connected to hexylene parts) x average number of repeating units of dimethylsiloxane-hexylene + average number of dimethyl units x molecular weight of dimethyl units + molecular weight of polyoxyalkyldimethylsiloxy groups at both ends of molecular chain

The NMR data of Silicone A-13 was as follows:
¹ H-NMR (solvent: deuterated chloroform, standard substance: TMS)
If the integral value of δ=0.05 to 0.15 ppm is 10.0,
The integral value for δ=1.20 to 1.40 ppm is 1.5
The integral value for δ=1.50 to 1.70 ppm is 0.6
The integral value for δ=3.50 to 3.70 ppm is 6.7.

The above data on the (A) siloxane compound (silicone oil) are summarized in Table 1. In Table 1, X represents ^X1 and ^X2 in the above formulas (1) and (2), and Y, ^Z1 , p, q, r, a, n, ^Z2 , b, and m each have the same meaning as in the above formulas (1) and (2), respectively.

The residual amount (wt%) in the table was measured by the method described below. Of the silicone oils shown in Table 1, the value of p in formula (1) for Silicone A-3 exceeds 13, which is thought to be why the residual amount increased.

((B) Hydrocarbon-based lubricating oil)
Ester oil: pentaerythritol fatty acid ester manufactured by NOF Corporation, product name: Unistar HR-32 (40°C kinematic viscosity: 33.5 mm ² /s, 100°C kinematic viscosity: 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: Unistar 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 Corporation (40°C kinetic viscosity: 32.0 ^mm2 /s, 100°C kinetic viscosity: 6.5 ^mm2 /s, VI: 146)
PAO oil: poly-alpha-olefin manufactured by Chevron Phillips, product name: Synfluid PAO 6 cSt (40° C. kinematic viscosity: 30.5 mm ² /s, 100° C. kinematic viscosity: 5.9 mm ² /s, VI: 137)
Ether oil: MORESCO Corporation's alkyl diphenyl ether "MORESCO HILUBE LB-100" (40°C kinematic viscosity: 102.6 mm ² /s, 100°C kinematic viscosity: 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 (40°C kinetic viscosity: 12.6 ^mm2 /s, 100°C kinetic viscosity: 2.9 ^mm2 /s, VI: 56)
PAG (polyalkylene glycol): "Newpol HB50-660" manufactured by Sanyo Chemical Industries, Ltd. (40°C kinetic viscosity: 130.1 ^mm2 /s, 100°C kinetic viscosity: 20.1 ^mm2 /s, VI: 178)

((C) Extreme Pressure Agent)
Sulfur-based extreme pressure agent: isobutene sulfide, manufactured by RheinChemie, "RC 2545"
・Sulfur-phosphorus extreme pressure agent: thiophosphate ester, LUBRIZOL "LUBRIZOL IC9AW31"
Phosphorus-based extreme pressure agent: Amine salt of fatty acid phosphate ester, King Industries "NA-LUBE AW-6400FG"

((D) Antioxidants)
Primary antioxidant: Aromatic amine compound manufactured by BASF, "IRGANOX L-57" Primary antioxidant: Phenol compound manufactured by BASF, "IRGANOX L-135" Secondary antioxidant: Phosphite ester compound manufactured by Johoku Chemical Industry Co., Ltd., "JP-310"

(others)
Metal deactivator: Benzotriazole compound "CUVAN303" manufactured by VANDERBILT
Silicone 1 used in the comparative test: Methylphenyl silicone, "SH-550" manufactured by Dow Corning Toray 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 the 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)

[Examples 1 to 22 and Comparative Examples 1 to 6]
In Examples 1 to 10, the various siloxane compounds (silicone oils) obtained in the above synthesis examples, as shown in Table 2, were used as they were. In Examples 11 to 22 and Comparative Examples 1 to 6, the respective components were blended in the proportions (mass%) shown in Tables 2 and 3 below, and the (A) silicone oil, (B) hydrocarbon oil, (C) extreme pressure agent, and (D) antioxidant, as well as other additives, were heated to 100° C. and mixed to prepare respective lubricating oil compositions.

[Evaluation method]
The lubricating properties of the resulting siloxane compounds and lubricating oil compositions of each of the Examples and Comparative Examples were evaluated by the following test methods.

(viscosity index)
The viscosity index (VI) was measured and calculated in accordance with JIS K 2283 (2000). The evaluation criteria were as follows:

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

(Measurement of Residue Amount)
0.2 g of each sample was weighed into a glass petri dish having an inner diameter of 3 cm, and heated in a thermostatic chamber at 140° C. for 100 hours, and then heated in a thermostatic chamber at 250° C. for 700 hours. After that, the amount of residue of each sample was measured. The evaluation criteria were as follows:

Residue percentage (weight %) is 10% or less ◎
Residue ratio (weight %) is between 10% and 20%.
Residue percentage (weight %) is over 20% ×
The results are shown in Tables 2 and 3.

(Consideration)
The results of Examples 1 to 10 demonstrate that the siloxane compound of the present invention can achieve both a high viscosity index and low residue even when used alone.

Furthermore, Examples 11 to 22 show that a high viscosity index and low residue can be achieved even when the siloxane compound of the present invention is used in a composition together with other components. In particular, the results of Examples 2 to 3 and 11 to 15 show that a larger amount of siloxane compound results in significantly less residue after heating. Furthermore, the results of Examples 16 to 17 show that a larger amount of siloxane compound also results in a better viscosity index.

On the other hand, in Comparative Examples 1 to 6, which did not use the siloxane compound of the present invention, the results were inferior to those of the Examples in at least one of the viscosity index and low residue properties.

In particular, the results of Comparative Examples 1 and 2 showed that the commonly used silicone oils had a high viscosity index but a large amount of residue. The synthetic oils used in Comparative Examples 3 to 5, ester oil and PAG oil, had a small amount of residue but did not show a sufficient viscosity index. Even PAG oil, known as a synthetic oil with a relatively high viscosity index, had a viscosity index of less than 180. In Comparative Example 6, a conventional silicone oil was combined with an ester oil with a low amount of residue, and although the amount of residue was reduced, the viscosity index also decreased.

This application is based on Japanese Patent Application No. 2019-229833, filed on December 20, 2019, the contents of which are incorporated herein by reference.

In order to express the present invention, the present invention has been properly and sufficiently described above through the embodiments with reference to specific examples, etc., but it should be recognized that a person skilled in the art can easily change and/or improve the above-mentioned embodiments. Therefore, as long as the changes or improvements made by a person skilled in the art are not at a level that deviates from the scope of the claims described in the claims, the changes or improvements are interpreted as being included in the scope of the claims.

The siloxane compound and lubricating oil composition of the present invention can be used as a lubricating oil having excellent lubrication properties, and therefore can be suitably used as a lubricant for various applications, such as a lubricant for turbomachinery, a lubricant for compressors, a lubricant for hydraulic equipment, a lubricant for machine tools, a grease base oil, a refrigeration oil, a plasticizer, etc. It is particularly suitable for applications under high loads.

Claims (13)

A lubricant using a siloxane compound represented by the following formula (1):
[In formula (1),
X ¹ is the same or different and is hydrogen or an alkyl group having 1 to 12 carbon atoms;
Y is an alkylene group having 2 to 12 carbon atoms;
^Z1 represents an alkylene group bonded to an adjacent silicon atom by a carbon-silicon bond and to the polyoxyalkylene block by an oxygen atom;
p is an integer of 0 to 13, r is an integer of 0 to 16, q is 0, n is an integer of 2 to 4, a is an integer of 1 to 11 , and r is an average number of 1.4 or more. A lubricant using a siloxane compound represented by the following formula (1):
[In formula (1),
X ¹ are the same or different and each is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a polyoxyalkyl group represented by the following formula (2), and at least one of X ¹ is a polyoxyalkyl group represented by the following formula (2),
Y is an alkylene group having 2 to 12 carbon atoms;
^Z1 represents an alkylene group bonded to an adjacent silicon atom by a carbon-silicon bond and to the 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 is the average number, 1.4 .
(In formula (2),
^Z2 represents an alkylene group bonded to the adjacent silicon atom by a carbon-silicon bond and to the polyoxyalkylene block by an oxygen atom;
^X2 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. The lubricant according to claim 1 or 2, wherein the siloxane compound has a mass average molecular weight of 500 to 11,000. 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 amount of residue after heating at 140°C for 100 hours and then at 250°C for 700 hours is 20% or less. (A) the siloxane compound according to any one of claims 1 to 4;
(B) a hydrocarbon lubricating oil; and
(C) at least one of an extreme pressure agent and (D) an antioxidant;
A lubricant comprising at least A grease using the lubricant according to any one of claims 1 to 5 . An emulsion using the lubricant according to any one of claims 1 to 5 . A lubricating method, comprising using the lubricant according to any one of claims 1 to 5 . A siloxane compound having a mass average molecular weight of 500 to 11,000 and represented by the following formula (1):
[In formula (1),
X ¹ is the same or different and is hydrogen or an alkyl group having 1 to 12 carbon atoms;
Y is an alkylene group having 2 to 12 carbon atoms;
^Z1 represents an alkylene group bonded to an adjacent silicon atom by a carbon-silicon bond and to the polyoxyalkylene block by an oxygen atom;
p is an integer of 0 to 13, r is an integer of 0 to 16, q is 0, n is an integer of 2 to 4, a is an integer of 1 to 11 , and r is an average number of 1.4 or more. 10. The siloxane compound according to claim 9 , which has a viscosity index of 200 or more and a residue amount of 20% or less after heating at 140°C for 100 hours and then at 250°C for 700 hours. (A) the siloxane compound according to claim 9 or 10 ;
(B) a hydrocarbon lubricating oil; and
(C) at least one of an extreme pressure agent and (D) an antioxidant;
A lubricating oil composition comprising at least A grease comprising the siloxane compound according to claim 9 or 10 or the lubricating oil composition according to claim 11 . An emulsion comprising the siloxane compound according to claim 9 or 10 or the lubricating oil composition according to claim 11 .