Polyolefin-based block copolymer, method for producing same, and lubricating oil composition

Abstract

The purpose of one embodiment of the present invention is to provide a polyolefin-based block copolymer which exhibits excellent low-temperature characteristics, exhibits a high hydrosilylation reaction rate, and is in a liquid state at room temperature.　Disclosed is a polyolefin-based block copolymer (X) which has a specific structure such as formula (1) and satisfies requirements (X1) and (X2). The polyolefin-based block copolymer (X) comprises: a block that is composed of a constituent unit (I) derived from an ethylene / α-olefin copolymer (A) which comprises a constituent unit (i) derived from ethylene and a constituent unit (ii) derived from an α-olefin having 3 to 10 carbon atoms; and a block that is composed of a constituent unit (II) derived from a polyorganosiloxane (B) which is mainly composed of a siloxane unit. The requirement (X1) specifies that the polyolefin-based block copolymer (X) is in a liquid state at room temperature (25°C). The requirement (X2) specifies that the polyolefin-based block copolymer (X) does not have a melting point detectable by a differential scanning calorimeter (DSC) in the range of -20°C to 140°C.

Description

Polyolefin block copolymer, its production method and lubricating oil composition

[0001] The present invention relates to a polyolefin-based block copolymer, a method for producing the polyolefin-based block copolymer, and a lubricating oil composition.

[0002] One known method for imparting liquid repellency to the surface of a polyolefin is to synthesize a block copolymer by reacting the polyolefin with an organosiloxane. Specifically, it is known that a polyolefin having an unsaturated bond at its terminal, synthesized by coordination polymerization, can be synthesized using an Si-H functional polyorganosiloxane and a platinum catalyst (Patent Documents 1 to 3).

[0003] Lubricating oil compositions are also known as one application of polymeric materials such as polyolefins. Lubricating oil compositions are widely used to ensure the operational stability and durability of various mechanical devices, such as engines. In lubricating oil compositions, additives generally known as viscosity modifiers are often added to the base oil to achieve desired viscosity characteristics. For example, they reduce losses associated with sliding and stirring within mechanical devices, improve energy efficiency, such as fuel economy, and contribute to improved durability of mechanical components. Therefore, in recent years, lubricating oil compositions used in mechanical devices are required to maintain fluidity at low temperatures, maintain appropriate viscosity at high temperatures, and suppress significant viscosity fluctuations associated with temperature changes. From this perspective, lubricating oil compositions containing an ethylene-α-olefin copolymer as a viscosity modifier have been investigated (see, for example, Patent Document 4). Furthermore, lubricating oil compositions containing an alkyl-modified silicone added to a mineral oil or synthetic oil have been investigated (see, for example, Patent Document 5).

[0004] Furthermore, lubricating oil compositions containing silicone oil as a base oil are used as lubricating oil base oils in a wide range of fields, including aerospace, electronic components, and medical devices, due to the silicone oil's high heat resistance, oxidation resistance, low-temperature fluidity, and electrical insulation properties. It is also possible to add a viscosity modifier to lubricating oil compositions using silicone oil as a base oil to achieve desired viscosity characteristics. For example, lubricating oil compositions using an ethylene-α-olefin copolymer as a viscosity modifier have been studied (see, for example, Patent Document 4). Furthermore, lubricating oil compositions using alkyl-modified silicone as a base oil have been studied (see, for example, Patent Document 5).

[0005] As the base oil of the lubricating oil composition as described above, mineral oil and synthetic oil have been generally used so far.In order to maintain the fluidity of the lubricating oil composition at low temperatures, improve thermal stability, and improve resistance to oxidation and thermal degradation, it is considered to use silicone oil in combination with mineral oil and / or synthetic oil as the base oil of the lubricating oil composition.For example, a lubricating oil composition containing a specific silicone oil and a hydrocarbon lubricating oil has been studied (for example, see Patent Document 5).

[0006] Japanese Patent Application Laid-Open No. 2023-177838 Japanese Patent Application Laid-Open No. 2010-37555 Japanese Patent Application Laid-Open No. 5-271677 International Publication No. 2023 / 002947 International Publication No. 2019 / 198377

[0007] However, the platinum catalyst used in the synthesis of polyolefin block copolymers, as disclosed in Patent Document 1, has low thermal stability and is unsuitable for hydrosilylation of high-melting-point polyolefins, resulting in low reaction yields. Furthermore, most of the polyolefin-organosiloxane block copolymers known in the art are in a solid state, as disclosed in Patent Document 2, because the polyolefin before the reaction is crystalline. Liquid polyolefin-organosiloxane block copolymers, on the other hand, are limited to those with an extremely small number of carbon atoms, as disclosed in Patent Document 3.

[0008] Lubricating oil compositions using mineral oil or synthetic oil as a base oil and adding an ethylene-α-olefin copolymer as a viscosity modifier can produce lubricating oil compositions that exhibit appropriate viscosity retention at high temperatures, but there is room for improvement in terms of obtaining a lubricating oil composition with a higher viscosity index. On the other hand, lubricating oil compositions to which alkyl-modified silicones have been added can easily produce lubricating oil compositions with a high viscosity index, but there is room for improvement in viscosity retention at high temperatures. As such, it has still been difficult to obtain a lubricating oil composition that combines a high viscosity index with high-temperature viscosity retention.

[0009] In lubricating oil compositions in which silicone oil is used as a base oil and an ethylene-α-olefin copolymer is used as a viscosity modifier, compatibility is insufficient, making it difficult to use the composition. Furthermore, compatibility problems may arise when alkyl-modified silicone is added to silicone oil. Therefore, there is a need for a material that can be used as a viscosity modifier with excellent compatibility with silicone oil, so that it can be used to achieve the desired viscosity characteristics even in lubricating oil compositions that use silicone oil as a base oil.

[0010] In lubricating oil compositions that use a mixture of mineral oil and / or synthetic oil and silicone oil as the base oil, the mineral oil or synthetic oil and silicone oil tend to be poorly compatible with each other and to easily undergo phase separation, and the relationship with the additives added to the lubricating oil may also cause stability problems.Therefore, even when using a base oil that is a mixture of mineral oil and / or synthetic oil and silicone oil, it is desired to have a lubricating oil composition that is excellent in stability and does not undergo phase separation of the components that make up the base oil.

[0011] An object of a first aspect of the present invention is to provide a polyolefin-based block copolymer that has excellent low-temperature properties, a high hydrosilylation reaction rate, and is liquid at room temperature.An object of a second aspect of the present invention is to provide a lubricating oil composition that has a high viscosity index and high-temperature viscosity retention.An object of a third aspect of the present invention is to provide a lubricating oil composition that has excellent viscosity characteristics and contains a viscosity modifier that is highly compatible with a silicone oil base oil.An object of a fourth aspect of the present invention is to provide a lubricating oil composition that is highly stable and does not undergo phase separation of the base oil components, even when a base oil that is a mixture of a mineral oil and / or a synthetic oil and a silicone oil is used.

[0012] As a result of extensive research aimed at solving the above problems, the present inventors have found that the above problems can be solved by the following embodiments, and have completed the present invention.

[0013] [1-1] A polyolefin block copolymer (X) having the following characteristics (X1) to (X3): (X1) Represented by the following formula (1), which has a block consisting of structural units (I) derived from an ethylene-α-olefin copolymer (A) having structural units (i) derived from ethylene and structural units (ii) derived from an α-olefin having 3 to 10 carbon atoms, and a block consisting of structural units (II) derived from a polyorganosiloxane (B) mainly composed of siloxane units; (X2) The polyolefin block copolymer (X) is liquid at room temperature (25°C); (X3) The polyolefin block copolymer (X) does not have a melting point detectable by differential scanning calorimetry (DSC) in the range of -20°C to 140°C. [In the formula (1), A １ , A ２ and A ３ are each independently an ethylene / α-olefin copolymer (A) chain or a hydrocarbon group having 1 to 20 carbon atoms. ３ If there are multiple A ３ may be the same or different from each other. １ , A ２ and A ３At least one of these represents an ethylene-α-olefin copolymer (A) chain. R represents a hydrocarbon group having 1 to 20 carbon atoms. Each R may be the same or different. n, m, and l each independently represent an integer of 1 to 1,000.]

[0014] [1-2] The number of hydrosilylated carbon atoms at the bond between the block consisting of the structural unit (I) derived from the ethylene-α-olefin copolymer (A) and the block consisting of the structural unit (II) derived from the polyorganosiloxane (B), which are produced by the hydrosilylation reaction, is 2 to 47 per 1,000 carbon atoms in the main chain of the ethylene-α-olefin copolymer (A). The polyolefin block copolymer (X) according to item [1-1].

[0015] [1-3] The polyolefin-based block copolymer (X) according to item [1-1] or [1-2], wherein the ethylene-α-olefin copolymer (A) has the following characteristic (A1): (A1) The content of the structural unit (i) is 30 to 70 mol % and the content of the structural unit (ii) is 30 to 70 mol % relative to 100 mol % of the total content of the structural unit (i) and the structural unit (ii).

[0016] [1-4] The ethylene-α-olefin copolymer (A) is soluble in a hydrocarbon solvent at room temperature (25°C) in an amount of 50 vol% or less. [1-1] - [1-3] Polyolefin block copolymer (X) according to any one of the above items.

[0017] [1-5] The polyolefin block copolymer (X) according to any one of [1-1] to [1-4], wherein the ethylene-α-olefin copolymer (A) has the following characteristic (A2): (A2) the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) and calculated in terms of polystyrene is 300 to 5,000.

[0018] [1-6] The polyolefin block copolymer (X) according to any one of items [1-1] to [1-5], which is contained in a coating agent, a lubricant, a release agent, a resin modifier, or a lubricant modifier.

[0019] [1-7] A method for producing a polyolefin-based block copolymer (X) according to any one of items [1-1] to [1-6], obtained by reacting an ethylene-α-olefin copolymer (A) having a structural unit (i) derived from ethylene and a structural unit (ii) derived from an α-olefin having 3 to 10 carbon atoms with a polyorganosiloxane (B) mainly composed of siloxane units.

[0020] [1-8] A method for producing a polyolefin-based block copolymer (X) according to item [1-7], wherein the ethylene-α-olefin copolymer (A) has the above characteristic (A2) and the following characteristics (A1) and (A3): (A1) the content of the structural unit (i) is 30 to 70 mol % and the content of the structural unit (ii) is 30 to 70 mol % relative to 100 mol % of the total content of the structural unit (i) and the structural unit (ii); (A3) １３ The total content of vinyl group ends and vinylidene group ends is more than 60%, relative to 100% of the total integrated intensity of the signals of vinyl group ends, vinylidene group ends, di-substituted olefin ends, tri-substituted olefin ends, and saturated ends determined by C-NMR.

[0021] [1-9] A method for producing the polyolefin block copolymer (X) according to item [1-7] or [1-8], obtained by reacting in a hydrocarbon solvent at 0 to 80 ° C. using a hydrosilylation catalyst.

[0022] [2-1] A lubricating oil composition containing a lubricating base oil (Y) and a polyolefin block copolymer (X) having the characteristics (X1) to (X3) described above, wherein the lubricating oil composition contains 0.1 mass % or more and less than 50.0 mass % of the polyolefin block copolymer (X), wherein the lubricating base oil (Y) is composed of a mineral oil (YA) and / or a synthetic oil (YB), and the synthetic oil (YB) is a hydrocarbon base oil.

[0023] [2-2] The lubricating oil composition according to item [2-1], wherein the polyolefin block copolymer (X) is a block copolymer produced by a hydrosilylation reaction between an ethylene-α-olefin copolymer (A) and a polyorganosiloxane (B), and the number of hydrosilylation carbon atoms at the bond between the block of the ethylene-α-olefin copolymer (A)-derived structural unit (I) and the block of the polyorganosiloxane (B)-derived structural unit (II) is 2 to 47 per 1,000 carbon atoms in the main chain of the ethylene-α-olefin copolymer (A).

[0024] [2-3] The lubricating oil composition according to item [2-1] or [2-2], wherein the ethylene-α-olefin copolymer (A) of the polyolefin block copolymer (X) satisfies the following requirement (A1): (A1) The content of the structural unit (i) is 30 to 70 mol % and the content of the structural unit (ii) is 70 to 30 mol %, relative to 100 mol % of the total content of the structural unit (i) and the structural unit (ii).

[0025] [2-4] The lubricating oil composition according to any one of items [2-1] to [2-3], wherein the lubricating base oil (Y) is a mineral oil (YA) having the following characteristics (YA1) to (YA3) and / or a synthetic oil (YB) having the following characteristics (YB1) to (YB3): (YA1) A kinematic viscosity at 100°C of 2.0 to 20.0 mm ２ (YA2) The viscosity index is 95 or more; (YA3) The pour point is -5°C or less; (YB1) The kinematic viscosity at 100°C is 1.0 to 20.0 mm ２ (YB2) kinematic viscosity at 40°C is 4.0 to 40.0 mm ２ (YB3) The pour point is -30°C or lower.

[0026] [3-1] A lubricating oil composition containing a lubricating base oil (Y) and a polyolefin block copolymer (X) having the characteristics (X1) to (X3) described above, wherein the lubricating oil composition contains 0.1 mass % or more and less than 50.0 mass % of the polyolefin block copolymer (X), and the lubricating base oil (Y) is composed of a silicone oil (YC).

[0027] [3-2] The lubricating oil composition according to item [3-1], wherein the polyolefin block copolymer (X) is a block copolymer produced by a hydrosilylation reaction between an ethylene-α-olefin copolymer (A) and a polyorganosiloxane (B), and the number of hydrosilylation carbon atoms at the bond between the block of the ethylene-α-olefin copolymer (A)-derived structural unit (I) and the block of the polyorganosiloxane (B)-derived structural unit (II) is 2 to 47 per 1,000 carbon atoms in the main chain of the ethylene-α-olefin copolymer (A).

[0028] [3-3] The lubricating oil composition according to item [3-1] or [3-2], wherein the ethylene-α-olefin copolymer (A) of the polyolefin block copolymer (X) has the following characteristic (A1): (A1) The content of the structural unit (i) is 30 to 70 mol % and the content of the structural unit (ii) is 70 to 30 mol %, relative to 100 mol % of the total content of the structural unit (i) and the structural unit (ii).

[0029] [3-4] The lubricating oil composition according to any one of items [3-1] to [3-3], wherein the lubricating base oil (Y) is a silicone oil (YC) having the following characteristics (YC1) to (YC3): (YC1) A kinematic viscosity at 100°C of 0.2 to 40.0 mm ２ (YC2) kinematic viscosity at 40°C is 0.4 to 80.0 mm ２ / s; (YC3) The pour point is -20°C or lower.

[0030] [4-1] A lubricating oil composition containing a lubricating base oil (Y) and a polyolefin block copolymer (X) having the characteristics (X1) to (X3) above, wherein the lubricating oil composition contains 0.1 mass % or more and less than 50.0 mass % of the polyolefin block copolymer (X), wherein the lubricating base oil (Y) comprises a mineral oil (YA) and / or a synthetic oil (YB), and a silicone oil (YC), and the synthetic oil (YB) is a hydrocarbon base oil.

[0031] [4-2] The lubricating oil composition according to item [4-1], wherein the polyolefin block copolymer (X) is a block copolymer produced by a hydrosilylation reaction between an ethylene-α-olefin copolymer (X) and a polyorganosiloxane (B), and the number of hydrosilylation carbon atoms at the bond between the block of the ethylene-α-olefin copolymer (A)-derived structural unit (I) and the block of the polyorganosiloxane (B)-derived structural unit (II) is 2 to 47 per 1,000 carbon atoms in the main chain of the ethylene-α-olefin copolymer (A).

[0032] [4-3] The lubricating oil composition according to item [4-1] or [4-2], wherein the ethylene-α-olefin copolymer (A) of the polyolefin block copolymer (X) has the following characteristic (A1): (A1) The content of the structural unit (i) is 30 to 70 mol % and the content of the structural unit (ii) is 70 to 30 mol %, relative to 100 mol % of the total content of the structural unit (i) and the structural unit (ii).

[0033] [4-4] The lubricating oil composition according to any one of items [4-1] to [4-3], wherein the mineral oil (YA) and / or synthetic oil (YB) contained in the lubricating base oil (Y) is a mineral oil (YA) having the following characteristics (YA1) to (YA3) and / or a synthetic oil (YB) having the following characteristics (YB1) to (YB3): (YA1) A kinematic viscosity at 100°C of 2.0 to 20.0 mm ２ (YA2) The viscosity index is 95 or more; (YA3) The pour point is -5°C or less; (YB1) The kinematic viscosity at 100°C is 1.0 to 20.0 mm２ (YB2) kinematic viscosity at 40°C is 4.0 to 40.0 mm ２ (YB3) The pour point is -30°C or lower.

[0034] [4-5] The lubricating oil composition according to any one of items [4-1] to [4-4], wherein the silicone oil (YC) contained in the lubricating base oil (Y) has the following characteristics (YC1) to (YC3): (YC1) A kinematic viscosity at 100°C of 0.2 to 40.0 mm ２ (YC2) kinematic viscosity at 40°C is 0.4 to 80.0 mm ２ / s; (YC3) The pour point is -20°C or lower.

[0035] According to a first aspect of the present invention, a polyolefin-based block copolymer can be provided that has excellent low-temperature properties, a high hydrosilylation reaction rate, and is liquid at room temperature. According to a second aspect of the present invention, a lubricating oil composition can be provided that has a high viscosity index and high-temperature viscosity retention. According to a third aspect of the present invention, a lubricating oil composition can be provided that has excellent viscosity properties and contains a viscosity modifier that is highly compatible with a silicone oil base oil. According to a fourth aspect of the present invention, a lubricating oil composition can be provided that is stable and does not experience phase separation of the base oil components, even when a base oil that is a mixture of a mineral oil and / or a synthetic oil and a silicone oil is used.

[0036] Figure 1 shows the GPC curve of Example 1-1. Figure 2 shows the GPC curve of Example 1-6.

[0037] The present invention will be described in detail below. In this specification, "room temperature" refers to 25°C. In this specification, the term "to" indicating a numerical range means a range that includes the numerical values ​​before and after it as the lower and upper limits. In this specification, when "to" is used to indicate a numerical range, for example, when written as "M to N" (where M and N are numerical values ​​that satisfy M<N), it means "greater than or equal to M and less than or equal to N" unless otherwise specified. Furthermore, the unit written after either numerical value before or after "to" is the unit of both numerical values ​​before and after "to" unless otherwise specified. Furthermore, when a numerical range is described in stages, the upper and lower limits of each numerical range can be arbitrarily combined. In this specification, when the amount of each component in a composition is referred to, if multiple substances corresponding to each component are present in the composition, the total amount of the multiple substances present in the composition is meant unless otherwise specified. In this specification, a combination of two or more preferred embodiments is a more preferred embodiment. In this specification, unless otherwise specified, each component in the composition or each structural unit in the polymer may be contained alone or in combination of two or more types. In this specification, the term "polymer" refers to both homopolymers and copolymers unless otherwise specified. In this specification, the various monomers used as raw materials for the polymer may be derived from fossil materials, biological sources such as biomass, or chemically recycled materials, or may be a mixture of two or more of these.

[0038] <Polyolefin Block Copolymer (X)> The polyolefin block copolymer (X) of the first aspect of the present invention (hereinafter also referred to as "block copolymer (X)") has the following characteristics (X1) to (X3).

[0039] <Requirement (X1)> The block copolymer (X) has, as structural units, a block consisting of structural units (I) derived from an ethylene-α-olefin copolymer (A) having structural units (i) derived from ethylene and structural units (ii) derived from an α-olefin having 3 to 10 carbon atoms, and a block consisting of structural units (II) derived from a polyorganosiloxane (B) mainly composed of siloxane units, and is represented by the following formula (1). For example, by including a block copolymer (X) having such a structure in the lubricating oil composition of the present invention described below, a lubricating oil composition having defoaming properties can be obtained. Furthermore, the block copolymer (X) is partially incompatible at low temperatures, making it possible to suppress an increase in viscosity at low temperatures.

[0040]

[0041] [In the formula (1), A １ , A ２ and A ３ are each independently an ethylene / α-olefin copolymer (A) chain or a hydrocarbon group having 1 to 20 carbon atoms. ３ If there are multiple A ３ may be the same or different from each other. １ , A ２ and A ３ At least one of these represents an ethylene-α-olefin copolymer (A) chain. R represents a hydrocarbon group having 1 to 20 carbon atoms. Each R may be the same or different. n, m, and l each independently represent an integer of 1 to 1,000.]

[0042] The above A １ , A ２ and A ３ At least one of the chains is an ethylene / α-olefin copolymer (A) chain, and two or more of the chains may be ethylene / α-olefin copolymer (A) chains, or all of the chains may be ethylene / α-olefin copolymer (A) chains.

[0043] In the formula (1), examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, and an aromatic hydrocarbon group. More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, and an octadecyl group. Examples of the cycloalkyl group include a cyclohexyl group. Examples of the aromatic hydrocarbon group include an aryl group or an aralkyl group such as a phenyl group, a tolyl group, a naphthyl group, a benzyl group, and a phenylethyl group. Among these, the hydrocarbon group having 1 to 20 carbon atoms is preferably a hydrocarbon group having 1 to 18 carbon atoms, more preferably a hydrocarbon group having 1 to 10 carbon atoms, even more preferably a hydrocarbon group having 1 to 5 carbon atoms, and particularly preferably a hydrocarbon group having 1 to 3 carbon atoms.

[0044] In the formula (1), n ​​is an integer of 1 to 1,000, preferably an integer of 1 to 500, more preferably an integer of 1 to 250; m is an integer of 1 to 1,000, preferably an integer of 1 to 500, more preferably an integer of 1 to 250; and l is an integer of 1 to 1,000, preferably an integer of 1 to 500, more preferably an integer of 1 to 250.

[0045] <Requirement (X2)> The block copolymer (X) is liquid at room temperature (25° C.). If the copolymer (X) is liquid at room temperature (25° C.), this is preferable in terms of handleability when used as a liquid material such as a coating agent, lubricant, mold release agent, resin modifier, or lubricant modifier.

[0046] <Requirement (X3)> The block copolymer (X) does not have a melting point detectable by differential scanning calorimetry (DSC) in the range of -20°C to 140°C. The phrase "not having a melting point in the range of -20°C to 140°C" includes cases where no melting point is observed. It is preferable that the copolymer (X) does not have a melting point in the range of -20°C to 140°C, as this will result in excellent shear stability as a lubricating oil or viscosity index improver. The melting point can be determined by the method described in the Examples.

[0047] The number of hydrosilylated carbon atoms at the bond between the block composed of the structural unit (I) and the block composed of the structural unit (II) formed by the hydrosilylation reaction is preferably 2 to 47, more preferably 5 to 40, still more preferably 7.5 to 30, and particularly preferably 8.8 to 16.3 per 1000 carbon atoms in the main chain of the ethylene-α-olefin copolymer (A) portion. A number of hydrosilylated carbon atoms within the above range indicates that the hydrosilylation reaction has proceeded quantitatively, and is preferred in that the characteristics of both the ethylene-α-olefin copolymer (A) and the organosiloxane (B) can be expressed.

[0048] The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the block copolymer (X), measured by gel permeation chromatography (GPC) and calculated in terms of polystyrene, is preferably 0.5 to 7.0, more preferably 0.7 to 5.0, even more preferably 1.0 to 4.0, particularly preferably 1.2 to 3.7, and especially preferably 1.3 to 3.5.

[0049] <Ethylene / α-olefin copolymer (A)> The ethylene / α-olefin copolymer (A) (hereinafter also referred to as "copolymer (A)") has a structural unit (i) derived from ethylene and a structural unit (ii) derived from an α-olefin having 3 to 10 carbon atoms, and preferably satisfies the following requirement (A1):

[0050] Examples of the α-olefin having 3 to 10 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and 1-decene, and are preferably α-olefins having 3 to 8 carbon atoms, more preferably α-olefins having 3 to 5 carbon atoms, and even more preferably propylene. α-olefins having 3 to 10 carbon atoms are preferred because the polyolefin block copolymer (X) obtained by the reaction does not have a melting point.

[0051] <Requirement (A1)> In copolymer (A), the content of structural unit (i) is preferably 30 to 70 mol%, more preferably 35 to 65 mol%, even more preferably 40 to 60 mol%, particularly preferably 45 to 55 mol%, and especially preferably 49 to 50 mol%, relative to the total content of structural unit (i) and structural unit (ii) (100 mol%). The content of structural unit (ii) is preferably 30 to 70 mol%, more preferably 35 to 65 mol%, even more preferably 40 to 60 mol%, particularly preferably 45 to 55 mol%, and especially preferably 50 to 51 mol%. Having the contents of structural units (i) and (ii) within the above ranges is preferable in terms of compatibility with hydrocarbon solvents and the fact that the polyolefin block copolymer (X) obtained by the reaction does not have a melting point. The contents of structural units (i) and (ii) can be determined by the method described in the Examples.

[0052] The copolymer (A) has at least one structural unit derived from an α-olefin having 3 to 10 carbon atoms, and may have two or more structural units derived from α-olefins having 3 to 10 carbon atoms.

[0053] The copolymer (A) more preferably satisfies the following requirement (A2) or (A3), further preferably satisfies the following requirements (A2) and (A3), and particularly preferably satisfies the above requirement (A1) and the following requirements (A2) and (A3).

[0054] <Requirement (A2)> The number average molecular weight (Mn) of the copolymer (A), measured by gel permeation chromatography (GPC) and calculated in terms of polystyrene, is 300 to 5,000, preferably 300 to 4,000, more preferably 350 to 3,000, even more preferably 400 to 2,000, and particularly preferably 1,140 to 1,280. When the block copolymer (X) of the present invention is used in a lubricating oil composition or the like, the number average molecular weight (Mn) of the copolymer (A) is preferably 500 to 4,000, more preferably 900 to 3,000, even more preferably 900 to 2,000, particularly preferably 1,000 to 2,000, and particularly preferably 1,140 to 1,280. A number average molecular weight (Mn) within the above range is preferable in terms of compatibility with hydrocarbon solvents and the fact that the polyolefin block copolymer (X) obtained by the reaction is liquid. The number average molecular weight (Mn) can be determined by the method described in the Examples.

[0055] <Requirement (A3)> Copolymer (A) 13 The total content of vinyl and vinylidene terminals is greater than 60%, preferably greater than 60% but not greater than 100%, more preferably 62% or more but not greater than 100%, even more preferably 64% or more but not greater than 100%, particularly preferably 65% ​​or more but not greater than 100%, and especially preferably 70% or more but not greater than 100%, relative to the total integrated intensity of the signals of vinyl terminals, vinylidene terminals, disubstituted olefin terminals, trisubstituted olefin terminals, and saturated terminals determined by C-NMR (100%). A total content of vinyl and vinylidene terminals within the above range is preferred in that the reaction catalyzed by the hydrosilylation catalyst proceeds quantitatively.

[0056] The copolymer (A) may further satisfy the following requirement (A4). <Requirement (A4)> The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the copolymer (A), as measured by gel permeation chromatography (GPC) and calculated in terms of polystyrene, is 1.5 to 5.0, preferably 1.6 to 4.7, more preferably 1.7 to 4.5, even more preferably 1.8 to 4.3, and particularly preferably 2.7 to 3.0. A ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) within the above range is preferable in that, when the polyolefin block copolymer (X) obtained by the reaction is used as a modifier, nonvolatile substances are reduced and processability is improved. Furthermore, when the block copolymer (X) of the present invention is used in a lubricating oil composition or the like, the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the copolymer (A) is 1.5 to 5.0, preferably 1.6 to 4.5, more preferably 1.7 to 4.2, even more preferably 1.8 to 3.8, particularly preferably 1.9 to 3.5, and especially preferably 2.7 to 3.0. When the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is within the above range, non-volatile substances can be reduced when the block copolymer (X) obtained by the reaction is incorporated into a lubricating oil composition.

[0057] The copolymer (A) is preferably soluble in hydrocarbon solvents at room temperature (25°C) at a concentration of preferably 50% by volume or less, more preferably from 0% to 45% by volume or less, and even more preferably from 5% to 40% by volume. When the copolymer (A) is soluble in hydrocarbon solvents at the above concentration at room temperature (25°C), the reaction with the hydrosilylation catalyst can be carried out at room temperature (25°C), which is preferable in that the reaction proceeds quantitatively. Examples of hydrocarbon solvents include aromatic hydrocarbon solvents such as toluene and xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane, and decane; alicyclic hydrocarbon solvents such as cyclohexane and methylcyclohexane; chlorinated hydrocarbon solvents such as trichloroethylene, perchloroethylene, dichloroethylene, dichloroethane, and chlorobenzene; aliphatic alcohol solvents such as ethanol and isopropanol; ketone solvents such as acetone, methyl isobutyl ketone, and methyl ethyl ketone; and ester solvents such as methyl acetate, ethyl acetate, and butyl acetate. The solvent may be used alone or in combination of two or more kinds.

[0058] <Method for Producing Ethylene / α-Olefin Copolymer (A)> The method for producing the ethylene / α-olefin copolymer (A) is not particularly limited. For example, the ethylene / α-olefin copolymer (A) can be produced by copolymerizing ethylene and at least one α-olefin having 3 to 10 carbon atoms in the presence of an olefin polymerization catalyst. Preferably, the method includes a step of polymerizing an olefin at a temperature of 60 to 130° C. in the presence of an activator and at least one metallocene compound.

[0059] The polymerization temperature is preferably 25 to 130° C., more preferably 30 to 125° C., and even more preferably 40 to 120° C. If the polymerization temperature is within the above range, it is preferable in that the molecular weight of the produced polymer can be controlled within the range described in requirement (A2).

[0060] Examples of the activator include at least one compound (b) selected from organometallic compounds (b-1), organoaluminum oxy compounds (b-2), and compounds (b-3) that react with a metallocene compound to form an ion pair.

[0061] Examples of the organometallic compound (b-1) (excluding the organoaluminum oxy compound (b-2)) include organoaluminum compounds such as trialkylaluminums such as trimethylaluminum, triethylaluminum, triisobutylaluminum, and tri-n-octylaluminum, tricycloalkylaluminums, isobutylaluminum dichloride, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, methylaluminum dichloride, dimethylaluminum chloride, and diisobutylaluminum hydride.

[0062] Examples of the organoaluminum oxy compound (b-2) include conventionally known aluminoxanes.

[0063] Examples of the compound (b-3) that reacts with a metallocene compound to form an ion pair include Lewis acids, ionic compounds, borane compounds, and carborane compounds described in JP-T-1-501950, JP-T-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, U.S. Pat. No. 5,321,106, and WO 2015 / 122415.

[0064] The polymerization pressure is usually between atmospheric pressure and 10 MPa gauge pressure, preferably between atmospheric pressure and 8 MPa gauge pressure. The copolymerization can be carried out batchwise, semi-continuously, or continuously. The reaction time (average residence time when the copolymerization reaction is carried out continuously) varies depending on conditions such as catalyst concentration and polymerization temperature and can be selected appropriately, but is usually between 1 minute and 3 hours, preferably between 5 minutes and 2.5 hours. Furthermore, the polymerization can be carried out in two or more stages with different reaction conditions. The molecular weight of the resulting ethylene-α-olefin copolymer (A) can be adjusted by varying the hydrogen concentration in the polymerization system or the polymerization temperature. It can also be adjusted by the amount of catalyst component used. When hydrogen is added to the polymerization system, the amount is suitably about 0.001 to 5,000 NL per kg of the ethylene-α-olefin copolymer produced. The amount of terminal unsaturation in the resulting ethylene-α-olefin copolymer (A) can be increased by minimizing the amount of hydrogen added.

[0065] <Polyorganosiloxane (B)> The polyorganosiloxane (B) is not particularly limited as long as it is mainly composed of siloxane units, and known polyorganosiloxanes can be used. The structure of the polyorganosiloxane is not particularly limited, but it is preferable that it has a linear, branched, or crosslinked polymer structure.

[0066] The polyorganosiloxane (B) is not particularly limited, and known ones can be used.Preferred polyorganosiloxane is a polymer containing a siloxane unit having a substituent such as an alkyl group, a vinyl group, or an aryl group, and among these, polyorganosiloxane having an alkyl group is particularly preferred, and polyorganosiloxane having a methyl group is more preferred.

[0067] Specific examples of polyorganosiloxanes having a methyl group include polydimethylsiloxane, polymethylphenylsiloxane, polymethylhydrogensiloxane, etc. Among these, polydimethylsiloxane is preferred.

[0068] The molecular weight Mn of the polyorganosiloxane (B) calculated by GPC analysis is preferably 100 to 15,000, more preferably 200 to 10,000, even more preferably 300 to 9,000, particularly preferably 400 to 8,500, and especially preferably 500 to 8,420.

[0069] Polyorganosiloxane (B) １ The Si—H group content calculated by H-NMR analysis is preferably 0.030 to 10.0 mmol / g, more preferably 0.060 to 5.0 mmol / g, even more preferably 0.080 to 4.0 mmol / g, particularly preferably 0.090 to 3.0 mmol / g, and especially preferably 0.094 to 2.5 mmol / g.

[0070] <Method for Producing Polyolefin Block Copolymer (X)> The method for producing the polyolefin block copolymer (X) is not particularly limited. For example, the polyolefin block copolymer (X) can be obtained by reacting an ethylene-α-olefin copolymer (A) having a structural unit (i) derived from ethylene and a structural unit (ii) derived from an α-olefin having 3 to 10 carbon atoms with a polyorganosiloxane (B) mainly composed of siloxane units. Preferably, the ethylene-α-olefin copolymer (A) satisfies the above requirements (A1) to (A4). More preferably, the polyolefin block copolymer (X) can be obtained by reacting the ethylene-α-olefin copolymer (A) in a hydrocarbon solvent at 0 to 80°C using a hydrosilylation catalyst.

[0071] The hydrosilylation catalyst is an addition reaction catalyst and is not particularly limited as long as it promotes the addition reaction, and examples thereof include addition reaction catalysts made of platinum group elements such as platinum-based catalysts, palladium-based catalysts, and rhodium-based catalysts (Group 8 metal-based catalysts such as Group 8 metals, Group 8 metal complexes, and Group 8 metal compounds of the periodic table). Platinum is particularly preferred as the Group 8 element metal of the periodic table.

[0072] The platinum catalyst may be a known one that is normally used in addition curing, and examples thereof include the fine powder metal platinum catalyst described in U.S. Pat. No. 2,970,150, the chloroplatinic acid catalyst described in U.S. Pat. No. 2,823,218, the complex compound of platinum and a hydrocarbon described in U.S. Pat. No. 3,159,601, the complex compound of chloroplatinic acid and an olefin described in U.S. Pat. No. 3,516,946, and the complex compound of platinum and a vinylsiloxane described in U.S. Pat. No. 3,775,452. More specifically, examples of the platinum catalyst include platinum itself (platinum black), chloroplatinic acid, platinum-olefin complexes, platinum-alcohol complexes, and platinum supported on a carrier such as alumina or silica, and examples thereof include platinum(0)-2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane complex and platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Karstedt catalyst).

[0073] The reaction temperature is preferably 0 to 80° C., more preferably 5 to 70° C., and even more preferably 10 to 60° C. A reaction temperature within this range is preferred because the reaction catalyzed by the hydrosilylation catalyst proceeds with high selectivity.

[0074] <Uses> The polyolefin block copolymer (X) of the first aspect of the present invention is used, for example, as a coating agent, a lubricant, a release agent, a resin modifier, a lubricant modifier, and the like.

[0075] Examples of coating agents include fluorine-based and silicone-based agents.

[0076] Examples of the release agent include lower (C1-4) alcohol esters of higher fatty acids (butyl stearate, etc.), polyhydric alcohol esters of fatty acids (C4-30) (hydrogenated castor oil, etc.), glycol esters of fatty acids, and liquid paraffin.

[0077] <Lubricant Composition> As described above, the polyolefin block copolymer (X) obtained by the present invention can be suitably used as a lubricant modifier. The lubricant composition of the present invention contains a lubricant base oil (Y) and a polyolefin block copolymer (X). Suitable examples of the lubricant composition of the present invention include: a lubricant composition according to a second aspect of the present invention, which contains a lubricant base oil (Y) and the polyolefin block copolymer (X), and the lubricant base oil (Y) contains 0.1 mass% or more and less than 50.0 mass% of the polyolefin block copolymer (X), the lubricant base oil (Y) being composed of a mineral oil (YA) and / or a synthetic oil (YB), and the synthetic oil (YB) being a hydrocarbon base oil; a lubricant composition according to a third aspect of the present invention, which contains a lubricant base oil (Y) and the polyolefin block copolymer (X), and the lubricant base oil (Y) contains 0.1 mass% or more and less than 50.0 mass% of the polyolefin block copolymer (X), and the lubricant base oil (Y) is composed of a silicone oil (YC); a fourth aspect of the present invention, which is a lubricating oil composition containing a lubricating base oil (Y) and the polyolefin block copolymer (X), the composition containing 0.1 mass % or more and less than 50.0 mass % of the polyolefin block copolymer (X), the lubricating base oil (Y) comprising a mineral oil (YA) and / or a synthetic oil (YB) and a silicone oil (YC), and the synthetic oil (YB) is a hydrocarbon base oil. The lubricating oil composition of the present invention will now be described.

[0078] <Lubricant base oil (Y)> Lubricant base oil (Y) differs in performance and quality, such as viscosity characteristics, heat resistance, and oxidation stability, depending on its production method, refining method, etc. API (American Petroleum Institute) classifies lubricant base oils into five types: Group I, II, III, IV, and V. These API categories are defined in API 1509, Engine Oil Licensing and Certification System, 22nd Edition, October 2023, and are as shown in Table 1.

[0079]

[0080] The lubricating base oil (Y) used in the lubricating oil composition of the second aspect of the present invention is composed of a mineral oil (YA) and / or a synthetic oil (YB), and when a synthetic oil (YB) is used as the lubricating base oil (Y), the synthetic oil (YB) is a hydrocarbon-based base oil. The lubricating base oil (Y) used in the lubricating oil composition of the third aspect of the present invention is a silicone oil (YC). The lubricating base oil (Y) used in the lubricating oil composition of the fourth aspect of the present invention is composed of a mineral oil (YA) and / or a synthetic oil (YB) and a silicone oil (YC), and when a synthetic oil (YB) is included as the lubricating base oil (Y), the synthetic oil (YB) is a hydrocarbon-based base oil. These lubricating base oils (Y) will be described in detail below.

[0081] <Mineral Oil (YA)> The mineral oil (YA) that can be used in the lubricating oil compositions of the second and fourth aspects of the present invention belongs to Groups I to III of the API category mentioned above.

[0082] The qualities of mineral oils are as described above, and mineral oils of the respective qualities can be obtained by the refining method.Specific examples of mineral oil (YA) include lubricating oil fractions obtained by vacuum distillation of atmospheric residue obtained by atmospheric distillation of crude oil, and then refined by one or more processes such as solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, and hydrorefining, as well as lubricating oil base oils such as wax isomerized mineral oil.

[0083] Gas-to-liquid (GTL) base oils obtained by the Fischer-Tropsch process are also suitable for use as Group III mineral oils. Such GTL base oils are sometimes referred to as Group III+ lubricant base oils, and are described, for example, in patent documents such as EP 776959, EP 668342, WO 97 / 21788, WO 00 / 15736, WO 00 / 14188, WO 00 / 14187, WO 00 / 14183, WO 00 / 14179, WO 00 / 08115, WO 99 / 41332, EP 1029029, WO 01 / 18156, and WO 01 / 57166.

[0084] The mineral oil (YA) preferably has at least one characteristic selected from the group consisting of the following (YA1) to (YA3), and more preferably has all of the following characteristics (YA1) to (YA3):

[0085] (YA1) Kinematic viscosity at 100 ° C. is 2.0 to 20.0 mm ２ This kinematic viscosity value is measured according to the method described in JIS K2283. The kinematic viscosity of mineral oil (YA) at 100°C is 2.0 to 20.0 mm ２ / s, preferably 2.0 to 18.0 mm ２ / s, more preferably 2.0 to 15.0 mm ２ When the kinematic viscosity at 100°C is within this range, the lubricating oil composition of the second or fourth aspect of the present invention is excellent in terms of temperature viscosity characteristics.

[0086] (YA2) Viscosity index of 95 or more This viscosity index value is measured according to the method described in JIS K2283. The viscosity index of the mineral oil (YA) is 95 or more, preferably 105 or more, more preferably 108 or more, and even more preferably 110 or more. When the viscosity index is within this range, the lubricating oil composition of the second or fourth aspect of the present invention has excellent temperature viscosity characteristics.

[0087] (YA3) Pour point of -5°C or less This pour point value is measured according to the method described in ASTM D97. The pour point of the mineral oil (YA) is -5°C or less, preferably -7°C or less. It is also preferable that the pour point of the mineral oil (YA) is at least -40°C or more. When the pour point is within this range, the lubricating oil composition of the second or fourth aspect of the present invention has excellent low-temperature viscosity characteristics when the mineral oil (YA) is used in combination with a pour point depressant.

[0088] The mineral oil (YA) may be used alone or in a mixture of two or more kinds.

[0089] <Synthetic Oil (YB)> The synthetic oil (YB) that can be used in the lubricating oil compositions of the second and fourth aspects of the present invention belongs to Group IV or Group V in the above-mentioned API category. The synthetic oil (YB) used in the present invention is a hydrocarbon-based base oil, and is a poly-α-olefin belonging to Group IV or a hydrocarbon belonging to Group V.

[0090] Poly-α-olefins belonging to Group IV can be obtained by oligomerizing higher α-olefins with an acid catalyst, as described in U.S. Pat. Nos. 3,780,128 and 4,032,591, and Japanese Patent Laid-Open Publication No. 1-163136. Among these, the poly-α-olefin can be a low-molecular-weight oligomer of at least one olefin selected from olefins having 8 or more carbon atoms. When a poly-α-olefin is used as the lubricating base oil (Y), a lubricating oil composition having excellent temperature viscosity characteristics, low-temperature viscosity characteristics, and heat resistance can be obtained.

[0091] Poly-α-olefins are commercially available, such as Spectrasyn manufactured by ExxonMobil Chemical, Durasyn manufactured by Ineos Oligomers, and Synfluid manufactured by Chevron Phillips Chemical.

[0092] Examples of hydrocarbons belonging to Group V that can be used as synthetic oils (YB) include alkylbenzenes, alkylnaphthalenes, isobutene oligomers or hydrogenated products thereof, and paraffins.

[0093] The majority of alkylbenzenes and alkylnaphthalenes are dialkylbenzenes or dialkylnaphthalenes, typically having alkyl chain lengths of 6 to 14 carbon atoms, and such alkylbenzenes or alkylnaphthalenes are produced by the Friedel-Crafts alkylation reaction of benzene or naphthalene with an olefin. The alkylated olefin used in the production of alkylbenzenes or alkylnaphthalenes may be a linear or branched olefin or a combination thereof. The production method thereof is described, for example, in U.S. Pat. No. 3,909,432.

[0094] The synthetic oil (YB) preferably has at least one characteristic selected from the group consisting of the following (YB1) to (YB3), and more preferably has all of the following characteristics (YB1) to (YB3):

[0095] (YB1) Kinematic viscosity at 100 ° C. is 1.0 to 20.0 mm ２ This kinematic viscosity value is measured according to the method described in JIS K2283. The kinematic viscosity of synthetic oil (YB) at 100°C is 1.0 to 20.0 mm / s. ２ / s, preferably 1.5 to 18.0 mm ２ / s, more preferably 1.5 to 15.0 mm ２ / s, more preferably 2.0 to 15.0 mm ２ / s, particularly preferably 2.0 to 12.0 mm ２ / s, particularly preferably 4.0 to 5.9 mm ２ When the kinematic viscosity at 100°C is within this range, the lubricating oil composition of the second or fourth aspect of the present invention is excellent in terms of volatility and temperature-viscosity characteristics.

[0096] (YB2) Kinematic viscosity at 40 ° C. is 4.0 to 40.0 mm ２ This kinematic viscosity value is measured according to the method described in JIS K2283. The kinematic viscosity of synthetic oil (YB) at 40°C is 4.0 to 40.0 mm ２ / s, but in the lubricating oil composition of the second aspect of the present invention, it is preferably 4.0 to 38.0 mm ２ / s, more preferably 8.0 to 35.0 mm ２ / s, more preferably 8.0 to 30.0 mm ２ / s, particularly preferably 10.0 to 30.0 mm ２ / s, particularly preferably 15.0 to 20.0 mm ２ In the lubricating oil composition of the fourth aspect of the present invention, the kinematic viscosity is preferably 4.0 to 38.0 mm ２ / s, more preferably 4.0 to 35.0 mm ２ / s, more preferably 10.0 to 33.0 mm ２ / s, particularly preferably 20.0 to 32.0 mm ２ / s, particularly preferably 30.0 to 31.0 mm ２ When the kinematic viscosity at 40°C is within the above range, the lubricating oil composition of the second or fourth aspect of the present invention is excellent in terms of flowability and handleability at room temperature.

[0097] (YB3) Pour point of -30°C or lower This pour point value is measured according to the method described in ASTM D97. The pour point of the synthetic oil (YB) is -30°C or lower, preferably -40°C or lower, more preferably -50°C or lower, even more preferably -55°C or lower, and particularly preferably -60°C or lower. It is also preferable that the pour point of the synthetic oil (YB) is at least -80°C or higher. When the pour point is within this range, the lubricating oil composition of the second or fourth aspect of the present invention will have excellent low-temperature viscosity characteristics.

[0098] The viscosity index of the synthetic oil (YB) is preferably 50 or higher, more preferably 80 or higher, even more preferably 100 or higher, and particularly preferably 120 or higher. The viscosity index of the synthetic oil (YB) is preferably 500 or lower, more preferably 300 or lower, even more preferably 200 or lower, and particularly preferably 150 or lower. The viscosity index can be determined by the method described in JIS K2283.

[0099] The hydrocarbon base oil used as the synthetic oil (YB) may be used alone or as a mixture of two or more kinds.

[0100] When the lubricating base oil (Y) used in the lubricating oil composition of the second aspect of the present invention contains a synthetic oil (YB), the synthetic oil (YB) preferably contains only a hydrocarbon base oil that is a synthetic oil (YB). In terms of quality stability, the lubricating base oil (Y) used in the lubricating oil composition of the second aspect of the present invention preferably is a synthetic oil (YB), and more preferably is a poly-α-olefin belonging to Group IV.

[0101] <Silicone oil (YC)> The silicone oil (YC) used in the lubricating oil composition according to the third and fourth aspects of the present invention belongs to Group V in the API category described above. The silicone oil (YC) is a silicone oil having a repeating unit (—SiR ２ -O-) ｎ (wherein R represents a hydrocarbon group such as a methyl group, an ethyl group, a propyl group, a phenyl group, etc., or a hydrocarbon group partially substituted with —NH ２ The term "silicone oil" refers to a silicone polymer having an Si—O bond in its skeleton, and the molecular chain has relatively high flexibility, excellent fluidity even at low temperatures, and heat and oxidation resistance that makes it difficult to decompose even at high temperatures.

[0102] Examples of silicone oils (YC) include straight silicone oils such as dimethyl silicone oil, methylphenyl silicone oil, and methylhydrogen silicone oil; and modified silicone oils such as long-chain alkyl silicone oil, fluorosilicone oil, and amino-modified silicone oil. Among these, dimethyl silicone oil is preferred.

[0103] The method for preparing the silicone oil (YC) is not particularly limited, but examples thereof include a method of subjecting a linear polysiloxane having SiH groups to an equilibration reaction with a low-polymerization polysiloxane such as hexamethyldisiloxane in the presence of an acid catalyst such as activated clay; and a method of subjecting a polysiloxane having SiH groups to an addition reaction with an olefin compound such as 1-octene in the presence of a hydrosilylation catalyst under a nitrogen atmosphere.

[0104] Silicone oil (YC) is commercially available, for example, KF-96 series of the KF series manufactured by Shin-Etsu Silicone Co., Ltd.

[0105] The silicone oil (YC) preferably has at least one characteristic selected from the group consisting of the following (YC1) to (YC3), and more preferably has all of the following characteristics (YC1) to (YC3):

[0106] (YC1) Kinematic viscosity at 100 ° C. is 0.2 to 40.0 mm ２ This kinematic viscosity value is measured according to the method described in JIS K2283. The kinematic viscosity of silicone oil (YC) at 100°C is 0.2 to 40.0 mm / s. ２ / s, preferably 0.3 to 30.0 mm ２ / s, more preferably 0.5 to 20.0 mm ２ / s, more preferably 1.0 to 15.0 mm ２ / s, particularly preferably 2.0 to 10.0 mm ２ / s, particularly preferably 5.0 to 7.0 mm ２ When the kinematic viscosity at 100°C is within this range, the lubricating oil composition of the third or fourth aspect of the present invention is excellent in terms of temperature viscosity characteristics.

[0107] (YC2) Kinematic viscosity at 40 ° C. is 0.4 to 80.0 mm ２ This kinematic viscosity value is measured according to the method described in JIS K2283. The kinematic viscosity of silicone oil (YC) at 40°C is 0.4 to 80.0 mm ２ / s, preferably 1.0 to 60.0 mm ２ / s, more preferably 2.0 to 40.0 mm２ / s, more preferably 4.0 to 35.0 mm ２ / s, particularly preferably 8.0 to 30.0 mm ２ / s, particularly preferably 12.0 to 18.0 mm ２ When the kinematic viscosity at 40°C is within this range, the lubricating oil composition of the third or fourth aspect of the present invention is excellent in terms of flowability and handleability at room temperature.

[0108] (YC3) Pour point of -20°C or lower This pour point value is measured according to the method described in ASTM D97. The pour point of the silicone oil (YC) is -20°C or lower, preferably -30°C or lower, more preferably -40°C or lower, and even more preferably -50°C or lower. The pour point of the silicone oil (YC) is preferably at least -100°C or higher. When the pour point is within this range, the lubricating oil composition of the third or fourth aspect of the present invention will have excellent low-temperature viscosity characteristics when the silicone oil (YC) is used in combination with a pour point depressant.

[0109] The viscosity index of the silicone oil (YC) is preferably 100 or more, more preferably 200 or more, even more preferably 300 or more, and particularly preferably 400 or more. The viscosity index of the silicone oil (YC) is preferably 800 or less, more preferably 700 or less, even more preferably 600 or less, and particularly preferably 500 or less. The viscosity index can be determined by the method described in JIS K2283.

[0110] The silicone oil (YC) may be used alone or as a mixture of two or more kinds.

[0111] The lubricating base oil (Y) used in the lubricating oil composition of the fourth aspect of the present invention may be a mixture of a mineral oil (YA) and a silicone oil (YC), a mixture of a synthetic oil (YB) and a silicone oil (YC), or a mixture of a mineral oil (YA), a synthetic oil (YB), and a silicone oil (YC).

[0112] When the lubricating base oil (Y) used in the lubricating oil composition of the fourth aspect of the present invention contains a synthetic oil (YB), the synthetic oil is preferably a hydrocarbon base oil that is a synthetic oil (YB) and / or a silicone oil (YC). That is, in one preferred embodiment, the lubricating base oil (Y) used in the present invention is preferably any one of a form consisting of only a mineral oil (YA) and a silicone oil (YC), a form consisting of only a synthetic oil (YB) and a silicone oil (YC), or a form consisting of only a mineral oil (YA), a synthetic oil (YB), and a silicone oil (YC).

[0113] In the lubricating base oil (Y) used in the lubricating oil composition of the fourth aspect of the present invention, the blending ratio of the mineral oil (YA) and / or synthetic oil (YB) to the silicone oil (YC) is not particularly limited as long as the required properties for the intended application are satisfied, but usually, the mass ratio of the mineral oil (YA) and / or synthetic oil (YB) to the silicone oil (YC) (mass of mineral oil (YA) and / or synthetic oil (YB) / mass of silicone oil (YC)) is preferably 10 / 90 to 90 / 10, more preferably 15 / 85 to 85 / 15, even more preferably 20 / 80 to 80 / 20, particularly preferably 25 / 75 to 75 / 25, and especially preferably 43 / 57 to 57 / 43.

[0114] The lubricating base oil (Y) used in the lubricating oil composition of the fourth aspect of the present invention is preferably a mixture of a synthetic oil (YB) and a silicone oil (YC) from the viewpoint of quality stability, and more preferably a mixture of a poly-α-olefin belonging to Group IV and a silicone oil (YC).

[0115] <Polyolefin Block Copolymer (X) Contained in Lubricating Oil Composition> The lubricating oil composition of the present invention contains the polyolefin block copolymer (X). By incorporating such a block copolymer (X) into the lubricating oil composition of the second aspect of the present invention, a lubricating oil composition with a high viscosity index and high-temperature viscosity retention can be obtained. By incorporating such a block copolymer (X) into the lubricating oil composition of the third aspect of the present invention, a lubricating oil composition with excellent viscosity characteristics containing a viscosity modifier that has excellent compatibility with the silicone oil base oil can be obtained. By incorporating such a block copolymer (X) into the lubricating oil composition of the fourth aspect of the present invention, a lubricating oil composition with excellent compatibility with the mineral oil (YA) and / or synthetic oil (YB) and the silicone oil (YC) can be obtained.

[0116] The lubricating oil compositions of the second to fourth aspects of the present invention contain 0.1 mass% or more and less than 50.0 mass% of polyolefin block copolymer (X). If the content of polyolefin block copolymer (X) is less than 0.1 mass%, sufficient viscosity index improving ability cannot be obtained. If the content of polyolefin block copolymer (X) is 50.0 mass% or more, fuel economy performance deteriorates. In the lubricating oil compositions of the second or third aspect of the present invention, the content of polyolefin block copolymer (X) relative to 100 mass% of the lubricating oil composition is preferably 1.0 mass% or more and 40.0 mass% or less, more preferably 2.0 mass% or more and 35.0 mass% or less, even more preferably 3.0 mass% or more and 30.0 mass% or less, particularly preferably 4.0 mass% or more and 25.0 mass% or less, and especially preferably 8.0 mass% or more and 12.0 mass% or less. In the lubricating oil composition of the fourth aspect of the present invention, the content of the polyolefin block copolymer (X) relative to 100% by mass of the lubricating oil composition is preferably 1.0% by mass or more and 50% by mass or less, more preferably 1.0% by mass or more and 45% by mass or less, even more preferably 1.0% by mass or more and 40% by mass or less, particularly preferably 2.0% by mass or more and 40% by mass or less, and especially preferably 30% by mass or more and 40% by mass or less.

[0117] In the lubricating oil composition of the present invention, the blending ratio of the lubricating base oil (Y) to the polyolefin block copolymer (X) is not particularly limited as long as the required properties for the intended application are satisfied. In the lubricating oil composition of the second or third aspect of the present invention, the mass ratio of the lubricating base oil (Y) to the polyolefin block copolymer (X) (mass of the lubricating base oil (Y) / mass of the block copolymer (X)) is preferably 60 / 40 to 99 / 1, more preferably 70 / 30 to 98 / 2, even more preferably 80 / 20 to 97 / 3, and particularly preferably 85 / 15 to 96 / 4. In the lubricating oil composition of the fourth aspect of the present invention, the mass ratio of the lubricating base oil (Y) to the polyolefin block copolymer (X) (mass of lubricating base oil (Y) / mass of block copolymer (X)) is preferably 30 / 70 to 99 / 1, more preferably 40 / 60 to 99 / 1, even more preferably 45 / 55 to 98 / 2, particularly preferably 60 / 40 to 98 / 2, and especially preferably 60 / 40 to 70 / 30.

[0118] The kinematic viscosity at 40°C of the lubricating oil composition of the second or third aspect of the present invention is preferably 1.0 to 100.0 mm ２ / s, more preferably 10.0 to 90.0 mm ２ / s, more preferably 15.0 to 80.0 mm ２ / s, particularly preferably 20.0 to 70.0 mm ２ / s, particularly preferably 26.2 to 63.4 mm ２ When the kinematic viscosity at 40°C is within this range, the lubricating oil composition of the second or third aspect of the present invention has an excellent balance between wear resistance and fluid properties. The kinematic viscosity can be determined by the method described in JIS K2283. The kinematic viscosity at 40°C of the lubricating oil composition of the fourth aspect of the present invention is preferably 100.0 to 1400 mm ２ / s, more preferably 200.0 to 1200 mm ２ / s, more preferably 400.0 to 1000 mm ２ / s, particularly preferably 450.0 to 950.0 mm ２ / s, particularly preferably 471.8 to 922.3 mm ２When the kinematic viscosity at 40°C is within this range, the lubricating oil composition of the fourth aspect of the present invention has excellent stability without phase separation of the components that make up the base oil, even when using a base oil that is a mixture of a mineral oil and / or a synthetic oil and a silicone oil. The kinematic viscosity can be determined by the method described in JIS K2283.

[0119] The kinematic viscosity at 100°C of the lubricating oil composition of the second or third aspect of the present invention is preferably 0.1 to 50.0 mm ２ / s, more preferably 1.0 to 40.0 mm ２ / s, more preferably 2.0 to 30.0 mm ２ / s, particularly preferably 3.0 to 25.0 mm ２ / s, particularly preferably 6.1 to 21.7 mm ２ When the kinematic viscosity at 100°C is within this range, the lubricating oil composition of the second or third aspect of the present invention can maintain lubricity at high temperatures. The kinematic viscosity can be determined according to JIS K2283. The kinematic viscosity at 100°C of the lubricating oil composition of the fourth aspect of the present invention is preferably 10.0 to 500.0 mm ２ / s, more preferably 30.0 to 300.0 mm ２ / s, more preferably 50.0 to 200.0 mm ２ / s, particularly preferably 70.0 to 170.0 mm ２ / s, particularly preferably 75.3 to 150.5 mm ２ When the kinematic viscosity at 100°C is within this range, the lubricating oil composition of the fourth aspect of the present invention exhibits excellent stability without phase separation of the components constituting the base oil, even when the base oil is a mixture of a mineral oil and / or a synthetic oil and a silicone oil. The kinematic viscosity can be determined by the method described in JIS K2283.

[0120] The viscosity index of the lubricating oil composition according to the second or third aspect of the present invention is preferably 50 or more, more preferably 100 or more, even more preferably 130 or more, particularly preferably 150 or more, and especially preferably 168 or more. The viscosity index of the lubricating oil composition according to the second or third aspect of the present invention is preferably 500 or less, more preferably 460 or less, even more preferably 440 or less, particularly preferably 420 or less, and especially preferably 405 or less. With a viscosity index within this range, the lubricating oil composition according to the second or third aspect of the present invention can maintain sufficient viscosity even at low temperatures. The viscosity index can be determined by the method specified in JIS K2283. The viscosity index of the lubricating oil composition according to the fourth aspect of the present invention is preferably 50 or more, more preferably 100 or more, even more preferably 150 or more, particularly preferably 200 or more, and especially preferably 230 or more. The viscosity index of the lubricating oil composition according to the fourth aspect of the present invention is preferably 600 or less, more preferably 500 or less, even more preferably 400 or less, particularly preferably 300 or less, and especially preferably 278 or less. If the viscosity index is within this range, the lubricating oil composition of the fourth aspect of the present invention can maintain a sufficient viscosity even at low temperatures. The viscosity index can be determined by the method specified in JIS K2283.

[0121] Furthermore, the lubricating oil composition of the present invention may contain additives such as detergent-dispersants, viscosity index improvers, antioxidants, corrosion inhibitors, anti-wear agents, friction modifiers, pour point depressants, rust inhibitors and anti-foaming agents, as needed, within the scope of the present invention.

[0122] Examples of additives that can be used in the lubricating oil composition of the present invention include the following, which can be used alone or in combination of two or more. Examples of detergent-dispersants include metal sulfonates, metal phenates, metal phosphanates, and succinimides. Alkali metal and alkaline earth metal salicylates, phenates, and sulfonate detergents are preferred in the lubricating oil composition of the present invention. Specific examples include calcium or magnesium sulfonates, phenates, salicylates, succinimides, and benzylamines. The detergent-dispersant can be used in an amount of 0 to 15 mass% based on 100 mass% of the lubricating oil composition, as needed. There are no particular restrictions on the base number of the detergent-dispersant, but it is preferably less than 350 mgKOH / g.

[0123] In addition to the polyolefin block copolymer (X), known viscosity index improvers such as olefin copolymers such as ethylene-α-olefin copolymers, methacrylate copolymers, liquid polybutene, etc., having a molecular weight of more than 50,000, can be used in combination. The viscosity index improver is used in an amount of 0 to 50% by mass relative to 100% by mass of the lubricating oil composition, as needed.

[0124] Examples of antioxidants include phenolic compounds such as 2,6-di-t-butyl-4-methylphenol and amine compounds. The antioxidant is used in an amount of 0 to 3 mass % based on 100 mass % of the lubricating oil composition, as needed.

[0125] Examples of the corrosion inhibitor include compounds such as benzotriazole, benzimidazole, thiadiazole, etc. The corrosion inhibitor is used in an amount of 0 to 3 mass % based on 100 mass % of the lubricating oil composition, as required.

[0126] Examples of anti-wear agents include inorganic or organic molybdenum compounds such as molybdenum disulfide, graphite, antimony sulfide, polytetrafluoroethylene, etc. The anti-wear agent is used in an amount of 0 to 3 mass % based on 100 mass % of the lubricating oil composition, as needed.

[0127] Examples of friction modifiers include amine compounds, imide compounds, fatty acid esters, fatty acid amides, and fatty acid metal salts, each of which has at least one alkyl or alkenyl group having 6 to 30 carbon atoms, particularly at least one linear alkyl or alkenyl group having 6 to 30 carbon atoms, in the molecule.

[0128] Examples of amine compounds include linear or branched, preferably linear, aliphatic monoamines having 6 to 30 carbon atoms, linear or branched, preferably linear aliphatic polyamines, and alkylene oxide adducts of these aliphatic amines. Examples of imide compounds include succinimides having linear or branched alkyl or alkenyl groups having 6 to 30 carbon atoms and / or compounds thereof modified with carboxylic acid, boric acid, phosphoric acid, sulfuric acid, etc. Examples of fatty acid esters include esters of linear or branched, preferably linear, fatty acids having 7 to 31 carbon atoms and aliphatic monohydric alcohols or aliphatic polyhydric alcohols. Examples of fatty acid amides include amides of linear or branched, preferably linear, fatty acids having 7 to 31 carbon atoms and aliphatic monoamines or aliphatic polyamines. Examples of fatty acid metal salts include alkaline earth metal salts (magnesium salts, calcium salts, etc.) and zinc salts of straight-chain or branched, preferably straight-chain, fatty acids having 7 to 31 carbon atoms.

[0129] The friction modifier is used in an amount of 0 to 5.0 mass % based on 100 mass % of the lubricating oil composition, as needed. Various known pour point depressants can be used as the pour point depressant. Specifically, a polymer compound containing an organic acid ester group is used, and a vinyl polymer containing an organic acid ester group is particularly preferred. Examples of vinyl polymers containing an organic acid ester group include alkyl methacrylate (co)polymers, alkyl acrylate (co)polymers, alkyl fumarate (co)polymers, alkyl maleate (co)polymers, and alkylated naphthalene.

[0130] Such pour point depressants have a melting point of -13°C or lower, preferably -15°C or lower, and more preferably -17°C or lower. The melting point of the pour point depressant is measured using a differential scanning calorimeter (DSC). Specifically, about 5 mg of a sample is placed in an aluminum pan, heated to 200°C, held at 200°C for 5 minutes, cooled to -40°C at 10°C / min, held at -40°C for 5 minutes, and then heated at 10°C / min. The melting point is determined from the endothermic curve obtained when the temperature is increased at 10°C / min.

[0131] The pour point depressant further has a weight average molecular weight (Mw) in the range of 20,000 to 400,000, preferably 30,000 to 300,000, more preferably 40,000 to 200,000, as determined by gel permeation chromatography (GPC) in terms of polystyrene standards.

[0132] The pour point depressant is used as needed in an amount of 0 to 2 mass % relative to 100 mass % of the lubricating oil composition.

[0133] Examples of the rust inhibitor include various amine compounds, metal carboxylates, polyhydric alcohol esters, phosphorus compounds, sulfonates, etc. The rust inhibitor is used in an amount of 0 to 3 mass % based on 100 mass % of the lubricating oil composition, as needed.

[0134] Examples of antifoaming agents include silicone compounds such as dimethylsiloxane and silica gel dispersions, alcohol-based or ester-based compounds, etc. The antifoaming agent is used in an amount of 0 to 0.2% by mass relative to 100% by mass of the lubricating oil composition, as needed.

[0135] In addition to the above additives, demulsifiers, colorants, oiliness agents (oiliness improvers), etc. may be used as needed. For lubricating oils, so-called DI packages, in which various necessary additives for this purpose are blended and concentrated and dissolved in lubricating oils such as mineral oils or synthetic hydrocarbon oils, are supplied industrially, and such DI packages can also be used in the lubricating oil composition of the present invention.

[0136] <Uses of Lubricating Oil Composition> The lubricating oil composition of the present invention can be suitably used as an automobile engine oil, automobile gear oil, automobile transmission oil, industrial lubricant, hydraulic oil, etc., and can be suitably used over a long period of time as a fuel-saving lubricant because it has a low viscosity but also a high viscosity index and high shear stability.

[0137] The present invention will be explained in more detail below based on examples, but the present invention is not limited to these examples in any way.

[0138] [Evaluation Methods] In the following examples and comparative examples, the physical properties of the ethylene-α-olefin copolymer, polyorganosiloxane, polyolefin block copolymer, lubricating oil composition, etc. were measured by the following methods.

[0139] <GPC Measurement> In the Synthesis Examples, Examples, Comparative Examples, etc., the weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) were determined by the following methods.

[0140] [Sample Pretreatment] 30 mg of the produced resin was dissolved in 20 ml of o-dichlorobenzene at 145° C., and the solution was then filtered through a sintered filter with a pore size of 1.0 μm to prepare an analytical sample.

[0141] [GPC Analysis] Using gel permeation chromatography (GPC), the weight average molecular weight (Mw) and number average molecular weight (Mn) were calculated in terms of polystyrene molecular weight, and a molecular weight distribution curve was obtained. The molecular weight distribution (Mw / Mn) was calculated from the weight average molecular weight (Mw) and number average molecular weight (Mn).

[0142] [Measurement conditions] Measuring device: Gel permeation chromatograph HLC-8321 GPC / HT type (manufactured by Tosoh Corporation) Analyzing device: Data processing software Empower2 (Waters, registered trademark) Column: TSKgel GMH ６ -2 tubes of HT and TSKgel GMH ６Two -HTLs (both 7.5 mm diameter x 30 cm length, Tosoh Corporation) Column temperature: 140°C Mobile phase: o-dichlorobenzene (containing 0.025% BHT) Detector: differential refractometer Flow rate: 1 mL / min Sample concentration: 0.15% (w / v) Injection volume: 0.4 mL Sampling time interval: 0.5 sec Column calibration: monodisperse polystyrene (Tosoh Corporation) Molecular weight conversion: PS conversion / standard conversion method

[0143] [Calculation of the Number of Hydrosilylated Carbon Atoms per 1000 Carbon Atoms in the Main Chain of the Ethylene-α-Olefin Copolymer (A) Portion of Polyolefin Block Copolymer (X)] In particular, a method for calculating the number of hydrosilylated carbon atoms per 1000 carbon atoms in the main chain of a polyolefin block copolymer synthesized from an ethylene-propylene copolymer block and polydimethylsiloxane will be described.

[0144] < １ H-NMR> [Measurement conditions] Measurement device: JEOL ECX400P nuclear magnetic resonance device Measurement nuclei: １ H (400 MHz) Measurement mode: Single pulse Pulse width: 45° (5.25 μsec) Number of points: 32k Measurement range: 20 ppm (-4 to 16 ppm) Repetition time: 7.0 seconds Number of accumulations: 64 Measurement solvent: o-dichlorobenzene-d4 Sample concentration: ca. 20 mg / 0.6 mL Measurement temperature: 120°C Window function: exponential (BF: 0.12 Hz) Chemical shift reference: o-dichlorobenzene (7.1 ppm)

[0145] the above １ The spectrum obtained by H-NMR measurement showed peaks corresponding to the methyl, methylene, and methine groups of the ethylene and propylene units in the main chain, as well as peaks corresponding to the methylene hydrogens on the hydrosilylated carbon bonded to the ethylene-propylene copolymer block and polydimethylsiloxane. The number of hydrosilylated carbon atoms per 1,000 carbon atoms in the main chain of the ethylene-propylene copolymer was calculated from the integrated intensity of each signal.

[0146]

[0147] In each formula, the dashed lines indicate bonds other than hydrogen atoms, and represent the block portion of an ethylene-propylene copolymer. The wavy lines indicate bonds to silicon atoms, and represent the block portion of polydimethylsiloxane. The peaks for each of hydrogen atoms 1 to 5 are observed near the following: Peak for hydrogen atom 1: 0.95 ppm to 1.4 ppm Peak for hydrogen atom 2: 0.95 ppm to 1.4 ppm Peak for hydrogen atom 3: 1.4 ppm to 1.7 ppm Peak for hydrogen atom 4: 0.45 ppm Peak for hydrogen atom 5: 1.7 ppm to 1.8 ppm

[0148] The number of hydrosilylated carbon atoms per 1000 carbon atoms in the main chain of the ethylene-propylene copolymer portion is given as follows: Number of hydrosilylated carbon atoms per 1000 carbon atoms in the main chain of the ethylene-propylene copolymer portion = 1000 × (integral intensity of signal 4 / 2 + integrated intensity of signal 5) / ({[(integral intensity of signal 1 + integrated intensity of signal 2) - 2 × integrated intensity of signal 3] / 4} × 2 + integrated intensity of signal 3 × 3) For example, an ethylene-propylene copolymer having a number average molecular weight (Mn) of 1000 and containing approximately equal amounts of ethylene and propylene has approximately 71 carbon atoms per chain. Assuming that all of the ethylene-propylene copolymer has reacted by the hydrosilylation reaction, the number of hydrosilylated carbon atoms per 1000 carbon atoms in the main chain of the ethylene-α-olefin copolymer (ethylene-propylene copolymer) portion will be approximately 14. Therefore, a value close to this value indicates that the hydrosilylation reaction has proceeded quantitatively.

[0149] [Calculation of ethylene and propylene contents in ethylene / α-olefin copolymer (A)] １ In the spectrum obtained by H-NMR measurement, ethylene units and propylene units in the main chain are observed. The ethylene and propylene contents of the ethylene / α-olefin copolymer (A) were calculated from the integrated intensity of each signal.

[0150] In each formula, dashed lines indicate bonds to atoms other than hydrogen atoms. The peaks of each hydrogen atom α to γ ​​are observed near the following ranges: - Hydrogen atom α peak: 0.95 ppm to 1.4 ppm - Hydrogen atom β peak: 0.95 ppm to 1.4 ppm - Hydrogen atom γ peak: 1.4 ppm to 1.7 ppm Furthermore, since the α and β peaks cannot be distinguished, the integrated intensity of α is calculated using the γ peak.

[0151] The quantitative formulas for the ethylene and propylene contents are as follows: Ethylene content (mol %) = 100 × [(integrated intensity of signal α + integrated intensity of signal β - 2 × integrated intensity of signal γ) / 4] / {[(integrated intensity of signal α + integrated intensity of signal β - 2 × integrated intensity of signal γ) / 4] + integrated intensity of signal γ} Propylene content (mol %) = 100 × integrated intensity of signal γ / {[(integrated intensity of signal α + integrated intensity of signal β - 2 × integrated intensity of signal γ) / 4] + integrated intensity of signal γ}

[0152] [Calculation of the content of vinyl or vinylidene terminal groups among all terminals of ethylene / α-olefin copolymer (A)] １３ The C-NMR spectrum showed vinyl end groups, vinylidene end groups, di-substituted olefin end groups, tri-substituted olefin end groups, and saturated end groups. The content of vinyl end groups in all end groups was calculated from the integrated intensity of each signal.

[0153] < １３ C-NMR> [Measurement conditions] Measurement device: AVANCE3 cryo-500 nuclear magnetic resonance device manufactured by Bruker Biospin Measurement nuclei: １３C (125 MHz) Measurement mode: Single pulse proton broadband decoupling Pulse width: 45° (5.00 μsec) Number of points: 64k Measurement range: 250 ppm (-55 to 195 ppm) Repetition time: 29.0 seconds Number of accumulations: 128 Measurement solvent: o-dichlorobenzene / benzene-d6 (4 / 1 v / v) Sample concentration: ca. 100 mg / 0.6 mL Measurement temperature: 120 °C, Window function: exponential (BF: 1.0 Hz) Chemical shift reference: δδ signal (29.73 ppm)

[0154]

[0155] In each formula, dashed lines indicate bonds to atoms other than hydrogen atoms. The peaks of carbon atoms a to e are observed near the following: Peaks of carbon atoms a and a': 115 ppm Peak of carbon atom b: 110 ppm Peak of carbon atom c: 130 ppm Peak of carbon atom d: 132 ppm Peak of carbon atom e: 23 ppm Peaks of carbon atoms e' to e''': 12 ppm

[0156] The quantitative formula for determining the content of vinyl groups in all terminals is as follows: Content (%) of vinyl groups in all terminals = 100 × {integrated intensity of signal a + integrated intensity of signal a' / [{integrated intensity of signal a + integrated intensity of signal a' + integrated intensity of signal b + (integrated intensity of signal c / 2) + integrated intensity of signal d + (integrated intensity of signal e / 2) + integrated intensity of signal e' + integrated intensity of signal e" + integrated intensity of signal e'" + integrated intensity of signal e""} / 2]}

[0157] The quantitative formula for determining the content of vinylidene terminal groups among all terminals is as follows: Content (%) of vinylidene terminal groups among all terminals = 100 × integrated intensity of signal b / [{integrated intensity of signal a + integrated intensity of signal a' + integrated intensity of signal b + (integrated intensity of signal c / 2) + integrated intensity of signal d + (integrated intensity of signal e / 2) + integrated intensity of signal e' + integrated intensity of signal e" + integrated intensity of signal e'" + integrated intensity of signal e""} / 2]

[0158] [Melt Point Measurement by DSC] DSC measurements were performed using a Seiko differential scanning calorimeter (DSC220) calibrated with an indium standard to determine the melting point (Tm). The measurement sample was weighed to approximately 10 mg on an aluminum DSC pan. A lid was crimped onto the pan to create a sealed atmosphere, yielding a sample pan. The sample pan was placed in a DSC cell, and an empty aluminum pan was placed as a reference. The DSC cell was heated from 30°C (room temperature) to 150°C at a rate of 10°C / min under a nitrogen atmosphere (first heating step). Next, after holding at 150°C for 5 minutes, the temperature was decreased at a rate of 10°C / min to cool the DSC cell to -30°C (temperature decrease step). After holding at -30°C for 5 minutes, the DSC cell was heated to 150°C at a rate of 10°C / min (second heating step). The melting peak top temperature of the enthalpy curve obtained in the second heating step was taken as the melting point (Tm). When two or more melting peaks are present, the one with the largest peak is defined as the melting point (Tm). When no melting peak is observed, it is evaluated as no melting point.

[0159] [Compatibility Test of Ethylene / α-olefin Copolymer (A)] 1 mL of various solvents was added to a 5 mL screw tube, and 1 mL of the ethylene / α-olefin copolymer (A) prepared in Synthesis Examples 1 and 2 below was added. The tube was left to stand at 25°C for 24 hours in an incubator, and the compatibility of the EPR in the screw tube was visually evaluated. The results are shown in Table 1-1.

[0160] [Evaluation criteria] Complete miscibility: No phase separation can be confirmed. Partial miscibility: Partial phase separation can be confirmed.

[0161] [State at Room Temperature (25° C.)] The state at room temperature (25° C.) was determined by visually observing the state of a target sample such as a polyolefin block copolymer at room temperature.

[0162] [Kinematic viscosity, viscosity index] Kinematic viscosity at 100°C (KV １００ ), kinematic viscosity at 40°C (KV ４０ ) and viscosity index were measured and calculated according to the method described in JIS K2283.

[0163] [Thickening property] The thickening property is determined by the KV of the lubricating oil composition.１００ From the value of KV of the base oil １００ The value obtained by subtracting the value of the difference was calculated and evaluated according to the following evaluation criteria. <Evaluation criteria> A: 2.0 or more and 10.0 or less B: Less than 2.0 or more than 10.0

[0164] [Viscosity Index Improvement Ability] The viscosity index improvement ability was calculated by subtracting the viscosity index value of the base oil from the viscosity index value of the lubricating oil composition, and evaluated according to the following evaluation criteria: <Evaluation Criteria> A: 42 or more B: Less than 42

[0165] [Evaluation of Compatibility] The lubricating oil compositions prepared in the Examples and Comparative Examples were divided into small portions in sample bottles and stored at room temperature. After 24 hours, the appearance was evaluated visually. <Evaluation Criteria> A: The solution was uniform and transparent. B: The solution was uniform but cloudy. Or, the solution was separated into layers.

[0166] <Raw Materials> <<Ethylene-α-Olefin Copolymer (A) (Single-Terminally Unsaturated Liquid Ethylene-Propylene Copolymer)>> [Synthesis Example 1] Ethylene-propylene copolymer (EPR-1) (ethylene-α-olefin copolymer (A)), a raw material for polyolefin block copolymer (X), was synthesized by the following method. 500 mL of xylene was placed in a 1.0 L glass reactor whose interior had been thoroughly purged with nitrogen, and the temperature was maintained at 110°C. While stirring the contents inside the reactor at 600 rpm, ethylene, propylene, and nitrogen were continuously fed at rates of 78 L / h, 44 L / h, and 52 L / h, respectively, to saturate the liquid and gas phases. While continuously supplying ethylene and propylene, 0.10 mL (0.10 mmol) of a toluene solution of triisobutylaluminum (1.0 mol / L), 2.5 mL (0.005 mmol) of a toluene solution of dimethylsilylbis(2-methyl-4-phenylindenyl)hafnium dichloride (0.002 mol / L), and then triphenylcarbenium tetrakis(pentafluorophenyl)borate (hereinafter referred to as Ph ３ CB (C ６ F ５ ) ４2.0 mL (0.020 mmol) of a toluene solution (0.01 mol / L) of ethylene-propylene copolymer (also referred to as ethylene-propylene copolymer) was added, and polymerization was carried out at 110°C for 16 minutes under normal pressure. The polymerization was terminated by adding a small amount of isobutanol. The obtained polymerization reaction solution was washed with dilute hydrochloric acid, and the organic layer obtained by separation was evaporated under reduced pressure to obtain an ethylene-propylene copolymer. The copolymer was dried under reduced pressure at 130°C for 10 hours to obtain 8.45 g of an ethylene-propylene copolymer. The obtained copolymer had Mw = 3850, Mn = 1280, Mw / Mn = 3.0, ethylene content = 50 mol%, propylene content = 50 mol%, １３ The vinyl and vinylidene groups in the total terminals, including unsaturated and saturated terminals, measured by C-NMR were 63% and 7%, respectively.

[0167] Synthesis Example 2 Ethylene-propylene copolymer (EPR-2) (ethylene-α-olefin copolymer (A)), a raw material for polyolefin block copolymer (X), was synthesized by the following method: 300 mL of toluene was placed in a 500 mL glass reactor, and while maintaining the temperature at 50° C. and stirring the contents inside the reactor at 600 rpm, ethylene and propylene were continuously fed at 9.9 L / h and 98.4 L / h, respectively, to saturate the liquid and gas phases. 5.0 mL (5.0 mmol) of a toluene solution (1.00 mol / L) of modified methylaluminoxane (hereinafter also referred to as MMAO) manufactured by Tosoh Fine Chemical Co., Ltd. was added, followed by 2.5 mL (0.005 mmol) of a toluene solution (0.002 mol / L) of bis(cyclopentadienyl)zirconium(IV) dichloride manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., and polymerization was carried out at normal pressure and 50°C for 30 minutes. Except for these, purification was carried out in the same manner as in Example 1, and 3.65 g of an ethylene-propylene copolymer was obtained. The obtained copolymer had Mw = 3030, Mn = 1140, Mw / Mn = 2.7, ethylene content = 49 mol%, propylene content = 51 mol%, １３ The vinyl group percentage and vinylidene group percentage in all terminals, including unsaturated terminals and saturated terminals, measured by C-NMR were 0% and 100%, respectively.

[0168] <<Polyorganosiloxane (B)>> [Both-end hydride-modified polydimethylsiloxane (PDMS)] PDMS-1 (XC96-C5071, manufactured by Shin-Etsu Silicones Co., Ltd., molecular weight calculated by GPC analysis: Mn = 1760, １ Si—H group content calculated by H-NMR analysis: 1.1 mmol / g) PDMS-2 (DMS-H03, manufactured by Gelest, molecular weight calculated by GPC analysis: Mn=500, １ Si—H group content calculated by H-NMR analysis: 2.5 mmol / g) PDMS-3 (DMS-H021, manufactured by Gelest, molecular weight calculated by GPC analysis: Mn=3220, １ Si—H group content calculated by H-NMR analysis: 0.28 mmol / g) PDMS-4 (DMS-H025, manufactured by Gelest, molecular weight calculated by GPC analysis: Mn=6710, １ Si—H group content calculated by H-NMR analysis: 0.14 mmol / g) [One-end hydride-modified polydimethylsiloxane (PDMS)] PDMS-5 (MCR-H021, manufactured by Gelest, molecular weight calculated by GPC analysis: Mn=8420, １ Si—H group content calculated by H-NMR analysis: 0.094 mmol / g)

[0169] <First Aspect> [Example 1-1] 1.0 g of (EPR-1) and 0.8 g of (PDMS-1) obtained in Synthesis Example 1 were placed in a 30 mL Schlenk tube equipped with a stirrer, and the mixture was dried at 80°C for 10 hours. Subsequently, at room temperature and in a nitrogen atmosphere, 7 mL of toluene and a Karstedt catalyst diluted with toluene (0.004 μmol in terms of Pt) were added while stirring using a magnetic stirrer, and the mixture was reacted for 2.5 hours. A small amount of methanol was then added to terminate the reaction. The solvent was then removed under reduced pressure, and the mixture was dried under reduced pressure at 130°C for 10 hours, yielding a liquid copolymer. As can be seen from the GPC curve shown in Figure 1, the peaks of the reaction product were hardly detected, which indicates that the hydrosilylation reaction proceeded with high efficiency and that the product was a polyolefin block copolymer (Block-1) having a block composed of structural units (I) derived from the ethylene-propylene copolymer (A) represented by general formula (1) and a block composed of structural units (II) derived from polydimethylsiloxane. １ Analysis by H-NMR revealed that the number of hydrosilylated carbon atoms per 1,000 carbon atoms in the main chain of the ethylene-propylene copolymer was 13.4. The physical properties of the copolymer obtained are shown in Table 1-2.

[0170] Example 1-2 A 30 mL Schlenk flask containing a stirrer was charged with 0.50 g of (EPR-1) and 0.16 g of (PDMS-2) obtained in Synthesis Example 1, and the mixture was dried at room temperature for 3 hours. The reaction was then carried out in the same manner as in Example 1, except that 5 mL of toluene and toluene-diluted Karstedt catalyst (0.002 μmol in terms of Pt) were added and reacted for 15 minutes while stirring using a magnetic stirrer at room temperature under a nitrogen atmosphere, to obtain a liquid block copolymer. The physical properties of the resulting copolymer are shown in Table 1-2.

[0171] Example 1-3 A 150 mL Schlenk flask containing a stirrer was charged with 8.0 g of (EPR-1) and 17.0 g of (PDMS-3) obtained in Synthesis Example 1, and the mixture was dried at room temperature for 3 hours. The reaction was then carried out in the same manner as in Example 1, except that 70 mL of toluene and a Karstedt catalyst (1.2 μmol in terms of Pt) diluted with toluene were added and the mixture was allowed to react for 1 hour while stirring using a magnetic stirrer at room temperature under a nitrogen atmosphere, to obtain a liquid block copolymer. The physical properties of the resulting copolymer are shown in Table 1-2.

[0172] Example 1-4 A 150 mL Schlenk flask containing a stirrer was charged with 5.0 g of (EPR-1) and 20.0 g of (PDMS-4) obtained in Synthesis Example 1, and the mixture was dried at room temperature for 3 hours. The reaction was carried out in the same manner as in Example 3, except that 80 mL of toluene and toluene-diluted Karstedt catalyst (0.8 μmol in terms of Pt) were added and reacted for 20 minutes while stirring at room temperature under a nitrogen atmosphere using a magnetic stirrer, yielding a liquid block copolymer. The physical properties of the resulting copolymer are shown in Table 1-2.

[0173] Example 1-5 A 30 mL Schlenk flask containing a stirrer was charged with 0.50 g of (EPR-1) obtained in Synthesis Example 1 and 2.5 g of (PDMS-5), and the mixture was dried at room temperature for 3 hours. The reaction was then carried out in the same manner as in Example 3, except that 10 mL of toluene and toluene-diluted Karstedt catalyst (0.08 μmol in terms of Pt) were added and reacted for 15 minutes while stirring using a magnetic stirrer at room temperature under a nitrogen atmosphere, to obtain a liquid block copolymer. The physical properties of the resulting copolymer are shown in Table 1-2.

[0174] [Example 1-6] A 30 mL Schlenk tube containing a stirrer was charged with 0.50 g of (EPR-2) and 0.58 g of (PDMS-1) obtained in Synthesis Example 2, and dried at 80 ° C. for 10 hours. Thereafter, at room temperature and under a nitrogen atmosphere, while stirring using a magnetic stirrer, 10 mL of toluene and a Karstedt catalyst (0.017 μmol in terms of Pt) diluted with toluene were added and reacted for 15 minutes. The reaction was carried out in the same manner as in Example 1, except that a liquid block copolymer was obtained. As shown in the GPC curve in Figure 2, the peaks of the reaction product were hardly detected, and the peaks derived from the raw materials EPR-2 and PDMS-1 were hardly detected. This indicates that the hydrosilylation reaction proceeded with high efficiency, and the product was a polyolefin-based block copolymer (Block-6) having a block composed of structural units (I) derived from an ethylene-propylene copolymer represented by the general formula (1) and a block composed of structural units (II) derived from polydimethylsiloxane. The physical properties of the copolymer obtained are shown in Table 1-2.

[0175] [Comparative Example 1-1] Silylated polyethylene was synthesized according to the method described in Synthesis Example 2 of JP 2021-91769 A. The physical properties of the obtained copolymer are shown in Table 1-2.

[0176] Comparative Example 1-2 TSF410, a higher fatty acid ester modified silicone oil manufactured by Momentive Corp., was used in Comparative Example 2. The physical properties of Comparative Example 1-2 are shown in Table 1-2.

[0177] Comparative Example 1-3 For Comparative Example 3, KF-4701, a long-chain alkyl-modified silicone oil manufactured by Shin-Etsu Silicones Co., Ltd., was used. The physical properties of Comparative Example 1-3 are shown in Table 1-2.

[0178]

[0179] <Second Aspect> [Polymerization Example 2-1-1] Polyolefin-Based Block Copolymer (X-2-1) 8.0 g of (EPR-1) obtained in Synthesis Example 1 and 17.0 g of (PDMS-3) were charged into a 150 mL Schlenk tube containing a stirrer and dried at room temperature for 3 hours. Thereafter, at room temperature and under a nitrogen atmosphere, while stirring using a magnetic stirrer, 70 mL of toluene and a Karstedt catalyst (1.2 μmol in terms of Pt) diluted with toluene were added and reacted for 2.5 hours, after which a small amount of methanol was added to terminate the reaction. Thereafter, the solvent was removed under reduced pressure, and the mixture was dried under reduced pressure at 130 °C for 10 hours to obtain a liquid polyolefin-based block copolymer (polyolefin-polyorganosiloxane block copolymer) (X-2-1). The physical properties of the obtained copolymer are shown in Table 2-2.

[0180] [Polymerization Example 2-1-2] Polyolefin-based block copolymer (X-2-2) A 30 mL Schlenk tube containing a stirrer was charged with 1.0 g of (EPR-1) obtained in Synthesis Example 1 and 0.8 g of (PDMS-1), and the mixture was dried at 80 ° C. for 10 hours. Thereafter, at room temperature and under a nitrogen atmosphere, while stirring using a magnetic stirrer, 7 mL of toluene and a Karstedt catalyst (0.004 μmol in terms of Pt) diluted with toluene were added and the reaction was carried out for 2.5 hours. The reaction was carried out in the same manner as in Polymerization Example 2-1-1, to obtain a liquid polyolefin-based block copolymer (polyolefin-polyorganosiloxane block copolymer) (X-2-2). The physical properties of the resulting copolymer are shown in Table 2-2.

[0181] Polymerization Example 2-2-1 Ethylene-α-olefin copolymer (D2-1) In a 2-L continuous polymerization reactor equipped with an agitator and thoroughly purged with nitrogen, 1 L of dehydrated and purified hexane was placed, and ethylaluminum sesquichloride (Al(C)) adjusted to 96 mmol / L was added thereto. ２ H ５ ) １．５ ・Cl １．５ ) in hexane was continuously fed at a rate of 500 mL / h for 1 hour, and then a 16 mmol / L solution of VO(OC) ２ H ５ ) Cl ２The hexane solution was continuously fed at a rate of 500 mL / h, and hexane was continuously fed at a rate of 500 mL / h. Meanwhile, the polymerization liquid was continuously withdrawn from the top of the reactor so that the volume of the polymerization liquid in the reactor was always 1 L.

[0182] Next, using a bubbling tube, ethylene gas was supplied at a rate of 36 L / h, propylene gas at a rate of 36 L / h, and hydrogen gas at a rate of 30 L / h. The copolymerization reaction was carried out at 35°C by circulating a coolant through a jacket attached to the outside of the reactor. This resulted in a polymerization solution containing an ethylene-propylene copolymer. The resulting polymerization solution was washed three times with 500 mL of 0.2 mol / L hydrochloric acid per 1 L of the polymerization solution, followed by three times with 500 mL of distilled water per 1 L of the polymerization solution. After drying over magnesium sulfate, the solvent was distilled off under reduced pressure. The resulting viscous liquid was dried under reduced pressure at 130°C for 24 hours to yield an ethylene-α-olefin copolymer (ethylene-propylene copolymer) (D2-1). The physical properties of the resulting copolymer are shown in Table 2-2.

[0183] Polymerization Example 2-2-2 Ethylene-α-olefin copolymer (D2-2) In a 2-L continuous polymerization reactor equipped with an agitator and thoroughly purged with nitrogen, 1 L of dehydrated and purified hexane was placed, and ethylaluminum sesquichloride (Al(C) ２ H ５ ) １．５ ・Cl １．５ ) in hexane was continuously fed at a rate of 500 mL / h for 1 hour, and then a 16 mmol / L solution of VO(OC) ２ H ５ ) Cl ２ The hexane solution was continuously fed at a rate of 500 mL / h, and hexane was continuously fed at a rate of 500 mL / h. Meanwhile, the polymerization liquid was continuously withdrawn from the top of the reactor so that the volume of the polymerization liquid in the reactor was always 1 L.

[0184] Next, using a bubbling tube, ethylene gas was supplied at a rate of 35 L / h, propylene gas at a rate of 35 L / h, and hydrogen gas at a rate of 80 L / h. The copolymerization reaction was carried out at 35°C by circulating a coolant through a jacket attached to the outside of the reactor. This resulted in a polymerization solution containing an ethylene-propylene copolymer. The obtained polymerization solution was treated in the same manner as in Polymerization Example 2-2-1 to obtain an ethylene-α-olefin copolymer (ethylene-propylene copolymer) (D2-2). The physical properties of the obtained copolymer are shown in Table 2-2.

[0185] Polymerization Example 2-2-3 Ethylene-α-olefin copolymer (D2-3) Into a 2-L continuous polymerization reactor equipped with an agitator and thoroughly purged with nitrogen, 1 L of dehydrated and purified hexane was placed, and ethylaluminum sesquichloride (Al(C)) adjusted to 96 mmol / L was added. ２ H ５ ) １．５ ・Cl １．５ ) in hexane was continuously fed at a rate of 500 mL / h for 1 hour, and then a 16 mmol / L solution of VO(OC) ２ H ５ ) Cl ２ The hexane solution was continuously fed at a rate of 500 mL / h, and hexane was continuously fed at a rate of 500 mL / h. Meanwhile, the polymerization liquid was continuously withdrawn from the top of the reactor so that the volume of the polymerization liquid in the reactor was always 1 L.

[0186] Next, using a bubbling tube, ethylene gas was supplied at a rate of 27 L / h, propylene gas at a rate of 26 L / h, and hydrogen gas at a rate of 100 L / h. The copolymerization reaction was carried out at 35°C by circulating a coolant through a jacket attached to the outside of the reactor. This resulted in a polymerization solution containing an ethylene-propylene copolymer. The obtained polymerization solution was treated in the same manner as in Polymerization Example 2-2-1 to obtain an ethylene-α-olefin copolymer (ethylene-propylene copolymer) (D2-3). The physical properties of the obtained copolymer are shown in Table 2-2.

[0187] Test Example 2-1-1 Alkyl-modified silicone oil (E2-1) In Test Example 2-1-1, the physical properties of TSF4421, an alkyl-modified silicone oil manufactured by Momentive Corp., were measured. The measurement results are shown in Table 2-2.

[0188] Test Example 2-1-2: Long-chain alkyl-modified silicone oil (E2-2) In Test Example 2-1-2, the physical properties of KF-4701, a long-chain alkyl-modified silicone oil manufactured by Shin-Etsu Silicones Co., Ltd., were measured. The measurement results are shown in Table 2-2.

[0189]

[0190] [Raw materials for the lubricating oil composition of the second embodiment] The components other than the polyolefin block copolymer (polyolefin-polyorganosiloxane block copolymer), ethylene-α-olefin copolymer, alkyl-modified silicone oil, and long-chain alkyl-modified silicone oil used in the preparation of the following lubricating oil composition are as follows. Lubricating oil base oil: The following lubricating oil base oil was used as the synthetic oil (YB). Synthetic oil (YB-2-1): kinematic viscosity (KV １００ ) is 4.0 mm ２ / s, kinematic viscosity (KV ４０ ) is 17.6 mm ２ / s, a viscosity index of 125, and a pour point of -60°C or less. Poly-α-olefin (Synfluid PAO4 manufactured by Chevron Phillips Chemical Company)

[0191] <Lubricating oil composition of second embodiment> [Example 2-1] A synthetic oil (YB-2-1) serving as a lubricating oil base oil and the polyolefin block copolymer (X) (X-2-1) obtained in Polymerization Example 2-1-1 were weighed into a beaker and mixed using a magnetic stirrer at 80°C for 1 hour to prepare a lubricating oil composition. The amounts of each component added and the physical properties of the resulting lubricating oil composition are shown in Table 2-3.

[0192] [Example 2-2, Comparative Examples 2-1 to 2-5] Lubricating oil compositions were prepared in the same manner as in Example 2-1, except that the types and amounts of components were changed as shown in Table 3. The physical properties of the obtained lubricating oil compositions are as shown in Table 2-3.

[0193] [Reference Example 2-1] The physical properties of synthetic oil (YB-2-1), which is a lubricating base oil, were measured. The measurement results are shown in Table 2-3.

[0194]

[0195] As shown in Table 2-3, when the Examples and Comparative Examples are compared, the Examples are superior in thickening properties and viscosity index improvement properties.

[0196] <Third Aspect> [Polymerization Example 3-1-1] Polyolefin-Based Block Copolymer (X-3-1) 8.0 g of (EPR-1) obtained in Synthesis Example 1 and 17.0 g of (PDMS-3) were charged into a 150 mL Schlenk tube containing a stirrer and dried at room temperature for 3 hours. Thereafter, at room temperature and under a nitrogen atmosphere, while stirring using a magnetic stirrer, 70 mL of toluene and a Karstedt catalyst (1.2 μmol in terms of Pt) diluted with toluene were added and reacted for 1 hour, and then a small amount of methanol was added to terminate the reaction. Thereafter, the solvent was removed under reduced pressure, and the mixture was dried under reduced pressure at 130 ° C. for 10 hours to obtain a liquid polyolefin-based block copolymer (polyolefin-polyorganosiloxane block copolymer) (X-3-1). The physical properties of the obtained copolymer are shown in Table 3-2.

[0197] [Polymerization Example 3-1-2] Polyolefin-based block copolymer (X-3-2) A 150 mL Schlenk tube containing a stirrer was charged with 5.0 g of (EPR-1) obtained in Synthesis Example 1 and 20.0 g of (PDMS-4), and the mixture was dried at room temperature for 3 hours. Thereafter, the mixture was stirred at room temperature under a nitrogen atmosphere using a magnetic stirrer, and 80 mL of toluene and a Karstedt catalyst (0.8 μmol in terms of Pt) diluted with toluene were added and reacted for 20 minutes. The reaction was carried out in the same manner as in Example 1, to obtain a liquid polyolefin-based block copolymer (polyolefin-polyorganosiloxane block copolymer) (X-3-2). The physical properties of the resulting copolymer are shown in Table 3-2.

[0198] Polymerization Example 3-2-1 Ethylene-α-olefin copolymer (D3-1) In a 2-L continuous polymerization reactor equipped with an agitator and thoroughly purged with nitrogen, 1 L of dehydrated and purified hexane was placed, and ethylaluminum sesquichloride (Al(C) ２ H ５ ) １．５ ・Cl １．５ ) in hexane was continuously fed at a rate of 500 mL / h for 1 hour, and then a 16 mmol / L solution of VO(OC) ２ H ５ ) Cl ２ The hexane solution was continuously fed at a rate of 500 mL / h, and hexane was continuously fed at a rate of 500 mL / h. Meanwhile, the polymerization liquid was continuously withdrawn from the top of the reactor so that the volume of the polymerization liquid in the reactor was always 1 L.

[0199] Next, using a bubbling tube, ethylene gas was supplied at a rate of 47 L / h, propylene gas at a rate of 47 L / h, and hydrogen gas at a rate of 20 L / h. The copolymerization reaction was carried out at 35°C by circulating a coolant through a jacket attached to the outside of the reactor. This resulted in a polymerization solution containing an ethylene-propylene copolymer. The resulting polymerization solution was washed three times with 500 mL of 0.2 mol / L hydrochloric acid per 1 L of the polymerization solution, followed by three times with 500 mL of distilled water per 1 L of the polymerization solution. After drying over magnesium sulfate, the solvent was distilled off under reduced pressure. The resulting viscous liquid was dried under reduced pressure at 130°C for 24 hours to yield an ethylene-α-olefin copolymer (ethylene-propylene copolymer) (D3-1). The physical properties of the resulting copolymer are shown in Table 3-2.

[0200] Polymerization Example 3-2-2 Ethylene-α-olefin copolymer (D3-2) Into a 2-L continuous polymerization reactor equipped with an agitator and thoroughly purged with nitrogen, 1 L of dehydrated and purified hexane was placed, and ethylaluminum sesquichloride (Al(C) ２ H ５ ) １．５ ・Cl １．５ ) in hexane was continuously fed at a rate of 500 mL / h for 1 hour, and then a 16 mmol / L solution of VO(OC) ２ H ５ ) Cl ２ The hexane solution was continuously fed at a rate of 500 mL / h, and hexane was continuously fed at a rate of 500 mL / h. Meanwhile, the polymerization liquid was continuously withdrawn from the top of the reactor so that the volume of the polymerization liquid in the reactor was always 1 L.

[0201] Next, using a bubbling tube, ethylene gas was supplied at a rate of 35 L / h, propylene gas at a rate of 35 L / h, and hydrogen gas at a rate of 80 L / h. The copolymerization reaction was carried out at 35°C by circulating a coolant through a jacket attached to the outside of the reactor. This resulted in a polymerization solution containing an ethylene-propylene copolymer. The obtained polymerization solution was treated in the same manner as in Polymerization Example 3-2-1 to obtain an ethylene-α-olefin copolymer (ethylene-propylene copolymer) (D3-2). The physical properties of the obtained copolymer are shown in Table 3-2.

[0202] Test Example 3-1-1 Alkyl-modified silicone oil (E3-1) In Test Example 3-1-1, the physical properties of TSF4421, an alkyl-modified silicone oil manufactured by Momentive Corp., were measured. The measurement results are shown in Table 3-2.

[0203]

[0204] [Raw materials for the lubricating oil composition of the third embodiment] The components other than the polyolefin block copolymer (polyolefin-polyorganosiloxane block copolymer), ethylene-α-olefin copolymer, and alkyl-modified silicone oil used in the preparation of the following lubricating oil composition are as follows. Lubricating oil base oil: The following lubricating oil base oil was used as the silicone oil (YC). Silicone oil (YC-3-1): kinematic viscosity (KV １００ ) is 6.5 mm ２ / s, kinematic viscosity (KV ４０ ) is 15.2 mm ２ / s, a viscosity index (VI) of 468, and a pour point of -60°C or lower (dimethyl silicone oil (PDMS): KF-96-20CS manufactured by Shin-Etsu Chemical Co., Ltd.)

[0205] <Lubricating oil composition of the third embodiment> [Example 3-1] A silicone oil (YC-3-1) serving as a lubricating oil base oil and the polyolefin block copolymer (X) (X-3-1) obtained in Polymerization Example 3-1-1 were weighed into a beaker and mixed using a magnetic stirrer at 80°C for 1 hour to prepare a lubricating oil composition. The amounts of each component added and the physical properties of the resulting lubricating oil composition are shown in Table 3-3.

[0206] [Example 3-2, Comparative Examples 3-1 to 3-3] Lubricating oil compositions were prepared in the same manner as in Example 3-1, except that the types and amounts of components were changed as shown in Table 3-3. The physical properties of the obtained lubricating oil compositions are as shown in Table 3-3.

[0207] [Reference Example 3-1] The physical properties of silicone oil (YC-3-1), a lubricating base oil, were measured, and the measurement results are shown in Table 3-3.

[0208]

[0209] As shown in Table 3-3, when Examples are compared with Comparative Examples, Examples have excellent compatibility.

[0210] <Fourth Aspect> [Polymerization Example 4-1-1] Polyolefin-Based Block Copolymer (X-4-1) 5.0 g of (EPR-1) obtained in Synthesis Example 1 and 20.0 g of (PDMS-4) were charged into a 150 mL Schlenk tube containing a stirrer and dried at room temperature for 3 hours. Thereafter, at room temperature and under a nitrogen atmosphere, while stirring using a magnetic stirrer, 80 mL of toluene and a Karstedt catalyst diluted with toluene (0.8 μmol in terms of Pt) were added and reacted for 1 hour, and then a small amount of methanol was added to terminate the reaction. Thereafter, the solvent was removed under reduced pressure, and the mixture was dried under reduced pressure at 130 ° C. for 10 hours to obtain a liquid polyolefin-based block copolymer (polyolefin-polyorganosiloxane block copolymer) (X-4-1). The physical properties of the obtained copolymer are shown in Table 4-2.

[0211] Polymerization Example 4-2-1 Ethylene-α-olefin copolymer (D4-1) Into a 2-L continuous polymerization reactor equipped with an agitator and thoroughly purged with nitrogen, 1 L of dehydrated and purified hexane was placed, and ethylaluminum sesquichloride (Al(C) ２ H ５ ) １．５ ・Cl １．５ ) in hexane was continuously fed at a rate of 500 mL / h for 1 hour, and then a 16 mmol / L solution of VO(OC) ２ H ５ ) Cl ２ The hexane solution was continuously fed at a rate of 500 mL / h, and hexane was continuously fed at a rate of 500 mL / h. Meanwhile, the polymerization liquid was continuously withdrawn from the top of the reactor so that the volume of the polymerization liquid in the reactor was always 1 L.

[0212] Next, using a bubbling tube, ethylene gas was supplied at a rate of 47 L / h, propylene gas at a rate of 47 L / h, and hydrogen gas at a rate of 20 L / h. The copolymerization reaction was carried out at 35°C by circulating a coolant through a jacket attached to the outside of the reactor. This resulted in a polymerization solution containing an ethylene-propylene copolymer. The resulting polymerization solution was washed three times with 500 mL of 0.2 mol / L hydrochloric acid per 1 L of the polymerization solution, followed by three times with 500 mL of distilled water per 1 L of the polymerization solution. After drying over magnesium sulfate, the solvent was distilled off under reduced pressure. The resulting viscous liquid was dried under reduced pressure at 130°C for 24 hours to yield an ethylene-α-olefin copolymer (ethylene-propylene copolymer) (D4-1). The physical properties of the resulting copolymer are shown in Table 4-2.

[0213] Test Example 4-1-1 Alkyl-modified silicone oil (F-1) In Test Example 4-1-1, the physical properties of TSF4421, an alkyl-modified silicone oil manufactured by Momentive Corp., were measured. The measurement results are shown in Table 4-2.

[0214]

[0215] [Raw materials for the lubricating oil composition of the fourth embodiment] The components other than the polyolefin block copolymer (polyolefin-polyorganosiloxane block copolymer), ethylene-α-olefin copolymer, and alkyl-modified silicone oil used in the preparation of the following lubricating oil composition are as follows. Lubricating oil base oil: The following lubricating oil base oils were used as synthetic oil (YB) and silicone oil (YC). Synthetic oil (YB-4-1): kinematic viscosity (KV １００ ) is 5.9 mm ２ / s, kinematic viscosity (KV ４０ ) is 30.9 mm ２ / s, a viscosity index (VI) of 137, and a pour point of -60°C or less. Synthetic oil (poly-α-olefin (PAO): Synfluid PAO6 manufactured by Chevron Phillips Chemical Co.) Silicone oil (YC-4-1): kinematic viscosity (KV １００ ) is 6.5 mm ２ / s, kinematic viscosity (KV ４０ ) is 15.2 mm ２ / s, a viscosity index (VI) of 468, and a pour point of -60°C or lower (dimethyl silicone oil (PDMS): KF-96-20CS manufactured by Shin-Etsu Chemical Co., Ltd.)

[0216] <Lubricating oil composition of the fourth embodiment> [Example 4-1] Synthetic oil (YB-4-1) and silicone oil (YC-4-1), which are lubricating oil base oils, and polyolefin block copolymer (X) (X-4-1) obtained in Polymerization Example 4-1-1, which is the polyolefin block copolymer (X), were weighed into a beaker and mixed using a magnetic stirrer at 80°C for 1 hour to prepare a lubricating oil composition. The amounts of each component added and the physical properties of the resulting lubricating oil composition are shown in Table 4-3.

[0217] [Examples 4-2 to 4-3, Comparative Examples 4-1 to 4-6] Lubricating oil compositions were prepared in the same manner as in Example 4-1, except that the types and amounts of components were changed as shown in Table 4-3. The physical properties of the obtained lubricating oil compositions are as shown in Table 4-3.

[0218]

[0219] As shown in Table 4-3, when the Examples and Comparative Examples are compared, the Examples have excellent compatibility.

Claims

1. A polyolefin block copolymer (X) having the following characteristics (X1) to (X3): (X1) Represented by the following formula (1), which has a block consisting of structural units (I) derived from an ethylene-α-olefin copolymer (A) having structural units (i) derived from ethylene and structural units (ii) derived from an α-olefin having 3 to 10 carbon atoms, and a block consisting of structural units (II) derived from a polyorganosiloxane (B) mainly composed of siloxane units; (X2) The polyolefin block copolymer (X) is a liquid at room temperature (25°C); (X3) The polyolefin block copolymer (X) does not have a melting point detectable by differential scanning calorimetry (DSC) in the range of -20°C to 140°C. [In the formula (1), A １ , A ２ and A ３ are each independently an ethylene / α-olefin copolymer (A) chain or a hydrocarbon group having 1 to 20 carbon atoms. ３ If there are multiple A ３ may be the same or different from each other. １ , A ２ and A ３ At least one of these represents an ethylene-α-olefin copolymer (A) chain. R represents a hydrocarbon group having 1 to 20 carbon atoms. Each R may be the same or different. n, m, and l each independently represent an integer of 1 to 1,000.] 2. The polyolefin block copolymer (X) according to claim 1, wherein the number of hydrosilylation carbon atoms at the bond between the block consisting of structural units (I) derived from the ethylene-α-olefin copolymer (A) and the block consisting of structural units (II) derived from the polyorganosiloxane (B), which are produced by a hydrosilylation reaction, is 2 to 47 per 1,000 carbon atoms in the main chain of the ethylene-α-olefin copolymer (A).

3. The polyolefin block copolymer (X) according to claim 1, wherein the ethylene-α-olefin copolymer (A) has the following characteristic (A1): (A1) The content of the structural unit (i) is 30 to 70 mol % and the content of the structural unit (ii) is 30 to 70 mol %, relative to 100 mol % of the total content of the structural unit (i) and the structural unit (ii).

4. The polyolefin block copolymer (X) according to claim 1, wherein the ethylene / α-olefin copolymer (A) is miscible with hydrocarbon solvents at room temperature (25°C) in an amount of 50 vol % or less.

5. The polyolefin block copolymer (X) according to claim 1, wherein the ethylene-α-olefin copolymer (A) has the following characteristic (A2): (A2) a number average molecular weight (Mn) of 300 to 5,000, as measured by gel permeation chromatography (GPC) and calculated in terms of polystyrene.

6. The polyolefin block copolymer (X) according to any one of claims 1 to 5, which is contained in a coating agent, lubricant, mold release agent, resin modifier, or lubricant modifier.

7. A method for producing the polyolefin block copolymer (X) according to claim 1, obtained by reacting an ethylene-α-olefin copolymer (A) having a structural unit (i) derived from ethylene and a structural unit (ii) derived from an α-olefin having 3 to 10 carbon atoms with a polyorganosiloxane (B) mainly composed of siloxane units.

8. The method for producing a polyolefin-based block copolymer (X) according to claim 7, wherein the ethylene / α-olefin copolymer (A) has the following characteristics (A1) to (A3): (A1) the content of the structural unit (i) is 30 to 70 mol % and the content of the structural unit (ii) is 30 to 70 mol % relative to 100 mol % of the total content of the structural unit (i) and the structural unit (ii); (A2) the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) and calculated in terms of polystyrene is 300 to 5,000; (A3) 13 The total content of vinyl group ends and vinylidene group ends is more than 60%, relative to 100% of the total integrated intensity of the signals of vinyl group ends, vinylidene group ends, di-substituted olefin ends, tri-substituted olefin ends, and saturated ends determined by C-NMR.

9. A method for producing the polyolefin block copolymer (X) according to claim 7 or 8, which is obtained by reacting in a hydrocarbon solvent at 0 to 80°C using a hydrosilylation catalyst.

10. A lubricating oil composition comprising a lubricating base oil (Y) and the polyolefin block copolymer (X) according to claim 1, wherein the lubricating base oil (Y) contains 0.1 mass % or more but less than 50.0 mass % of the polyolefin block copolymer (X), the lubricating base oil (Y) comprises a mineral oil (YA) and / or a synthetic oil (YB), and the synthetic oil (YB) is a hydrocarbon base oil.

11. The lubricating oil composition according to claim 10, wherein the polyolefin block copolymer (X) is a block copolymer produced by a hydrosilylation reaction between an ethylene-α-olefin copolymer (A) and a polyorganosiloxane (B), and the number of hydrosilylation carbon atoms at the bond between the block of structural units (I) derived from the ethylene-α-olefin copolymer (A) and the block of structural units (II) derived from the polyorganosiloxane (B) in the polyolefin block copolymer (X) is 2 to 47 per 1,000 carbon atoms in the main chain of the ethylene-α-olefin copolymer (A).

12. The lubricating oil composition according to claim 10, wherein the ethylene / α-olefin copolymer (A) of the polyolefin block copolymer (X) satisfies the following requirement (A1): (A1) The content of the structural unit (i) is 30 to 70 mol % and the content of the structural unit (ii) is 70 to 30 mol %, relative to 100 mol % of the total content of the structural unit (i) and the structural unit (ii).

13. The lubricating oil composition according to claim 10, wherein the lubricating base oil (Y) comprises a mineral oil (YA) having the following characteristics (YA1) to (YA3) and / or a synthetic oil (YB) having the following characteristics (YB1) to (YB3): (YA1) a kinematic viscosity at 100°C of 2.0 to 20.0 mm ２ (YA2) The viscosity index is 95 or more; (YA3) The pour point is -5°C or less; (YB1) The kinematic viscosity at 100°C is 1.0 to 20.0 mm ２ (YB2) kinematic viscosity at 40°C is 4.0 to 40.0 mm ２ (YB3) The pour point is -30°C or lower.

14. A lubricating oil composition comprising a lubricating base oil (Y) and the polyolefin block copolymer (X) according to claim 1, wherein the polyolefin block copolymer (X) is contained in an amount of 0.1 mass % or more and less than 50.0 mass %, and the lubricating base oil (Y) is composed of a silicone oil (YC).

15. The lubricating oil composition according to claim 14, wherein the polyolefin block copolymer (X) is a block copolymer produced by a hydrosilylation reaction between an ethylene-α-olefin copolymer (A) and a polyorganosiloxane (B), and the number of hydrosilylation carbon atoms at the bond between the block of structural units (I) derived from the ethylene-α-olefin copolymer (A) and the block of structural units (II) derived from the polyorganosiloxane (B) in the polyolefin block copolymer (X) is 2 to 47 per 1,000 carbon atoms in the main chain of the ethylene-α-olefin copolymer (A).

16. The lubricating oil composition according to claim 14, wherein the ethylene / α-olefin copolymer (A) of the polyolefin block copolymer (X) has the following characteristic (A1): (A1) The content of the structural unit (i) is 30 to 70 mol % and the content of the structural unit (ii) is 70 to 30 mol %, relative to 100 mol % of the total content of the structural unit (i) and the structural unit (ii).

17. The lubricating oil composition according to claim 14, wherein the lubricating base oil (Y) comprises a silicone oil (YC) having the following characteristics (YC1) to (YC3): (YC1) a kinematic viscosity at 100°C of 0.2 to 40.0 mm ２ (YC2) kinematic viscosity at 40°C is 0.4 to 80.0 mm ２ / s; (YC3) The pour point is -20°C or lower.

18. A lubricating oil composition comprising a lubricating base oil (Y) and the polyolefin block copolymer (X) according to claim 1, wherein the lubricating base oil (Y) comprises 0.1 mass % or more and less than 50.0 mass % of the polyolefin block copolymer (X), the lubricating base oil (Y) comprises a mineral oil (YA) and / or a synthetic oil (YB) and a silicone oil (YC), and the synthetic oil (YB) is a hydrocarbon base oil.

19. The lubricating oil composition according to claim 18, wherein the polyolefin block copolymer (X) is a block copolymer produced by a hydrosilylation reaction between an ethylene-α-olefin copolymer (X) and a polyorganosiloxane (B), and the number of hydrosilylation carbon atoms at the bond between the block of structural units (I) derived from the ethylene-α-olefin copolymer (A) and the block of structural units (II) derived from the polyorganosiloxane (B) in the polyolefin block copolymer (X) is 2 to 47 per 1,000 carbon atoms in the main chain of the ethylene-α-olefin copolymer (A) portion.

20. The lubricating oil composition according to claim 18, wherein the ethylene / α-olefin copolymer (A) of the polyolefin block copolymer (X) has the following characteristic (A1): (A1) The content of the structural unit (i) is 30 to 70 mol % and the content of the structural unit (ii) is 70 to 30 mol %, relative to 100 mol % of the total content of the structural unit (i) and the structural unit (ii).

21. The lubricating oil composition according to claim 18, wherein the mineral oil (YA) and / or synthetic oil (YB) contained in the lubricating base oil (Y) is a mineral oil (YA) having the following characteristics (YA1) to (YA3) and / or a synthetic oil (YB) having the following characteristics (YB1) to (YB3): (YA1) a kinematic viscosity at 100°C of 2.0 to 20.0 mm ２ (YA2) The viscosity index is 95 or more; (YA3) The pour point is -5°C or less; (YB1) The kinematic viscosity at 100°C is 1.0 to 20.0 mm ２ (YB2) kinematic viscosity at 40°C is 4.0 to 40.0 mm ２ (YB3) The pour point is -30°C or lower.

22. The lubricating oil composition according to claim 18, wherein the silicone oil (YC) contained in the lubricating base oil (Y) has the following characteristics (YC1) to (YC3): (YC1) a kinematic viscosity at 100°C of 0.2 to 40.0 mm ２ (YC2) kinematic viscosity at 40°C is 0.4 to 80.0 mm ２ / s; (YC3) The pour point is -20°C or lower.

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