WO2022186276A1

WO2022186276A1 - Modified polyalkylene diol

Info

Publication number: WO2022186276A1
Application number: PCT/JP2022/008875
Authority: WO
Inventors: 冬樹相田; 義隆真鍋
Original assignee: Ｅｎｅｏｓ株式会社
Priority date: 2021-03-03
Filing date: 2022-03-02
Publication date: 2022-09-09
Also published as: JPWO2022186276A1

Abstract

A modified polyalkylene diol represented by general formula (1), wherein the number average molecular weight of the corresponding polyalkylene diol is 100-8000. (In general formula (1), the multiple R1 may be the same or different and each independently represent a C2-5 linear alkylene group or a C3-8 branched chain alkylene group in which the main chain of the branched chain alkylene group has 2-5 carbon atoms, Q1 and Q2 may be the same or different and each independently represent a silyl group represented by general formula (3), and n represents an integer of 2 or more.) (In general formula (2), R2, R3, and R4 may be the same or different and each independently is a C1-9 hydrocarbon group.)

Description

Modified polyalkylenediol

The present invention relates to a polyalkylenediol-modified product, and more particularly to a polyalkylenediol-modified product that can be preferably used as a synthetic lubricating base oil with a high viscosity index.

　Lubrication is an essential element for reducing friction and wear of members in various mechanical devices with moving parts, and for improving the energy saving and life of the device.

As lubricants, lubricating compositions containing a lubricating base oil, optionally a thickener, and optionally one or more performance additives are used in a wide variety of fields. Examples of such lubricating compositions include lubricating oils and greases (semi-solid lubricants).

The lubricating base oil is the base material of the lubricating composition. A lubricating base oil is required to have a viscosity suitable for lubrication in the temperature range in which the lubricating composition is used. In general, the viscosity of fluids decreases at higher temperatures and increases at lower temperatures. In order for the lubricating composition to be usable over a wide temperature range, it is desirable that the temperature dependence of the viscosity of the lubricating base oil is small, that is, that the viscosity index of the lubricating base oil is high.

The API base oil classification stipulated by the American Petroleum Institute (API) classifies lubricating base oils into five categories, Groups IV. Group I base oils are mineral base oils having a sulfur content of greater than 0.03 mass % and/or a saturate content of less than 90 mass % and a viscosity index of 80 or more and less than 120. Group II base oils are mineral base oils having a sulfur content of 0.03 mass % or less, a saturate content of 90 mass % or more, and a viscosity index of 80 or more and less than 120. Group III base oils are mineral base oils having a sulfur content of 0.03% by weight or less, a saturates content of 90% by weight or more, and a viscosity index of 120 or more. Group IV base oils are polyalphaolefin base oils. Group V base oils are base oils other than Groups I-IV above.

Group III base oils, the highest viscosity index mineral base oils, are generally produced via hydrocracking and hydrorefining processes or obtained by the Fischer-Tropsch process wax (FT Waxes) and waxes obtained by the Gas-to-Liquid process (GTL waxes) are isomerized by a wax isomerization process. The achievable viscosity index of these conventional mineral base oils is approximately 135. For applications requiring a higher viscosity index, poly-α-olefin base oils (group IV base oils) and ester base oils ( Synthetic base oils such as Group V base oils are used.

International publication WO2018/207549

However, these conventional synthetic base oils do not necessarily have chemical properties suitable for all uses.

An object of the present invention is to provide a novel functional fluid that can be suitably used as a lubricating base material with a high viscosity index.

The present invention includes the following embodiments [1] to [6].
[1] A modified polyalkylenediol represented by the following general formula (1), wherein the corresponding polyalkylenediol has a number average molecular weight of 100 to 8,000.

(In general formula (1), a plurality of R ¹ may be the same or different, and each independently represents a linear alkylene group having 2 to 5 carbon atoms or a branched alkylene group having 3 to 8 carbon atoms. represents a branched alkylene group having a main chain of 2 to 5 carbon atoms, Q ¹ and Q ² may be the same or different and are each independently represented by the following general formula (2) It is a silyl group, and n represents an integer of 2 or more.)

(In general formula (2), R ² , R ³ and R ⁴ may be the same or different and each independently represents a hydrocarbon group having 1 to 9 carbon atoms.)

[2] In general formula (1), R ¹ is ethane-1,2-diyl group, propane-1,2-diyl group, butane-1,2-diyl group, butane-2,3-diyl group , or a butane-1,4-diyl group, or a combination thereof, the modified polyalkylenediol according to [1].

[3] In the general formula (1), Q ¹ and Q ² are a trimethylsilyl group, an ethyldimethylsilyl group, a dimethylpropylsilyl group, a butyldimethylsilyl group, an octyldimethylsilyl group, a triethylsilyl group, and a dimethylisopropylsilyl group; Diethylisopropylsilyl group, triisopropylsilyl group, tributylsilyl group, tert-butyldimethylsilyl group, dimethylphenylsilyl group, benzyldimethylsilyl group, methyldiphenylsilyl group, tert-butyldiphenylsilyl group, triphenylsilyl group, di- The polyalkylenediol-modified product according to [1] or [2], which is one or more silyl groups selected from a tert-butylisobutylsilyl group, a tricyclohexylsilyl group, a dicyclohexylphenylsilyl group, and a cyclohexyldiphenylsilyl group.

[4] Any of [1] to [3], wherein Q ¹ and Q ² are the same silyl group or the same combination of two or more silyl groups in the general formula (1) The modified polyalkylenediol according to 1.

[5] A lubricating base oil containing the modified polyalkylenediol according to any one of [1] to [4].

[6] A lubricating oil composition containing the lubricating base oil according to [5].

The polyalkylenediol-modified product, which is the functional fluid according to the first aspect of the present invention, can be suitably used as a lubricating base material with a high viscosity index.
According to the lubricating base oil according to the second aspect of the present invention, it is possible to increase the viscosity index by containing the polyalkylenediol-modified product according to the first aspect of the present invention.
According to the lubricating oil composition according to the third aspect of the present invention, by containing the lubricating base oil according to the second aspect of the present invention, the temperature-viscosity characteristics of the entire composition can be improved. It is possible.

The present invention will be described in detail below. In this specification, unless otherwise specified, the notation "A to B" for numerical values A and B is equivalent to "A or more and B or less". If a unit is attached only to the numerical value B in such notation, the unit is applied to the numerical value A as well. As used herein, the terms "or" and "or" shall mean a logical sum unless otherwise specified. As used herein, the notation “E ₁ and/or E ₂ ” for elements E ₁ and E ₂ is equivalent to “E ₁ or E ₂ , or a combination thereof” and N elements E ₁ , . _, _E _i _, _. _{_} _{_} , or a combination thereof” (i is a variable whose value is all integers satisfying 1<i<N). In this specification, magnesium is also included in the "alkaline earth metal".

As used herein, "(meth)acrylate" means "acrylate and/or methacrylate".

As used herein, "diol" is interpreted in the broadest sense and means a dihydric alcohol. Unless otherwise specified, the positional relationship of the two hydroxy groups in the "diol" is not restricted.

In this specification, unless otherwise specified, the content of each element of calcium, magnesium, zinc, phosphorus, sulfur, boron, barium, and molybdenum in oil is determined by inductively coupled plasma atomic emission spectrometry in accordance with JIS K0116. method (intensity ratio method (internal standard method)). Also, the nitrogen element content in the oil shall be measured by a chemiluminescence method in accordance with JIS K2609. In the present specification, "weight average molecular weight" and "number average molecular weight" mean weight average molecular weight and number average molecular weight in terms of standard polystyrene measured by gel permeation chromatography (GPC). GPC measurement conditions are as follows.
[GPC measurement conditions]
Apparatus: ACQUITY (registered trademark) APC UV RI system manufactured by Waters Corporation Column: ACQUITY (registered trademark) APC XT125A manufactured by Waters Corporation (gel particle size 2.5 μm, column size (inner diameter x length) 4.6 mm, in order from the upstream side) × 150 mm) and two ACQUITY (registered trademark) APC XT45A manufactured by Waters Corporation (gel particle size 1.7 μm, column size (inner diameter × length) 4.6 mm × 150 mm) are connected in series Column temperature: 40 ℃
Sample solution: Tetrahydrofuran solution with a sample concentration of 1.0% by mass Eluent: Tetrahydrofuran solution Injection volume: 20.0 μL
Flow rate: 0.7 mL/min Detector: Differential refractive index detector Reference material: Standard polystyrene (Agilent EasiCal (registered trademark) PS-1 manufactured by Agilent Technologies) 10 points (molecular weight: 30230, 9590, 2970, 890, 786, 682, 578, 474, 370, 266)

<1. Modified polyalkylenediol>
The polyalkylenediol-modified product (hereinafter sometimes simply referred to as "polyalkylenediol-modified product") according to the first aspect of the present invention is a polyalkylenediol having a number average molecular weight of 100 to 8,000. It is a diol-modified product and has a structure represented by the following general formula (1).

The corresponding polyalkylenediol is obtained by replacing Q ¹ and Q ² in general formula (1) with hydrogen atoms, and is represented by general formula (3) below.

The number average molecular weight of the corresponding polyalkylenediol is 100 or more, preferably 150 or more, more preferably 200 or more from the viewpoint of reducing volatility and improving abrasion resistance. From the viewpoint of reducing the viscosity to improve energy saving, it is 8,000 or less, preferably 6,000 or less, more preferably 5,000 or less, and in one embodiment, 2,500 or less. In one embodiment it may be 100-8000, or 150-6000, or 200-5000, or 200-2500.

Given a polyalkylenediol modification, the number average molecular weight of the corresponding polyalkylenediol can be determined as follows.
i) Identify the silyl groups Q ¹ , Q ² . The number of different silyl groups and their abundance ratio can be confirmed by measuring the ²⁹ Si NMR spectrum of the polyalkylenediol-modified product. Furthermore, the structure of the silyl group can be identified by subjecting the polyalkylenediol-modified product to cleavage of the Si—O bond and isolating the resulting low-molecular-weight silicon compound. If the abundance ratio of a plurality of different silyl groups cannot be determined by measuring the ²⁹ Si NMR spectrum of the polyalkylenediol-modified product, the abundance ratio of each silyl group should be confirmed from the amount of each isolated silicon compound. can be done. Treatment to cleave the Si—O bond of the polyalkylenediol-modified polyalkylenediol modification involves using a reagent that acts as a source of fluoride ions (typically tetrabutylammonium fluoride (TBAF) or HF-pyridine), silyl alcohol Deprotection can be carried out under the same conditions (for example, using TBAF in a tetrahydrofuran solvent and reacting at room temperature for 1 to 5 hours). The silicon compound obtained by this reaction corresponding to the silyl group of general formula (3) has the structure of F-SiR ³ R ⁴ R ⁵ . Determination of R ³ to R ⁵ can be carried out by a common-sense method in the field of organic chemistry using known analytical means such as ¹ H NMR spectrum and, if necessary, ¹³ C NMR spectrum, IR spectrum, and mass spectrometry (MS). can be done based on
ii) The polyalkylenediol simultaneously obtained in the Si—O cleavage reaction (deprotection reaction) of i) above is recovered, and its number average molecular weight Mn′ is measured by GPC. The measured Mn' is equal to the number average molecular weight Mn ^PAG of the corresponding polyalkylenediol.
When the silyl groups Q ¹ and Q ² are the same and one type of silyl group, the following step ii′) may be performed as a simple method instead of the above step ii).
ii') The number average molecular weight Mn'' of the entire polyalkylenediol-modified product is measured by GPC. Based on the measured Mn″ and the molecular weight M ^silyl of the silyl group, the number average molecular weight Mn ^PAG of the corresponding polyalkylenediol is determined by the following formula (1).
Mn ^PAG =Mn″−M ^{silyl +2.016} (1)

In general formula (1), R ¹ is a linear alkylene group having 2 to 5 carbon atoms, or a branched alkylene group having 3 to 8 carbon atoms and having a main chain of 2 to 5 carbon atoms. is the base. When R ¹ is a linear alkylene group, R ¹ preferably has 2 to 4 carbon atoms. When R ¹ is a branched alkylene group, R ¹ preferably has 3 to 6 carbon atoms and the main chain of R ¹ preferably has 2 to 4 carbon atoms. However, the number of carbon atoms in R ¹ is always equal to or greater than the number of carbon atoms in the main chain. As used herein, the number of carbon atoms in the main chain of R ¹ means the number of carbon atoms in the shortest carbon chain connecting two oxygen atoms bonded to R ¹ , and the selection of the main chain used in naming R ¹ determined regardless. For example, when R ¹ is a butane-1,2-diyl group, the main chain of R ¹ has 2 carbon atoms. When R ¹ is a linear alkylene group, the number of carbon atoms in the main chain of R ¹ is equal to the number of carbon atoms in R ¹ . When R ¹ is a branched alkylene group, the side chain of R ¹ is a linear or branched alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, in one embodiment can be a methyl group. The repeating unit R ¹ O having an alkylene group R ¹ (the number of carbon atoms in the main chain is Z (Z is an integer of 2 to 5, Y≧Z)) having Y carbon atoms (Y is an integer of 2 to 8), It can be obtained by ring-opening polymerization of an unsubstituted or substituted Z+1-membered saturated aliphatic cyclic ether having Y carbon atoms. Ring-opening polymerization of an unsubstituted cyclic ether gives an alkylene oxide repeating unit R ¹ O where R ¹ is a linear alkylene group, and ring-opening polymerization of a substituted cyclic ether gives a repeating unit R ¹ O where R ¹ is a branched alkylene group. give. Preferred examples of the alkylene group R ¹ include ethane-1,2-diyl, propane-1,2-diyl, butane-1,2-diyl, butane-2,3-diyl, pentane-1, 2-diyl group, hexane-1,2-diyl group, heptane-1,2-diyl group, octane-1,2-diyl group, and other alkylene groups having a main chain of 2 carbon atoms; propane-1,3-diyl 3-methylbutane-1,3-diyl group, 2,2-dimethylpropane-1,3-diyl group, and other alkylene groups having 3 main chain carbon atoms; butane-1,4-diyl group, pentane-1 ,4-diyl group, 2-methylbutane-1,4-diyl group, hexane-1,4-diyl group, 4-methylpentane-1,4-diyl group, hexane-2,5-diyl group and the like. An alkylene group having a chain carbon number of 4; and an alkylene group having a main chain carbon number of 5 such as a pentane-1,5-diyl group and a 3-methylpentane-1,5-diyl group can be mentioned. R ¹ may be a single alkylene group or a combination of two or more alkylene groups.

In one preferred embodiment, the alkylene group R ¹ is ethane-1,2-diyl, propane-1,2-diyl, butane-1,2-diyl, butane-2,3-diyl, or butane-1,4-diyl groups, or combinations thereof.

Preferable examples of cyclic ethers that give alkylene oxide repeating units R ¹ O by ring-opening polymerization include ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide and 1,2-pentylene. unsubstituted or substituted 3-membered ring ethers such as oxide, 1,2-hexylene oxide, 1,2-heptylene oxide, 1,2-octylene oxide; oxetane (trimethylene oxide), 2,2-dimethyl Unsubstituted or substituted 4-membered ring ethers such as oxetane, 3,3-dimethyloxetane, etc.; and unsubstituted or substituted 5-membered ring ethers such as , and unsubstituted or substituted 6-membered ring ethers such as tetrahydropyran and 4-methyltetrahydropyran. The alkylene oxide repeating unit R ¹ O may consist of repeating units corresponding to one type of cyclic ether, or may be a combination of repeating units corresponding to two or more types of cyclic ethers.

In general formula (1), n is an integer of 2 or more. Normally, n has a distribution, and the number average molecular weight is determined according to the distribution of n.

In general formula (2), R ² , R ³ and R ⁴ may be the same or different and each independently represents a hydrocarbon group having 1 to 9 carbon atoms. Preferred examples of hydrocarbon groups include alkyl groups (which may have a ring structure), aryl groups, alkylaryl groups, and arylalkyl groups.

For R ² to R ⁴ , the alkyl group may be a straight-chain alkyl group, a branched-chain alkyl group, or may have a ring structure. Examples of chain alkyl groups having 1 to 9 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, 1 -ethylpropyl group, hexyl group, isohexyl group, 1,1-dimethylbutyl group, 2,2-dimethylbutyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, heptyl group, octyl group, isooctyl group, 2 -ethylhexyl group, and nonyl group. Examples of the ring structure that the alkyl group may have include cycloalkyl rings having 5 to 7 carbon atoms such as cyclopentyl ring, cyclohexyl ring and cycloheptyl ring. The cycloalkyl ring may further have alkyl substituents and/or alkylene substituents, and their substitution positions on the cycloalkyl ring are arbitrary. Preferred examples of the alkyl group having 1 to 9 carbon atoms and having a ring structure include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a methylcyclopentyl group, a cyclopentylmethyl group, a methylcyclohexyl group, a cyclohexylmethyl group, and the like. .

Examples of aryl, alkylaryl and arylalkyl groups having 1 to 9 carbon atoms for R ² to R ⁴ are phenyl, tolyl, xylyl, mesityl, cumyl and benzyl. can be done.

Preferred examples of the silyl group represented by the general formula (2) for Q ¹ and Q ² include a trimethylsilyl group, an ethyldimethylsilyl group, a dimethylpropylsilyl group, a butyldimethylsilyl group, an octyldimethylsilyl group, and a triethylsilyl group. , dimethylisopropylsilyl group, diethylisopropylsilyl group, triisopropylsilyl group, tributylsilyl group, tert-butyldimethylsilyl group, dimethylphenylsilyl group, benzyldimethylsilyl group, methyldiphenylsilyl group, tert-butyldiphenylsilyl group, tri phenylsilyl group, di-tert-butylisobutylsilyl group, tricyclohexylsilyl group, dicyclohexylphenylsilyl group, cyclohexyldiphenylsilyl group, and the like.
In one embodiment, Q ¹ and Q ² are one selected from a trimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, a tert-butyldimethylsilyl group, a dimethylphenylsilyl group, and a tert-butyldiphenylsilyl group. The above silyl groups can be preferably employed.

In one embodiment, Q ¹ and Q ² can be the same and one silyl group. Such a polyalkylenediol-modified product can be obtained by using a single silylating agent as a silylating agent in the production method described below. In another embodiment, Q ¹ and Q ² can be the same combination of two or more silyl groups. Such a polyalkylenediol-modified product can be obtained by using a combination of two or more silylating agents as the silylating agent in the production method described below.

(Manufacturing)
In the polyalkylenediol-modified product of the present invention, the corresponding polyalkylenediol and a silylating agent corresponding to the silyl group of general formula (2) ( X ¹ -SiR ² R ³ R ⁴ ), for example, by the reaction represented by the following general formula (4). As the silylating agent, one silylating agent may be used alone, or two or more silylating agents may be used in combination. For example, a polyalkylenediol-modified product (silylation product) obtained by using a combination of a silylating agent A' corresponding to a silyl group A and a silylating agent B' corresponding to a silyl group B has the general formula In (1), a polyalkylenediol-modified product in which both ^Q1 and ^Q2 are silyl groups A, a polyalkylenediol-modified product in which both ^Q1 and ^Q2 are silyl groups B, and ^Q1 and ^Q2 It is a mixture with a modified polyalkylenediol in which one is a silyl group A and the other is a silyl group B. In addition, the silylating agent A' corresponding to the silyl group A is used alone to produce a first polyalkylenediol-modified product in which both ^Q1 and ^Q2 are silyl groups A, and the silylating agent corresponding to the silyl group B is prepared. Agent B′ is used alone to prepare a second polyalkylenediol modification in which both Q ¹ and Q ² are silyl groups B and optionally one or more other silyl groups C (, D, . . . ) corresponding to the silylating agent C′ (, D′, . By mixing modified products, a mixture of two or more polyalkylenediol-modified products in which Q ¹ and Q ² are the same silyl group may be obtained.

In general formula (4), R ¹ to R ⁴ and n are as defined in general formulas (1) to (3) above. X ¹ represents a leaving group of the silylating agent. Preferred examples of X ¹ include halogeno groups such as -Cl group, -Br group and -I group, trifluoromethanesulfonyloxy group (-OTf group) and the like. In general formula (4), “base” is a base for neutralizing the acid H—X generated from the terminal hydroxy group of the polyalkylenediol and Si—X, or for deprotonating the hydroxy group. Preferred examples of bases include amines such as triethylamine, diisopropylethylamine, imidazole, N-methylimidazole, pyridine, and 2,6-lutidine; metal hydrides such as lithium hydride, sodium hydride, potassium hydride; organometallic compounds such as alkyllithiums and Grignard reagents; and active metals such as metallic lithium, metallic sodium, metallic potassium, and metallic calcium.

The reaction of general formula (4) can be carried out in an aprotic solvent or without solvent. Examples of solvents include hydrocarbon solvents such as benzene, toluene, xylene, hexane, petroleum ether, cyclohexane, and methylcyclohexane; halogenated hydrocarbon solvents such as dichloromethane, chloroform, carbon tetrachloride, chlorobenzene, and dichlorobenzene; Ether solvents such as tetrahydrofuran and 4-methyltetrahydropyran; amine solvents that also serve as bases such as triethylamine and pyridine; and aprotic organic solvents such as dimethylsulfoxide, acetonitrile and N,N-dimethylformamide. can. As the solvent, it is preferable to use a solvent capable of dissolving both the starting polyalkylenediol and the silylated product.

The reaction of general formula (4) can be carried out by a known procedure as a silylation reaction. For example, a silylation reaction can be carried out by adding and mixing a base to a solution of a polyalkylenediol and then adding and mixing a silylating agent to the reaction mixture. Addition and mixing of the silylating agent can be performed, for example, by dropping the silylating agent or its solution into a mixture of the polyalkylenediol solution and the base at a low temperature (for example, 0°C). After adding the silylating agent to the reaction mixture, the silylation reaction can be allowed to proceed by stirring the reaction mixture at a low temperature or normal temperature for a certain period of time (for example, 0.01 to 100 hours). The reactivity of the silylating agent varies depending on the structure of the polyalkylenediol and/or the substituents R ² to R ⁴ on the silicon atom. When the progress of the reaction is slow at room temperature, it is preferable to carry out the reaction at a higher temperature (for example, reflux conditions for the solvent).

In the reaction of general formula (4), for example, 1 to 10 mol of a base and 0.5 to 2 mol, preferably 1.0 to 1.2 mol of a silylating agent can be used per 1 mol of the hydroxy group of the polyalkylenediol. can. When the silylating agent was used in an amount less than the equivalent of the hydroxy group, only the hydroxy group at one end of the polyalkylenediol was silylated together with the completely silylated product in which the hydroxy groups at both ends of the polyalkylenediol were silylated. A partial silylation product is formed. Depending on the reactivity of the silylation reaction, a partially silylated product may be produced together with a fully silylated product, but a mixture containing a fully silylated product and a partially silylated product may be used as it is.

Post-treatment after completion of the reaction may be carried out in the same manner as in general alcohol silylation reactions. Unreacted silylating agent can be quenched by water or alcohol treatment. The silylated products have improved hydrophobicity due to the conversion of the terminal hydroxy groups to silyl ethers. Therefore, by washing the reaction mixture with water, the salt in the reaction mixture (for example, triethylamine hydrochloride when the base is triethylamine and the leaving group X ¹ of the silylating agent is a —Cl group). and incompletely silylated polyalkylenediol (that is, unreacted polyalkylenediol that is not silylated, and a partially silylated product in which only the hydroxy group at one end of the polyalkylenediol is silylated) are removed. to obtain an organic solvent solution of the silylated product.
However, when the ratio of polyethylene oxide repeating units in the repeating units of the starting polyalkylenediol is high (that is, when the ratio of ethane-1,2-diyl groups in the alkylene groups R ¹ is high), the reaction mixture is mixed with water. When mixed, the silylated product may migrate from the organic layer to the aqueous layer, reducing the yield. In such cases, it is possible to recover the silylated product by a waterless workup. Specifically, after the reaction is carried out using a solvent having a certain degree of polarity (for example, toluene, etc.) in order to dissolve the raw material polyalkylenediol, the remaining unreacted silylating agent is removed with an alcohol ( For example, methanol, ethanol, etc.), a hydrophobic solvent (e.g., hexane, petroleum ether, cyclohexane, benzene, further a hydrocarbon solvent such as toluene) is added to the slurry reaction mixture, and the precipitated salt is filtered off. By removing, an organic solvent solution of the silylated product can be obtained.
The silylated product can be separated by distilling off the organic solvent (for example, under reduced pressure) from the obtained organic solvent solution of the silylated product.

(physical properties)
The polyalkylene diol modifications of the present invention have improved viscosity indexes over the corresponding non-silylated polyalkylene diols due to the conversion of the terminal hydroxy groups to silyl ethers, resulting in high viscosity index can be preferably used as a lubricating base material.

In addition, the polyalkylenediol-modified product of the present invention has higher polarity than conventional mineral oil-based base oils and poly-α-olefin base oils, and silicone oil (polydimethylsiloxane), which is a conventional general-purpose high viscosity index lubricating base material. Therefore, it is advantageous in terms of solubility of polar additives. Furthermore, in conventional ester-based synthetic base oils, the carbonyl carbon of the ester bond is susceptible to nucleophilic attack, whereas the ether bond and silyl ether bond of the polyalkylenediol-modified product of the present invention are nucleophilic under basic conditions. It is more robust against attack than an ester bond. Therefore, the polyalkylenediol-modified product of the present invention can be combined with additives that have been difficult to use in combination with conventional ester-based synthetic base oils due to their nucleophilicity.

The modified polyalkylenediol of the present invention has a viscosity index improved over that of the corresponding polyalkylenediol. Generally, the bulkier the silyl group, the higher the chemical stability of the silyl ether bond, so the silyl group can be selected in consideration of the stability and viscosity index required for the intended use. A specific viscosity index of the polyalkylenediol modification can be, for example, 100-300, and in one embodiment 150-300.

As explained above, the modified polyalkylenediol of the present invention can be produced by silylating the hydroxy groups of the polyalkylenediol. The kinematic viscosity of the polyalkylenediol-modified product of the present invention can vary depending on the kinematic viscosity of the corresponding polyalkylenediol and the silyl groups (Q ¹ and Q ² in general formula (1)). The higher the kinematic viscosity of the corresponding polyalkylenediol, the higher the kinematic viscosity of the resulting polyalkylenediol-modified product. Further, if the corresponding polyalkylenediol is the same, the kinematic viscosity of the polyalkylenediol-modified product tends to increase as the silyl group is bulkier. A mixture of two or more polyalkylenediols may be used as the starting polyalkylenediol in order to obtain a polyalkylenediol-modified product having the desired kinematic viscosity and viscosity index. In addition, two or more polyalkylenediol-modified products may be mixed in order to obtain a polyalkylenediol-modified product having a desired kinematic viscosity and viscosity index.

<2. Lubricant base oil>
The lubricating base oil according to the second aspect of the present invention (hereinafter sometimes simply referred to as "lubricating base oil") is the polyalkylenediol-modified product according to the first aspect of the present invention (hereinafter referred to as " (a) may be referred to as "component"). The lubricating base oil may contain one polyalkylenediol-modified product alone, or may contain two or more polyalkylenediol-modified products. In one embodiment, the lubricating base oil consists of one or more polyalkylenediol modifications. The lubricating base oil may further contain as an impurity an incompletely silylated polyalkylenediol that was not removed during the refining process of the modified polyalkylenediol. Examples of incompletely silylated polyalkylene diols include non-silylated polyalkylene diols and polyalkylene diols in which only one terminal hydroxy group is silylated (partially silylated product). In one embodiment, the content of these incompletely silylated polyalkylenediols can be, for example, less than 50 parts by weight, or less than 30 parts by weight per 100 parts by weight of polyalkylenediol modification. The content of incompletely silylated polyalkylenediol can be measured by ¹³ C NMR under the conditions described below. In one embodiment, the content of non-silylated hydroxy groups of the polyalkylenediol can be, for example, less than 0.5 mol, or less than 0.3 mol, per mol of silyl groups of the polyalkylenediol modification.
In one embodiment, the lubricating base oil may further comprise one or more base oil components other than the polyalkylenediol modified product. Such other base oil components can be mineral base oils, conventional synthetic base oils, or combinations thereof.

In one embodiment, examples of mineral base oils include solvent deasphalting, solvent extraction, hydrocracking, hydroisomerization, and hydroisomerization of lubricating oil fractions obtained by atmospheric distillation and/or vacuum distillation of crude oil. Paraffinic mineral oil, normal paraffinic base oil, refined by one or a combination of two or more selected from refining treatments such as dewaxing, solvent dewaxing, catalytic dewaxing, solvent refining, hydrorefining, chemical washing, clay treatment, etc. Isoparaffinic base oils, naphthenic base oils, mixtures thereof, and the like can be mentioned.

In one embodiment, preferred examples of the mineral base oil include any one of the following (1) to (8) as a raw material oil, and / or a lubricating oil distillate recovered from the raw material oil Base oils obtained by refining fractions may be mentioned.
(1) Distillate oil obtained by atmospheric distillation of paraffin-based crude oil and/or mixed-base crude oil (2) Distillate oil obtained by vacuum distillation of atmospheric distillation residue oil of paraffin-based crude oil and/or mixed-base crude oil ( WVGO)
(3) Waxes (such as slack waxes) obtained by lubricating oil dewaxing processes and/or Fischer-Tropsch (FT) processes (e.g. Gas-to-Liquid (GTL) processes etc.) (for example, FT wax such as GTL wax), synthetic wax obtained by oligomerization of ethylene (4) feed oil (1), (2), or (3), or a mild mixture thereof Hydrocracked oil (5) Mixed oil of two or more selected from feedstock oils (1) to (4) (6) Feedstock oil (1), (2), (3), (4) or (5) Deasphalted oil (DAO)
(7) Mild hydrocracking treated oil (MHC) of raw material oil (6)
(8) Mixed oil of two or more selected from raw materials (1) to (7)

A particularly preferred example of the mineral base oil is the following (9 ) or the base oil of (10).
(9) Hydrocracking the raw material oil selected from (1) to (8) above or the lubricating oil fraction recovered from the raw material oil, and the product or lubricating oil recovered from the product by distillation or the like Hydrocracking base oil (10) obtained by subjecting the fraction to dewaxing treatment such as solvent dewaxing or catalytic dewaxing, or by distillation after the dewaxing treatment (10) selected from the above (1) to (8) The raw oil or the lubricating oil fraction recovered from the raw oil is hydroisomerized, and the product or the lubricating oil fraction recovered from the product by distillation or the like is subjected to dewaxing such as solvent dewaxing or catalytic dewaxing. A hydroisomerized base oil obtained by performing a waxing treatment or by distillation after the dewaxing treatment. As the dewaxing step, a base oil produced through a catalytic dewaxing step is preferred.

In addition, when obtaining the mineral base oil of (9) or (10) above, a solvent refining treatment and/or hydrofinishing treatment step may be further performed at an appropriate stage, if necessary.

In one embodiment, the mineral base oil includes Group I base oil of API base oil classification (hereinafter sometimes referred to as "API Group I base oil"), Group II base oil (hereinafter referred to as "API Group II Group III base oils (hereinafter sometimes referred to as "API Group III base oils"), or combinations thereof can be used. The API base oil classification is as described above. API Group I base oils are typically produced via solvent refining processes, and API Group II and Group III base oils are typically manufactured via hydrocracking processes. As used herein, the viscosity index means a viscosity index measured according to JIS K 2283-2000. Also, in this specification, the "sulfur content in the lubricating base oil" shall be measured in accordance with JIS K 2541-2003. In addition, the "content of saturates in the lubricating base oil" as used herein means the value measured according to ASTM D 2007-93.

Conventional synthetic base oils include API base oil classification group IV base oils (poly-α-olefin base oils, hereinafter sometimes referred to as "API group IV base oils"), or conventional API base oil classification group V Base oils (hereinafter sometimes referred to as "API Group V base oils") or combinations thereof can be used.

The content of the component (a) in the lubricating base oil is not particularly limited, but for example, 1 to 100% by mass, or 5 to 100% by mass, or 10 to 100% by mass based on the total amount of the lubricating base oil , or 20-100% by weight, or 50-100% by weight, or 80-100% by weight.

<3. Lubricating Oil Composition>
The lubricating oil composition according to the third aspect of the present invention (hereinafter sometimes simply referred to as "lubricating oil composition") is the lubricating base oil according to the second aspect of the present invention (hereinafter referred to as "( A) may be referred to as “component”). In one embodiment, the lubricating oil composition may consist of the (A) component. In another embodiment, the lubricating oil composition may comprise component (A) and one or more additives.

The content of component (A) in the lubricating oil composition is not particularly limited, but can be, for example, 60 to 100% by mass, or 60 to 99% by mass based on the total amount of the composition.

As additives, known additives in the field of lubricating oils can be used. Examples of such additives include (B) antioxidants, (C) ashless dispersants, (D) metallic detergents, (E) friction modifiers, (F) antiwear or extreme pressure agents, (G) a viscosity index improver or pour point depressant, (H) a corrosion inhibitor, (I) a rust inhibitor, (J) a metal deactivator, (K) a demulsifier, (L) a defoamer, and (M) A coloring agent can be mentioned.

Examples of (B) antioxidants (hereinafter sometimes referred to as "component (B)") include aromatic amine antioxidants, hindered amine antioxidants, and phenolic antioxidants. can.

Examples of aromatic amine antioxidants include primary aromatic amine compounds such as alkylated α-naphthylamine; - secondary aromatic amine compounds such as naphthylamine and alkylated phenyl-β-naphthylamine.

Examples of hindered amine antioxidants include compounds having a 2,2,6,6-tetraalkylpiperidine skeleton (2,2,6,6-tetraalkylpiperidine derivatives). As the 2,2,6,6-tetraalkylpiperidine derivative, a 2,2,6,6-tetraalkylpiperidine derivative having a substituent at the 4-position is preferred. Also, two 2,2,6,6-tetraalkylpiperidine skeletons may be bonded via their respective 4-position substituents. Also, the N-position of the 2,2,6,6-tetraalkylpiperidine skeleton may be unsubstituted, or the N-position may be substituted with an alkyl group having 1 to 4 carbon atoms. The 2,2,6,6-tetraalkylpiperidine skeleton is preferably 2,2,6,6-tetramethylpiperidine skeleton.

Examples of phenolic antioxidants include 4,4'-methylenebis(2,6-di-tert-butylphenol); 4,4'-bis(2,6-di-tert-butylphenol); 4,4' -bis(2-methyl-6-tert-butylphenol); 2,2'-methylenebis(4-ethyl-6-tert-butylphenol); 2,2'-methylenebis(4-methyl-6-tert-butylphenol); 4,4′-butylidenebis(3-methyl-6-tert-butylphenol); 4,4′-isopropylidenebis(2,6-di-tert-butylphenol); 2,2′-methylenebis(4-methyl-6 -nonylphenol); 2,2′-isobutylidenebis(4,6-dimethylphenol); 2,2′-methylenebis(4-methyl-6-cyclohexylphenol); 2,6-di-tert-butyl-4 -methylphenol; 2,6-di-tert-butyl-4-ethylphenol; 2,4-dimethyl-6-tert-butylphenol; 2,6-di-tert-butyl-4-(N,N'-dimethyl aminomethyl)phenol; 4,4′-thiobis(2-methyl-6-tert-butylphenol); 4,4′-thiobis(3-methyl-6-tert-butylphenol); 2,2′-thiobis(4- methyl-6-tert-butylphenol); bis(3-methyl-4-hydroxy-5-tert-butylbenzyl) sulfide; bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide; 3-( 3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid esters; 3-methyl-5-tert-butyl-4-hydroxyphenol fatty acid esters, hindered phenol compounds and bisphenol compounds can be done.

When the lubricating oil composition contains component (B), its content may be, for example, 0.01 to 5.0% by mass, or 0.1 to 5.0% by mass, based on the total amount of the composition. From the viewpoint of suppressing autoxidation of the polyalkylenediol-modified product (component (a)), the lubricating oil composition preferably contains at least the component (B).

(C) As the ashless dispersant, a known ashless dispersant such as a succinimide-based ashless dispersant can be used. Examples of ashless dispersants include polybutenylsuccinimide, polybutenylbenzylamine, polybutenylamine having a polybutenyl group with a number average molecular weight of 900 to 3,500, and derivatives thereof (for example, modified with boric acid). etc.).
When the lubricating oil composition contains an ashless dispersant, its content can be, for example, 0.01 to 20% by weight, or 0.1 to 10% by weight, based on the total amount of the composition.

(D) As the metallic detergent, a known metallic detergent in the lubricating oil field can be used. In general, in the field of lubricating oils, metallic detergents include organic acid metal salts capable of forming micelles in base oils (e.g. alkali or alkaline earth metal alkyl salicylates, alkali or alkaline earth metal alkyl benzene sulfonates, and alkali or alkaline earth metal alkylphenate, etc.), or the organic acid metal salt and a basic metal salt (for example, alkali or alkaline earth metal hydroxides, carbonates, and boric acids constituting the organic acid metal salt) salt etc.) are used. Alkaline earth metals are preferred as metals, and Ca and/or Mg are preferred as alkaline earth metals.
When the lubricating oil composition contains a metallic detergent, its content may be, for example, 0.001 to 5.0% by mass in terms of metal element based on the total amount of the composition.

(E) As the friction modifier, a known friction modifier in the lubricating oil field can be used, examples of which include oily agent-based friction modifiers; organic molybdenum compounds; organic boron compounds such as alkyl mercaptyl borate; molybdenum disulfide; antimony sulfide; boron compounds; polytetrafluoroethylene;

When the lubricating oil composition contains a friction modifier, its content may be, for example, 0.05 to 5.0% by mass based on the total amount of the composition.

(F) As the anti-wear agent or extreme pressure agent, an anti-wear agent or extreme pressure agent known in the lubricating oil field can be used. Examples thereof include metal salts of dithiocarbamates (Zn salts, Pb salts, Sb salts, etc.), sulfur additives such as disulfides, sulfurized oils, sulfurized olefins, sulfurized mineral oils, dialkyl polysulfides, diarylalkyl polysulfides, and diaryl polysulfides; dithiophosphoric acid Metal salts (Zn salts, Pb salts, Sb salts, Mo salts, etc.), phosphate esters, phosphites, amine salts of phosphoric acid partial esters, metal salts of phosphoric acid partial esters (Zn salts, etc.), (monothio- or metal and amine salts of full and partial esters and partial esters of (monothio- or dithio-)phosphoric acid, metal and amine salts of full and partial and partial esters of (monothio- or dithio-)phosphorous acid and phosphorus-sulfur additives such as , and naphthenic acid metal salts (Pb salts, etc.), fatty acid metal salts (Pb salts, etc.), boron compounds, and the like.
When the lubricating oil composition contains an antiwear agent or extreme pressure agent, its content may be, for example, 0.05 to 5% by mass based on the total amount of the composition.

As the viscosity index improver or pour point depressant (G), a known viscosity index improver or pour point depressant in the lubricating oil field can be used. Examples of viscosity index improvers include dispersant or non-dispersant polyalkyl (meth)acrylates; non-dispersant or dispersant ethylene-α-olefin copolymers and hydrogenated products thereof; polyisobutylene and hydrogenated products thereof; Hydrogenated products of styrene-diene copolymers; styrene-maleic anhydride ester copolymers; and polyalkylstyrenes.
Examples of pour point depressants include polymethacrylate-based polymers and ethylene vinyl acetate.
When the lubricating oil composition contains a viscosity index improver or a pour point depressant, its content may be, for example, 0.01 to 20% by mass based on the total amount of the composition.

(H) As the corrosion inhibitor, a known corrosion inhibitor in the lubricating oil field can be used. Examples thereof include benzotriazole-based compounds, tolyltriazole-based compounds, thiadiazole-based compounds, and imidazole-based compounds.
When the lubricating oil composition contains a corrosion inhibitor, its content may be, for example, 0.005 to 5% by mass based on the total amount of the composition.

(I) As the rust preventive agent, a known rust preventive agent in the lubricating oil field can be used. Examples include petroleum sulfonate, alkylbenzene sulfonate, dinonylnaphthalene sulfonate, alkylsulfonate, fatty acid, alkenyl succinic acid half ester, fatty acid soap, polyhydric alcohol fatty acid ester, fatty acid amine, paraffin oxide, alkyl polyoxyethylene ether, etc. can be mentioned.
When the lubricating oil composition contains a rust inhibitor, its content may be, for example, 0.005 to 5% by mass based on the total amount of the composition.

(J) As the metal deactivator, a metal deactivator known in the lubricating oil field can be used. Examples include imidazolines, pyrimidine derivatives, alkylthiadiazoles, mercaptobenzothiazoles, benzotriazoles and their derivatives, 1,3,4-thiadiazole polysulfides, 1,3,4-thiadiazolyl-2,5-bisdialkyldithiocarbamates, 2 -(Alkyldithio)benzimidazole and β-(o-carboxybenzylthio)propiononitrile.
When the lubricating oil composition contains a metal deactivator, its content may be, for example, 0.005 to 1% by mass based on the total amount of the composition.

(K) As the demulsifier, for example, a known demulsifier such as a polyalkylene glycol-based nonionic surfactant can be used. When the lubricating oil composition contains a demulsifier, its content may be, for example, 0.005 to 5% by mass based on the total amount of the composition.

(L) As the antifoaming agent, an antifoaming agent known in the lubricating oil field can be used. Examples include silicones, fluorosilicones, fluoroalkyl ethers, and the like. When the lubricating oil composition contains an antifoaming agent, its content may be, for example, 0.0001 to 0.1% by mass based on the total amount of the composition.

(M) As the colorant, for example, a known colorant such as an azo compound can be used.

Hereinafter, the present invention will be described more specifically based on examples and comparative examples. However, the present invention is not limited to these examples.
<Example>
(Molecular weight and molecular weight distribution measurement)
In the following examples, the number average molecular weight (Mn) of the samples was measured by gel permeation chromatography (GPC) as the number average molecular weight in terms of standard polystyrene. GPC measurement conditions are as follows.
Apparatus: ACQUITY (registered trademark) APC UV RI system manufactured by Waters Corporation Column: ACQUITY (registered trademark) APC XT125A manufactured by Waters Corporation (gel particle size 2.5 μm, column size (inner diameter x length) 4.6 mm, in order from the upstream side) × 150 mm) and two ACQUITY (registered trademark) APC XT45A manufactured by Waters Corporation (gel particle size 1.7 μm, column size (inner diameter × length) 4.6 mm × 150 mm) are connected in series Column temperature: 40 ℃
Sample solution: Tetrahydrofuran (THF) solution with a sample concentration of 1.0% by mass Eluent: THF
Solution injection volume: 20.0 μL
Flow rate: 0.7 mL/min Detector: Differential refractive index detector Reference material: Standard polystyrene (Agilent EasiCal (registered trademark) PS-1 manufactured by Agilent Technologies) 10 points (molecular weight: 30230, 9590, 2970, 890, 786, 682, 578, 474, 370, 266)

(Measurement of kinematic viscosity and viscosity index)
In the following examples, the kinematic viscosity of the samples was measured according to JIS K 2283-2000 using an automatic viscometer (trade name "CAV-2000", manufactured by Cannon Instruments) as a measuring device. The viscosity index of the sample was determined based on the measured values of kinematic viscosity at 40°C and 100°C in accordance with JIS K 2283-2000.

(Example 1)
The hydroxy group of polypropylene glycol (PPG) is silylated with a trimethylsilyl (TMS) group by the following procedure, and the corresponding polyalkylenediol is PPG (in general formula (1), R ¹ is a propane-1,2-diyl group). A polyalkylenediol-modified product (TMS-modified PPG) in the form of general formula (1) in which ^Q1 and ^Q2 are TMS groups was produced.
10.00 g of PPG (Mn=200) was weighed into a 200 mL eggplant flask, and 50 mL of dehydrated THF was added thereto. To this, 200 mmol of triethylamine (TEA) was added, and 101 mmol of trimethylchlorosilane (TMS-Cl) was added dropwise over 1 hour under ice-cooling (0°C) with vigorous stirring, and the slurry-like reaction mixture was further stirred for 1 hour. Stirred continuously. After completion of the reaction, 20 mL of water was slowly added to dissolve the white insoluble matter, THF was distilled off with an evaporator, and organic matter was extracted from the residue twice with 50 mL of hexane. The hexane layer was washed with saturated saline, and the washed hexane layer was dried with magnesium sulfate. From the hexane solution from which the desiccant was removed by filtration, hexane was distilled off under reduced pressure to obtain TMS-modified PPG. The kinematic viscosity of the resulting modified product was measured. The results are shown in Table 1.

(Comparative example 1)
PPG used as a raw material in Example 1 was measured for kinematic viscosity at 40°C and 100°C. The results are shown in Table 1.

(Example 2)
A polyalkylenediol-modified product (TMS-modified PPG) in which the corresponding polyalkylenediol is PPG and Q ¹ and Q ² are TMS groups in general formula (1) was produced by the following procedure.
20.00 g of PPG (Mn=750) having a different number average molecular weight from the PPG used in Example 1 was used as the polyalkylenediol, the amount of TEA was changed to 150 mmol, and the amount of TMS-Cl was changed to 68 mmol. A TMS-modified PPG was synthesized by the same procedure as in Example 1, except for the changes. Table 1 shows the kinematic viscosity of the resulting modified product.

(Comparative example 2)
PPG used as a raw material in Example 2 was measured for kinematic viscosity at 40°C and 100°C. The results are shown in Table 1.

(Example 3)
A polyalkylenediol-modified product (TMS-modified PPG) in which the corresponding polyalkylenediol is PPG and Q ¹ and Q ² are TMS groups in general formula (1) was produced by the following procedure.
As the polyalkylenediol, 9.82 g of PPG (Mn=1120) having a different number average molecular weight from the PPG used in Example 1 was used, the amount of TEA was changed to 60 mmol, and the amount of TMS-Cl was changed to 22 mmol. A TMS-modified PPG was synthesized by the same procedure as in Example 1, except for the changes. Table 1 shows the kinematic viscosity of the resulting modified product.

(Comparative Example 3)
PPG used as a raw material in Example 3 was measured for kinematic viscosity at 40°C and 100°C. The results are shown in Table 1.

(Example 4)
A polyalkylenediol-modified product (TMS-modified PPG) in which the corresponding polyalkylenediol is PPG and Q ¹ and Q ² are TMS groups in general formula (1) was produced by the following procedure.
20.00 g of PPG (Mn=2110) having a different number average molecular weight from the PPG used in Example 1 was used as the polyalkylenediol, the amount of TEA was changed to 50 mmol, and the amount of TMS-Cl was changed to 24 mmol. A TMS-modified PPG was synthesized by the same procedure as in Example 1, except for the changes. Table 1 shows the density and kinematic viscosity of the resulting modified product.

(Comparative Example 4)
PPG used as a raw material in Example 4 was measured for kinematic viscosity at 40°C and 100°C. The results are shown in Table 1.

(Example 5)
By the following procedure, a polyalkylenediol-modified product (DMPS-modified PPG) in which the corresponding polyalkylenediol is PPG and Q ¹ and Q ² are dimethylphenyl groups (DMPS groups) in general formula (1) is produced. did.
19.56 g of PPG used in Example 3 was weighed into a 200 mL eggplant flask, and 50 mL of dehydrated hexane was added thereto. TEA (46 mmol) was added thereto, followed by slowly adding dimethylphenylchlorosilane (DMPS-Cl, 38 mmol), and the reaction mixture was heated to reflux for 3 hours. After cooling the reaction mixture to room temperature, water (20 mL) was added to dissolve the white precipitate. The hexane layer was separated and the aqueous layer was extracted twice with 50 mL of toluene. The organic layers were combined, washed with saturated brine, and the washed organic layer was dried over anhydrous magnesium sulfate. The desiccant was separated by filtration, and the solvent was distilled off under reduced pressure to obtain DMPS-modified PPG. Table 2 shows the kinematic viscosity of the resulting modified product.

(Example 6)
According to the following procedure, the corresponding polyalkylenediol is PPG, and in the general formula (1), Q ¹ and Q ² are tert-butyldimethylsilyl groups (TBDMS groups) polyalkylenediol-modified products (TBDMS-modified PPG ) was manufactured.
Sodium hydride (NaH, 60% in oil, 40 mmol) was weighed into a 200 mL round-bottomed flask, 10 mL of dehydrated hexane was added, stirred, left to stand, and the supernatant was removed with a syringe. This hexane washing operation was repeated three times, and 100 mL of dehydrated toluene was added to the washed NaH. The PPG (11.12 g) used in Example 3 was slowly added thereto while being careful of foaming. Furthermore, tert-butyldimethylchlorosilane (TBDMS-Cl, 22 mmol) was added, and the mixture was stirred at 80°C for 2 hours. The reaction mixture was cooled to room temperature and 20 mL of water was added to dissolve the white precipitate. The toluene layer was separated and the aqueous layer was extracted twice with 50 mL of toluene. The organic layers were combined and washed with saturated brine. The washed toluene solution was dried over anhydrous magnesium sulfate, the drying agent was removed by filtration, and the toluene was distilled off under reduced pressure to obtain TBDMS-modified PPG. Table 2 shows the kinematic viscosity of the resulting modified product.

(Example 7)
According to the following procedure, a polyalkylenediol-modified product (TIPS-modified PPG) in which the corresponding polyalkylenediol is PPG and Q ¹ and Q ² are triisopropylsilyl groups (TIPS groups) in general formula (1) manufactured.
Example 6 except that the amount of PPG used in Example 3 was 10.48 g, the amount of toluene was 200 mL, and triisopropylchlorosilane (TIPS-Cl, 20 mmol) was used instead of TBDMS-Cl. TIPS-modified PPG was obtained by the same procedure. Table 2 shows the kinematic viscosity of the resulting modified product.

(Example 8)
According to the following procedure, the corresponding polyalkylenediol is PPG, and in the general formula (1), Q ¹ and Q ² are tert-butyldiphenylsilyl groups (TBDPS groups) polyalkylenediol-modified products (TBDPS-modified PPG ) was manufactured.
The amount of PPG used in Example 3 was changed to 16.01 g, the amount of toluene used was changed to 200 mL, and tert-butyldiphenylchlorosilane (TBDPS-Cl, 30 mmol) was used instead of TBDMS-Cl. A TBDPS-modified PPG was obtained by the same procedure as in Example 6. Table 2 shows the kinematic viscosity of the resulting modified product.

(Example 9)
A modified polyalkylenediol (TMS-modified PEG) in which the corresponding polyalkylenediol is polyethylene glycol (PEG) and Q ¹ and Q ² are TMS groups in general formula (1) was produced by the following procedure. .
11.19 g of PEG (Mn=810) was weighed into a 200 mL eggplant flask, and 50 mL of dehydrated toluene was added thereto. TEA (70 mmol) was added thereto, and TMS-Cl (48 mmol) was added dropwise over 1 hour under ice-cooling (0°C) with vigorous stirring, and the slurry-like reaction mixture was further stirred for 1 hour. did. The reaction mixture was filtered under reduced pressure, and the soluble matter was extracted from the cake portion with 300 mL of hexane and mixed with the previous filtrate (toluene solution). A white precipitate was formed again and vacuum filtration was performed again. The solvent was distilled off from the filtrate under reduced pressure to obtain TMS-modified PEG. Table 3 shows its kinematic viscosity.

(Comparative Example 5)
For PEG used as a raw material in Example 9, kinematic viscosity at 40°C and 100°C was measured. The results are shown in Table 3.

(Example 10)
According to the following procedure, the corresponding polyalkylene diol is a propylene oxide (PO, 90% by mass)-ethylene oxide (EO, 10% by mass) copolymer, and Q ¹ and Q ² are TMS groups in the general formula (1). Certain forms of polyalkylenediol modifications have been prepared.
21.07 g of polyalkylenediol (PO (90% by mass)-EO (10% by mass) copolymer (Mn=1210)) was dissolved in THF (50 mL), and TEA (70 mmol) was added thereto. TMS-Cl (50 mmol) was added dropwise to this solution over 1 hour while being vigorously stirred under ice cooling. Stirring was continued for 1 hour after the completion of dropping. 20 mL of water was added to this reaction solution, and THF was distilled off under reduced pressure. Organic matter was extracted from the residual liquid twice with 50 mL of hexane. The resulting hexane solution was washed with saturated saline and dried over anhydrous magnesium sulfate. The desiccant was removed by filtration, and hexane was distilled off under reduced pressure to obtain a modified TMS product. The kinematic viscosity of the resulting modified product was measured. The results are shown in Table 4.

(Comparative Example 6)
The kinematic viscosity at 40° C. and 100° C. was measured for the PO—EO copolymer (PO:EO copolymerization ratio=90:10 w/w) used as a raw material in Example 10. The results are shown in Table 4.

(Example 11)
According to the following procedure, a polyalkylenediol-modified product in which the corresponding polyalkylenediol is a butene oxide (BO) polymer and Q ¹ and Q ² are TMS groups in general formula (1) was produced.
A TMS-modified product was obtained in the same manner as in Example 10, except that 19.60 g of a BO polymer (Mn=910) was used instead of the PO-EO copolymer. Table 4 shows the kinematic viscosity of the obtained TMS-modified product.

(Comparative Example 7)
The kinematic viscosity at 40°C and 100°C was measured for the BO polymer used as a raw material in Example 11. The results are shown in Table 4.

(Example 12)
By the following procedure, the corresponding polyalkylene diol is a BO polymer having a different number average molecular weight from that used in Example 11, and Q ¹ and Q ² are TMS groups in general formula (1). An alkylenediol modified product was produced.
As the polyalkylenediol, 20.50 g of a BO polymer (Mn=570) having a different number average molecular weight from that used in Example 11 was used, the amount of TEA used was 100 mmol, and the amount of TMS-Cl was 70 mmol. A TMS-modified product was obtained by the same procedure as in Example 10 except that Table 4 shows the kinematic viscosity of the modified TMS obtained.

(Comparative Example 8)
The kinematic viscosity at 40°C and 100°C was measured for the BO polymer having a number average molecular weight of 570, which was used as a raw material in Example 12. The results are shown in Table 4.

(Example 13)
By the following procedure, the corresponding polyalkylene diol is a THF (45% by mass)-EO (55% by mass) copolymer, and in the general formula (1), Q ¹ and Q ² are TMS groups. A diol modification was produced.
Using 19.29 g of a THF (45% by mass)-EO (55% by mass) copolymer (Mn=1760) as the polyalkylenediol, using 150 mmol of TEA and 103 mmol of TMS-Cl. A TMS-modified product was obtained by the same procedure as in Example 10 except that Table 4 shows the kinematic viscosity of the modified TMS obtained.

(Comparative Example 9)
The kinematic viscosity at 40° C. and 100° C. was measured for the THF-EO copolymer (THF:EO copolymerization ratio=45:55 w/w) used as a raw material in Example 13. The results are shown in Table 4.

(Example 14)
By the following procedure, the corresponding polyalkylene diol is a THF (60% by mass)-EO (40% by mass) copolymer, and in the general formula (1), Q ¹ and Q ² are TMS groups. A diol modification was produced.
Example except that 20.36 g of THF (60% by mass)-EO (40% by mass) copolymer is used as the polyalkylenediol, the amount of TEA is 70 mmol, and the amount of TMS-Cl is 50 mmol. A TMS modified product was obtained by the same procedure as in 10. Table 4 shows the kinematic viscosity of the modified TMS obtained.

(Comparative Example 10)
The kinematic viscosity at 40° C. and 100° C. was measured for the THF-EO copolymer (THF:EO copolymerization ratio=60:40 w/w) used as a starting material in Example 14. The results are shown in Table 4.

Claims

A modified polyalkylenediol represented by the following general formula (1), wherein the corresponding polyalkylenediol has a number average molecular weight of 100 to 8,000.

(In general formula (1), a plurality of R 1 may be the same or different, and each independently represents a linear alkylene group having 2 to 5 carbon atoms or a branched alkylene group having 3 to 8 carbon atoms. represents a branched alkylene group having a main chain of 2 to 5 carbon atoms, Q 1 and Q 2 may be the same or different and are each independently represented by the following general formula (2) It is a silyl group, and n represents an integer of 2 or more.)

(In general formula (2), R 2 , R 3 and R 4 may be the same or different and each independently represents a hydrocarbon group having 1 to 9 carbon atoms.)
In general formula (1), R 1 is ethane-1,2-diyl group, propane-1,2-diyl group, butane-1,2-diyl group, butane-2,3-diyl group, or butane -1,4-diyl group, or a combination thereof, the polyalkylenediol modified product according to claim 1.
In the general formula (1), Q 1 and Q 2 are a trimethylsilyl group, an ethyldimethylsilyl group, a dimethylpropylsilyl group, a butyldimethylsilyl group, an octyldimethylsilyl group, a triethylsilyl group, a dimethylisopropylsilyl group, and a diethylisopropylsilyl group. group, triisopropylsilyl group, tributylsilyl group, tert-butyldimethylsilyl group, dimethylphenylsilyl group, benzyldimethylsilyl group, methyldiphenylsilyl group, tert-butyldiphenylsilyl group, triphenylsilyl group, di-tert-butyl 3. The modified polyalkylenediol according to claim 1, which is one or more silyl groups selected from an isobutylsilyl group, a tricyclohexylsilyl group, a dicyclohexylphenylsilyl group, and a cyclohexyldiphenylsilyl group.
4. The poly according to any one of claims 1 to 3, wherein in the general formula (1), Q 1 and Q 2 are the same silyl group or the same combination of two or more silyl groups. Modified alkylenediol.
A lubricating base oil containing the polyalkylenediol-modified product according to any one of claims 1 to 4.
A lubricating oil composition containing the lubricating base oil according to claim 5.