JP3977665B2 - Lubricant - Google Patents

Description

【００４３】
【発明の効果】
本発明のポリエーテル系潤滑油は下記の効果を奏する。そのため、潤滑油として極めて好適である。
（１）鉱物油等の炭化水素系潤滑油との相溶性に優れる。
（２）潤滑性に優れる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a polyether-based lubricating oil. More specifically, the present invention relates to a polyether-based lubricating oil excellent in compatibility with a hydrocarbon-based lubricating oil, lubricity and the like.
[0002]
[Prior art]
Conventionally, hydrocarbon-based lubricating oils such as mineral oil and olefin polymerization oil are used for hydraulic fluids, metalworking oils, engine oils, gear oils, compressor oils, etc., because these applications require high lubricity. An extreme pressure agent containing an element such as chlorine or phosphorus is added to a hydrocarbon-based lubricating oil to improve lubricity.
[0003]
[Problems to be solved by the invention]
However, chlorinated extreme pressure agents are difficult to use due to environmental problems such as ozone depletion and phosphorus extreme pressure eutrophication by wastewater. Furthermore, polyethers having better lubricity than hydrocarbon-based lubricants have poor compatibility with hydrocarbon-based lubricants such as mineral oils, so it is difficult to make the product appearance uniform. It was difficult to use.
An object of this invention is to provide the polyether-type lubricating oil excellent in compatibility with hydrocarbon-type lubricating oil, and lubricity.
[0004]
[Means for Solving the Problems]
As a result of intensive studies in view of the above problems, the present inventors have reached the present invention.
That is, the present invention relates to a polyether (E) represented by the following general formula (1) and having a number average molecular weight of 500 to 30,000, a carboxylic acid, an acid anhydride thereof, a lower alkyl ester thereof, or an acid halide thereof. (A) And a lubricant (G) having an HLB value of 6.0 or less.
_{^{R 1 - {(OCH 2 CH}} 2 CH 2 CH 2) m (OA) n} -OH (1)
[Wherein R ¹ is a hydrocarbon group having 1 to 24 carbon atoms, A is an alkylene group having 2 to 24 carbon atoms excluding 1,4-butylene group, and m and n have a number average molecular weight of (E) of 500 It is an integer greater than or equal to 1 and 30,000. ]
[0005]
DETAILED DESCRIPTION OF THE INVENTION
R1 in the general formula (1) is a linear or branched hydrocarbon group having 1 to 24 carbon atoms, specifically, a linear or branched aliphatic hydrocarbon group, an aromatic hydrocarbon group, and an alicyclic group. A hydrocarbon group is mentioned. When the number of carbon atoms exceeds 24, the viscosity index of (G) is deteriorated.
Examples of the linear or branched aliphatic hydrocarbon group include an alkyl group (methyl group, ethyl group, n- and i-propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, Decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, heneicosyl group, docosyl group, tricosyl group, tetracosyl group, etc.); unsaturated hydrocarbon group (Alkenyl or alkynyl groups such as ethenyl, 1-, 2- and i-propenyl, butenyl, pentynyl, hexenyl, peptenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, Tetradecenyl group, pentadecenyl group, hexadecenyl group Heptadecenyl, octadecenyl, nonadecenyl, eicosenyl group, heneicosenyl group, docosenyl, tricosenyl group, and tetracosenyl group) and the like.
[0006]
As the aromatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 24 carbon atoms such as a phenyl group, an alkylaryl group (o, m or p-methylphenyl group, m, p-dimethylphenyl group, 2,6- Dimethylphenyl group, o, m or p-ethylphenyl group, pn-butylphenyl group, p-octylphenyl group, p-nonylphenyl group, etc.), aralkyl group (benzyl group, phenethyl group, etc.), substituted aralkyl group (O, m or p-methylbenzyl group, pn-butylphenethyl group, etc.), styrylphenyl group, benzylphenyl group and the like.
Examples of the alicyclic hydrocarbon group include a cyclopentyl group and a cyclohexyl group.
Among these, an aliphatic or alicyclic hydrocarbon group having 4 to 20 carbon atoms is preferable, and an aliphatic or alicyclic hydrocarbon group having 8 to 18 carbon atoms is particularly preferable.
[0007]
A in General formula (1) is a C2-C24 alkylene group except a 1, 4- butylene group. Examples of the alkylene group having 2 to 24 carbon atoms include ethylene group, 1,2- and 1,3-propylene group, 1,2- and 2,3-butylene group, isobutylene group, and undecylene group. A mixture of two or more of these may be used. Among these, an alkylene group having 2 to 16 carbon atoms is preferable, an ethylene group, a 1,2-propylene group, and a 1,2-butylene group are more preferable, and a 1,2-propylene group is particularly preferable. And a branched alkylene group such as a 1,2-butylene group. When the branched alkylene group is present in A, the compatibility with the hydrocarbon is improved.
[0008]
M and n in General formula (1) are 1 or more integers from which the number average molecular weight of polyether (E) becomes 500-30,000. The ratio of m to n (m / n) is preferably 5/95 to 45/55. That is, it is preferably 5 to 45 mol% of the total amount of content of the content of _{(OCH 2 CH 2 CH 2 CH} 2) is _{(OCH 2 CH 2 CH 2 CH} 2) and (OA).
In addition, (E) may be an oxytetramethylene group (OCH ₂ CH ₂ CH ₂ CH ₂ ) and another oxyalkylene group (OA group), which may be a random bond or a block bond. It is preferable in that the flow characteristics of (G) are excellent. It is more preferable that 80% by mass or more of oxytetramethylene groups constituting (E) are present as a random bond portion.
[0009]
As a method for producing the polyether (E) represented by the general formula (1), a hydrocarbon alcohol having 1 to 24 carbon atoms represented by R1OH is preferably used at a temperature of 30 to 120 ° C. in the presence of a catalyst. Can be prepared by adding tetrahydrofuran (hereinafter referred to as THF) and alkylene oxide having 2 to 24 carbon atoms (hereinafter referred to as AO) randomly or in blocks at a pressure of 0 to 0.6 MPa.
The hydrocarbon alcohol having 1 to 24 carbon atoms represented by R ¹ OH is an alcohol having a linear or branched hydrocarbon group having 1 to 24 carbon atoms represented by R ¹ in the general formula (1). Specific examples include linear or branched aliphatic alcohols, aromatic hydrocarbon alcohols and alicyclic hydrocarbon alcohols. Preferred are the same as those represented by R1.
[0010]
With respect to the above catalyst, a conventionally known catalyst can be used, but the preferred range differs depending on the case in addition of THF or AO.
Examples of the catalyst for the addition of THF alone or copolymerization with AO include, for example, Lewis acids such as BF ₃ , BCl ₃ , AlCl ₃ , FeCl ₃ , SnCl ₃ , and complexes thereof [for example, BF ₃ ether complex, BF ₃ Tetrahydrofuran complex (BF ₃ · THF)]; Protic acids such as H ₂ SO ₄ and HClO ₄ ; Perchlorates of alkali metals such as KClO ₄ and NaClO ₄ ; Ca (ClO ₄ ) ₂ and Mg (ClO ₄ ) ₂ And alkaline earth metal perchlorates such as Al (ClO ₄ ) _{3 and} other metal perchlorates.
Of these, BF ₃ ether complex and BF ₃ tetrahydrofuran complex (BF ₃ · THF) are preferable.
The catalyst for adding AO alone may be a known catalyst that is usually used. In addition to the above-mentioned catalysts, alkali catalysts such as hydroxide [KOH, NaOH, CsOH, Ca (OH) ₂ Metal or alkaline earth metal hydroxides]; oxides (alkali metals such as K ₂ O, CaO, BaO, etc. or oxides of alkaline earth metals); alkali metals (Na, K, etc.) and their hydrogen Compound (NaH, KH, etc.); amines such as triethylamine, trimethylamine and the like.
[0011]
Among these, KOH, NaOH, CsOH, BF ₃ ether complex and BF ₃ tetrahydrofuran complex (BF ₃ · THF) are preferable.
As AO to be added, A in the general formula (1) is an alkylene group having 2 to 24 carbon atoms, and examples thereof include ethylene oxide (hereinafter referred to as EO), propylene oxide (hereinafter referred to as PO), and 1,2-butylene. Examples thereof include oxide, 2,3-butylene oxide, isobutylene oxide, and undecylene oxide. Of these, EO, PO, 1,2-butylene oxide, and undecylene oxide are preferable, and PO is particularly preferable. These may be used in combination, and the polymerization form may be random or block.
The added mole number m of THF is 3 to 100, and the added mole number n of AO is preferably 5 to 150, more preferably 4 to 20, and more preferably 6 to 50. Moreover, although THF and AO may be random addition or block addition, random addition is preferable in that the flow characteristics of the above (G) at low temperature are excellent. It is more preferable that 80% by mass or more of the addition of THF is random addition.
[0012]
Number average molecular weight Mn of (E) [Measurement method is based on hydroxyl value measurement. The same applies to the following. ] Is 500 to 30,000, preferably 700 to 10,000, and more preferably 800 to 5,000. If it is less than 500, the lubricity of said (G) will fall, and if it exceeds 30,000, kinematic viscosity of (G) will become high too much.
[0013]
The reaction product (G) in the present invention comprises the above (E) and a carboxylic acid or its acid anhydride or its lower alkyl ester or its acid halide (a), polyisocyanate (b), or polyhalide (c). It is a reaction product with one or more compounds (F) selected from the group.
As the carboxylic acid or its acid anhydride or its lower alkyl ester or its acid halide (a) in this compound (F), the following carboxylic acid having 2 to 30 carbon atoms or its acid anhydride or its lower alkyl (carbon Examples thereof include alkyl groups of 1 to 3, such as methyl, ethyl, propyl) esters or acid halides thereof, and specific examples thereof include the following (a-1) to (a-9). This compound may preferably contain 1 to 3, particularly preferably 1 heteroatom (sulfur, phosphorus, etc.).
(A-1); aliphatic monocarboxylic acid acetic acid, propionic acid, thiopropionic acid, butanoic acid, hexanoic acid, lauric acid, myristic acid, palmitic acid, oleic acid, etc. (a-2); aliphatic divalent carboxylic acid Oxalic acid, malonic acid, succinic acid, propanedicarboxylic acid, thiodipropionic acid, tetrahydrophthalic acid, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, hymic acid, tetrabromophthalic acid, tetrachlorophthalic acid, etc.
(A-3); aliphatic polyvalent (3 to 4 or more) carboxylic acid propanetricarboxylic acid, methylcyclohexanetricarboxylic acid, cyclohexentricarboxylic acid, methylcyclohexentricarboxylic acid, cyclohexanetetracarboxylic acid and the like (a-4); Aromatic monocarboxylic acid benzoic acid, phenylacetic acid, naphthalenecarboxylic acid (a-5); aromatic divalent carboxylic acid phthalic acid, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid, xylylene dicarboxylic acid and the like (a-6); Aromatic polyvalent (3 to 4 or more) carboxylic acid benzenetricarboxylic acid, benzenetetracarboxylic acid, naphthalenetetracarboxylic acid and the like (a-7); (a-1) to (a-6) acid anhydrides (A-8); lower alkyl of (a-1) to (a-6) (alkyl group having 1 to 3 carbon atoms, for example, Methyl, ethyl, propyl) ester (a-9); acid halides (chlorine, bromine, etc.) of (a-1) to (a-6)
Among these, (a-2), (a-5), and (a-7) are preferable, and oxalic acid (anhydride), malonic acid (anhydride), and succinic acid (anhydride) are more preferable. ), Propanedicarboxylic acid (anhydride), thiodipropionic acid, tetrahydrophthalic acid (anhydride), methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride (anhydride), hymic acid (anhydride), norbornene dicarboxylic acid (anhydride) Product), phthalic acid (anhydride), isophthalic acid, terephthalic acid, particularly preferred are oxalic acid (anhydride), malonic acid (anhydride), succinic acid (anhydride), propanedicarboxylic acid (anhydride) ), Thiodipropionic acid. (G) using these has a low viscosity and facilitates handling of the composition.
[0016]
The reaction conditions for (E) and (a) are not particularly limited, and the reaction can be carried out under general esterification reaction conditions. For example, in the case of a one-step synthesis method, an esterification catalyst, preferably an acid catalyst (for example, paratoluenesulfonic acid, sulfuric acid, etc.) is used, preferably 50 to 150 ° C., more preferably 70 to 130 ° C. for 8 to 20 hours. Can be synthesized. The equivalent ratio of the functional description of (E) and (a) is preferably 0.5 to 2.0, more preferably 0.9 to 1.5. When it is 0.5 or more, a large amount of unreacted polycarboxylic acid does not remain and treatment such as washing is unnecessary, and when it is 2.0 or less, the lubricity of (G) is good. Moreover, solvents, such as toluene and benzene, can be used for reaction as needed. The esterification reaction can be carried out at normal pressure, reduced pressure, or increased pressure, but the reduced pressure is preferable because the reaction time becomes shorter. The degree of reduced pressure is preferably 30 mmHg or less, particularly preferably 10 mmHg or less, at the final stage of the reaction. The progress of the esterification reaction can be judged by the amount of water distilled from the reaction system, the amount of lower alcohol, the acid value of the reaction system, the viscosity, the number average molecular weight of the reaction system and the like.
[0017]
As the polyisocyanate (b) used in the present invention, diisocyanates having 2 to 6 or more valences are used, and those conventionally used for the production of polyurethane can be mentioned, specifically, (b-1) to (B-4).
(B-1) Aromatic polyisocyanate 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4′- and / Or 4,4′-diphenylmethane diisocyanate (MDI), 4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4 '-Diisocyanatodiphenylmethane and the like;
(B-2) Aliphatic polyisocyanate ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene isocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcapro Ate, bis (2-isocyanatoethyl) fumarate, etc .;
[0018]
(B-3) Alicyclic polyisocyanate Isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI) and the like;
(B-4) araliphatic polyisocyanate m- and / or p-xylylene diisocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI) and the like;
Among these, (b-1) and (b-2) are preferable, and 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6- are more preferable. Tolylene diisocyanate (TDI), crude TDI, 2,4′- and / or 4,4′-diphenylmethane diisocyanate (MDI) ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI).
[0019]
The reaction conditions for (E) and (b) are not particularly limited, and the reaction can be performed under the conditions for general urethanization reaction. For example, a urethanization catalyst, preferably a transition metal catalyst (for example, dibutyltin dilaurate) is used, and it can be synthesized at 50 to 150 ° C., more preferably at 70 to 130 ° C. for 8 to 20 hours. The equivalent ratio of the functional description of (E) and (b) is preferably 0.5 to 2.0, more preferably 0.9 to 1.5. When it is 0.5 or more and 2.0 or less, the lubricity of (G) becomes good. Further, if necessary, a solvent such as toluene, xylene, dimethylformamide, butyl acetate or the like can be used for the reaction. The urethanization reaction can be carried out at normal pressure or under pressure. The progress of the urethanization reaction can be judged by the isocyanate group content of the reaction system, the viscosity, the number average molecular weight of the reaction system, and the like.
[0020]
Examples of the polyhalide (c) in the present invention include divalent to tetravalent or higher C1-5 chlorides or bromides. Specifically, the following (c-1) and (c-2) ).
(C-1) C1-C2 polyhalide dichloromethane, dichloroethane, dibromomethane, dibromoethane, trichloroethylene and the like;
(C-2) Among these, preferred are polyvalent halides having 3 or more carbon atoms such as 1,3-dichloropropane, 1,3-trichloropropane, 1,2 dibromobutane, and divalent chlorides. More preferred are dichloromethane and dichloroethane. (G) using these is low in viscosity and easy to handle.
[0021]
The reaction conditions of (E) and (c) are not particularly limited, and can be synthesized under the general etherification reaction conditions. For example, an alkali, preferably an inorganic alkali (for example, sodium hydroxide, potassium hydroxide) is added in an amount of 0.9 to 1.5 equivalents to the halogen, preferably 50 to 150 ° C, more preferably 70 to 130 ° C. It can be synthesized in 6 to 24 hours. The equivalent ratio of the functional notation of (E) and (c) is preferably 0.5 to 2.0, more preferably 0.9 to 1.5. When it is 0.5 or more and 2.0 or less, the lubricity of (G) becomes good. Also. If necessary, a solvent such as toluene or benzene can be used for the reaction. The etherification reaction can be carried out at normal pressure or under pressure. The progress of the etherification reaction can be judged by the alkali number of the reaction system, the viscosity, the number average molecular weight of the reaction system, and the like.
[0022]
The HLB value of the reaction product (G) of (E) and (F) thus obtained is usually 6.0 or less, preferably 5.0 or less, more preferably 2 to 4. . When the HLB value exceeds 6.0, the compatibility between the hydrocarbon such as mineral oil and (G) becomes poor.
The HLB value is a value calculated by the Oda formula based on an organic conceptual diagram, and this calculation method is described in, for example, “Emulsification / Solubilization Technology” (Showa 51, Engineering Book Co., Ltd.). For the organic and inorganic values for deriving the HLB values, see the inorganic base table described in "Organic Conceptual Diagram-Fundamentals and Applications-" [Sankyo Publishing Co., Ltd. 1984] (Showa 49, Fujita et al. (Reported value).
[0023]
The number average molecular weight (Mn) of (G) is preferably 600 to 30,000, more preferably 1,200 to 10000, and particularly preferably 2,000 to 5000. When it is 600 or more, the lubricity becomes good, and when it is 30,000 or less, the kinematic viscosity does not become too high.
[0024]
The polyether-based lubricating oil of the present invention is composed of a reaction product (G) of (E) and (F), but (G) may be a mixture of different compositions, molecular weights, etc. A hydrocarbon-based oil may be added as necessary. Further, those in which (E) remains unreacted can also be used.
Hydrocarbon oils include solvent refined oils, paraffinic mineral oils, naphthenic mineral oils, alkyl (10 to 100 carbon atoms) benzene, alkyl (10 to 100 carbon atoms) naphthalene, poly-α-olefins (2 to 50 carbon atoms). , Polybutene (weight average molecular weight 200 to 4000), polyisobutene (weight average molecular weight 200 to 4000) and the like. Preference is given to solvent refined oils, paraffinic mineral oils, naphthenic mineral oils and polybutenes. The kinematic viscosity (measured according to JIS K 2283) of these hydrocarbon oils is preferably 1 to 520 mm ² / s at 40 ° C.
The blending ratio of the polyether-based lubricating oil and the hydrocarbon-based oil may be arbitrary, but is preferably a polyether-based lubricating oil / hydrocarbon-based oil mass ratio of 5/95 to 95/5, more preferably 10/90. It is -90/10, Most preferably, it is 20 / 80-80 / 20. The mixed oil can exhibit the features of both polyether and hydrocarbon.
Further, if necessary, other polyethers [polyether etc. in which R1 in the general formula (1) is a hydrogen atom, etc.] can be blended. Its content is less than 90% by weight.
[0025]
The polyether-based lubricating oil (G) of the present invention is a detergent / dispersant, antioxidant, oiliness agent, extreme pressure agent, metal deactivator, rust inhibitor, antifoaming agent, viscosity index improver, flow as required. Optional components such as point depressants can be added.
[0026]
The detergent / dispersant may be neutral or basic sulfonates (eg, petroleum sulfonates such as calcium petroleum sulfonate (normal salt) or basic barium sulfonates, or positive or negative alkyl sulfonate-substituted aromatic sulfonates). Basic metal salts, etc.]; neutral or basic phenates [e.g., alkyl (C1-C36) phenol, alkyl (C1-C36) phenol sulfide, alkyl (C1-36) phenol aldehyde condensate Positive or basic metal salts, etc.]; neutral or basic phosphonates, thiophosphonates; alkyl (C1-C36) substituted salicylates; alkyl (C5-C36) methacrylates or methacrylates and polar groups Mono (including amines, amides, imides, hydroxyls, carboxyls, nitriles, etc.) -(Molar ratio 99/1 to 10/90) copolymer [for example, alkyl (carbon number 1 to 36) methacrylate-vinylpyrrolidinone copolymer (weight average molecular weight: 1,000 to 100,000), alkyl ( C1-C36) methacrylate-diethylaminoethyl methacrylate copolymer (weight average molecular weight: 1,000-100,000), alkyl (C1-C36) methacrylate-polyethylene glycol-methacrylate copolymer (weight average molecular weight: N-substituted alkenyl (C5-C36) succinimide (eg N-tetraethylenepentamine polyisobutenyl succinimide); high molecular weight amide [eg polystearamide (Weight average molecular weight: 1,000 to 100,000) etc.] The amount of the cleaning dispersant used is preferably 15% or less.
[0027]
Antioxidants include phenolic antioxidants (eg 2,4-dimethyl-6-tert-butylphenol, 4,4-butylidenebis (6-tert-butylmetacresol), etc.); amine antioxidants (eg monooctyl) Diphenylamine, dioctyldiphenylamine and the like); dialkyl (carbon number 1 to 36) zinc dithiophosphate; diallyl (carbon number 2 to 36) zinc dithiophosphate; organic sulfide; organic selenide and the like. The amount of antioxidant used is preferably 2% or less.
Oils and fats such as lard oil; long-chain fatty acids having 8 to 36 carbon atoms (octylic acid, lauric acid, palmitic acid, oleic acid, stearic acid, etc.) and their fatty acids and monohydric and polyhydric alcohol esters; carbon Examples include higher alcohols of several 8 to 36 (octyl alcohol, lauryl alcohol, palmityl alcohol, oleyl alcohol, stearyl alcohol, etc.) and esters thereof. The amount of the oily agent used is preferably 15% or less.
[0028]
As extreme pressure agents, lead soap (lead naphthenate, etc.); sulfur compounds (sulfurized fatty acid esters, sulfide palm oil, sulfurized terpene, dibenzyl disulfide, etc.); chlorine compounds (chlorinated paraffin, chloronaphthazanate, etc.); phosphorus Compound (tricresyl phosphate, tributyl phosphate, tricresyl phosphite, n-butyl di-n-octyl phosphinate, di-n-butyl dihexyl phosphonate, di-n-butyl phenyl phosphonate, dibutyl phosphoramidate, amine dibutyl Phosphate, etc.). The amount of extreme pressure agent used is preferably 10% or less.
Examples of the metal deactivator include benzotriazole, mercaptobenzothiazole, N, N′-disalicylidene-1,2-diaminopropane, alizarin and the like. The amount of the metal deactivator used is preferably 2% or less.
[0029]
Examples of rust inhibitors include aliphatic carboxylic acids having 6 to 36 carbon atoms (caprylic acid, lauric acid, nonanoic acid, decanoic acid, oleic acid, etc.), alkali metal salts, amine salts; alkenyl succinic acids having 6 to 36 carbon atoms. (Octenyl succinic acid, dodecenyl succinic acid, pentadecenyl succinic acid, octadecenyl succinic acid, etc.) and alkali metal salts, amine salts; dibasic acids having 6 to 24 carbon atoms (azelaic acid, dodecanedioic acid sebacate, Dimer acids, etc.) and alkali metal salts, amine salts; aromatic carboxylic acids (benzoic acid, p-tertbutylbenzoic acid, nitrobenzoic acid, etc.) and alkali metal salts, amine salts; (alkyl phosphorus having 8 to 18 carbon atoms) Acid ester salt; (cyclo) alkylamine (C1-C36) or heterocyclic amine (C4-C36) alkylene oxide (C2-C4) ( -10 mol) adducts (eg, cyclohexylamine EO 2 mol adduct, cyclohexylamine PO 2 mol adduct, morpholine EO 1 mol adduct, morpholine PO 1 mol adduct, etc.); petroleum sulfonates; alkyl (C 1-36) naphthalene sulfonic acid Salts and sorbitan esters (for example, sorbitan laurate, sorbitan stearate, etc.), the above-mentioned aliphatic carboxylic acids, alkenyl succinic acids, dibasic acids, amines and amides of ammonia, etc. Preferably it is 5% or less.
[0030]
Examples of the antifoaming agent include polyorganosiloxane (for example, polydimethylsiloxane). The amount of antifoaming agent used is preferably 0.1% or less.
As the viscosity index improver, polyalkyl (1 to 18 carbon atoms) methacrylate or polyalkyl (1 to 18 carbon atoms) acrylate having a weight average molecular weight of 20,000 to 1,500,000; Mw of 5,000 to 300, 000 polyisobutylene; Mw of 10,000 to 300,000 polyalkyl (8 to 12 carbon atoms) styrene; olefin (2 to 12 carbon atoms) copolymer [eg ethylene-propylene (molar ratio 5/95 to 95) / 5) copolymer, styrene-isoprene (molar ratio 5/95 to 95/5) copolymer hydrogenated product, etc.]. The amount of the viscosity index improver used is preferably 15% or less.
[0031]
As pour point depressants, polyalkyl (6 to 24 carbon atoms) methacrylate; naphthalene-chlorinated paraffin condensation product; ethylene-vinyl acetate (molar ratio 5/95 to 95/5) copolymer; polyacrylamide; vinyl carboxy Examples thereof include a rate (carbon number 1 to 36) -dialkyl (carbon number 1 to 36) fumarate (molar ratio 5/95 to 95/5) copolymer. These pour point depressants all have a weight average molecular weight of 1,000 to 100,000. The amount of pour point depressant used is preferably 1% or less.
Two or more of these additives may be used in combination.
[0032]
In addition, if necessary, an emulsifier such as a surfactant may be added to these and used as a water-containing hydraulic fluid such as an emulsion hydraulic fluid that is diluted 1.1 to 100 times with water. Can do. The amount of the emulsifier is the amount added to the base oil (a polyether lubricant or a lubricant which is a mixture of a polyether lubricant / hydrocarbon oil) unless otherwise specified, and% represents mass%. .
[0033]
As emulsifiers, Na and K salts of sulfonic acids (alkylbenzenesulfonic acid, petroleum sulfonic acid, alkylnaphthalenesulfonic acid, etc.), fatty acids (lauric acid, palmitic acid, myristic acid, oleic acid, castor oil fatty acid, etc.) Na, K Salts and monoethanolamine, diethanolamine, triethanolamine, and the like, PEG esters obtained by esterifying these fatty acids and polyethylene glycol, and alcohols having 8 to 24 carbon atoms (octyl alcohol, decyl alcohol, dodecyl alcohol, tridecyl alcohol, tetra Decyl alcohol, hexadecyl alcohol, oleyl alcohol, stearyl alcohol, etc.) non-ionic active agent, sorbitan fatty acid ester and these ethylene oxides added with ethylene oxide Nonionic surfactants such as the like. The amount of emulsifier used is usually 30% or less.
[0034]
The polyether-based lubricating oil (G) of the present invention is used as a power transmission fluid for the operation of hydraulic equipment and devices in a wide range of construction machines, machine tools, metal and plastic processing machines, vehicles, ships, aircraft, etc. Hydraulic oil used, (2) cutting oil, polishing oil, rolling oil, drawing oil, press oil, forging oil, metal working oil used for polishing and cutting silicon wafers, (3) internal combustion engines such as automobiles It can be applied to engine oil, (3) gear oil, and (4) compressor oil.
[0035]
【Example】
The present invention will be described in detail by the following examples, but the present invention is not limited thereto.
[0036]
The test method is as follows.
(1) Spindle oil compatible with hydrocarbon-based lubricating oil [SYC spindle oil manufactured by Cosmo Oil Co., Ltd. The same shall apply hereinafter. ] Was evaluated by measuring the critical temperature.
The critical temperature was 0 ° C. to 85 ° C., and the temperature at which the lubricating oils of Examples and Comparative Examples and the hydrocarbons were mixed in a test tube at a mass ratio of 30/70 and separated was measured.
(2) Using a lubricating vibration friction wear tester (SRV tester), the friction coefficient in point contact between a steel ball and a flat steel disk and the wear scar diameter on the steel ball were observed and evaluated.
<Lubricity test conditions>
Frequency: 50Hz
Vibration width: 2mm
Load: 200N, 300N, 500N
Time: 10 minutes Temperature: 30 ° C
Friction coefficient: Average value for 10 minutes Wear diameter (mm): 10 mm steel ball (SUJ-2)
Oil film breakage: Friction coefficient (μ) variation was observed.
○: Stable, Δ: Slight variation, × large variation Unless otherwise specified, the part in the sentence represents part by mass.
[0037]
Example 1
Isotridecanol (manufactured by Kyowa Hakko Kogyo Co., Ltd .; trade name “Tridecanol”) in a glass autoclave. The same shall apply hereinafter. 200 parts (1.0 mol), 468 parts (6.5 mol) of tetrahydrofuran (THF) and 7.9 parts of BF 3 · THF were charged, and 580 parts (10.0 mol) of PO 580 (10.0 mol) were added in an amount of 35 to 50 from the pressure-resistant dropping funnel. It was dripped at 10 degreeC over 10 hours. Then, it reacted at 50 degreeC for 5 hours, and cooled. Further, after adding 4.8 parts of 48% NaOH aqueous solution, an adsorption treatment agent [manufactured by Kyowa Chemical Industry Co., Ltd .; Kyoward 600 and Kyoward 1000. The same shall apply hereinafter. ], Filtered, and dehydrated under reduced pressure at 130 ° C. and 30 mmHg or less to obtain 1120 parts (e1) of isotridecanol in THF 6.5 mol / PO 10.0 mol random adduct. 1120 parts (1 mol) of the obtained (e1) and 50 parts (0.5 mol) of succinic anhydride were reacted at 120 ° C. for 12 hours while introducing nitrogen in the liquid, and the liquid acid value at room temperature (according to JIS K 1557). Measurement.) A polyether lubricating oil (g1) of 3.0 was obtained.
[0038]
Example 2
A glass autoclave was charged with 130 parts (1.0 mol) of 2-ethylhexyl alcohol, 504 parts (7.0 mol) of THF, and 7.9 parts of BF3 · THF, and 580 parts (10.0 mol) of PO from a pressure dropping funnel. The solution was added dropwise at 35 to 50 ° C. over 10 hours. Then, it reacted at 50 degreeC for 5 hours, and cooled. Further, 4.8 parts of 48% NaOH aqueous solution was added, treated with an adsorption treatment agent, filtered, dehydrated under reduced pressure at 30 mmHg or less, and then 1100 parts of 2-ethylhexyl alcohol in THF 7.0 mol / PO 10.0 mol random adduct. (E2) 1100 parts (1 mole) obtained and (50 parts (0.5 mole)) of succinic anhydride were reacted at 120 ° C. and 30 mmHg or less for 12 hours while flowing nitrogen in the liquid at room temperature. As a result, a liquid polyether lubricant (g2) having an acid value of 0.5 was obtained.
[0039]
Example 3
THF6.5 mol /PO10.0 mole random adduct of isotridecanol obtained in the same manner as in Example 1 (e1) 1120 parts (1 mole) and thiodi 89 parts of propionic acid (0.5 moles) 120 The reaction was carried out for 12 hours while nitrogen was bubbled in the liquid at 30 ° C. and below 30 mmHg to obtain a polyether type lubricating oil (g3) having a liquid acid value of 1.0 at room temperature.
[0040]
Comparative Example 1
Into a glass autoclave, 200 parts (1.0 mol) of isotridecanol and 3.3 parts of KOH were charged, and 1102 parts (19.0 mol) of PO was dropped from a pressure-resistant dropping funnel at 105 ° C. over 33 hours. Then, it was made to react at 130 degreeC for 10 hours, and was cooled. Further, after treatment with an adsorption treating agent, filtration, and dehydration under reduced pressure at 130 ° C. and 30 mmHg or less, 1184 parts of a 19.0 mol PO adduct of isotridecanol was obtained.
[0041]
Comparative Example 2
Comparative Example 2 was obtained by using 1120 parts (e1) of THF 6.5 mol / PO 10.0 mol random adduct of isotridecanol obtained in Example 1.
Comparative Example 3
In Example 1, except that 440 parts (10.0 mol) of EO was used instead of 580 parts (10.0 mol) of PO, in the same manner as in Example 1, THF 6.5 mol / EO10 of isotridecanol was used. 1.0 mol random adduct 1100 parts (e3) was obtained. 1100 parts (1 mol) of the obtained (e3) and 50 parts (0.5 mol) of succinic anhydride were reacted at 120 ° C. for 12 hours while introducing nitrogen in the solution, and a polyester having a liquid acid value of 3.0 at room temperature was reacted. -A tellurium lubricating oil (g4) was obtained.
Comparative Example 4
A spindle oil was used as a comparative example.
[0042]
[Table 1]

[0043]
【The invention's effect】
The polyether-based lubricating oil of the present invention has the following effects. Therefore, it is extremely suitable as a lubricating oil.
(1) Excellent compatibility with hydrocarbon-based lubricating oil such as mineral oil.
(2) Excellent lubricity.

Claims (3)

A polyether (E) represented by the following general formula (1) and having a number average molecular weight of 500 to 30,000, a carboxylic acid or an acid anhydride thereof, a lower alkyl ester thereof, or an acid halide thereof (a) A lubricating oil comprising (G) and a reaction product (G) with an HLB of 6.0 or less.
_{^{R 1 - {(OCH 2 CH}} 2 CH 2 CH 2) m (OA) n} -OH (1)
[Wherein R ¹ is a hydrocarbon group having 1 to 24 carbon atoms, A is an alkylene group having 2 to 24 carbon atoms excluding a 1,4-butylene group, and m and n have a number average molecular weight of (E) of 500. It is an integer greater than or equal to 1 and 30,000. ] The lubricating oil according to claim 1, wherein (OCH ₂ CH ₂ CH ₂ CH ₂ ) and (OA) constituting the polyether (E) are random bonds. The lubricating oil according to claim 1 or 2, wherein the valence of the carboxylic acid or its acid anhydride or its lower alkyl ester or its acid halide (a) is 2 to 4.