CN1213133C - Lubricating oil composition for papermaker - Google Patents

Lubricating oil composition for papermaker Download PDF

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Publication number
CN1213133C
CN1213133C CNB011407271A CN01140727A CN1213133C CN 1213133 C CN1213133 C CN 1213133C CN B011407271 A CNB011407271 A CN B011407271A CN 01140727 A CN01140727 A CN 01140727A CN 1213133 C CN1213133 C CN 1213133C
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butyl
carbon
ester
composition
tert
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CN1346872A (en
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富永英二
小西徹
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Eneos Corp
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Nippon Mitsubishi Oil Corp
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/08—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic sulfur-, selenium- or tellurium-containing compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/04—Hydroxy compounds
    • C10M129/10—Hydroxy compounds having hydroxy groups bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04—Phosphate esters

Abstract

A lubricating oil composition for a paper machine is provided which has good thermostability and simultaneously excellent corrosion resistance and wear resistance. The lubricating oil composition for a paper machine comprises a base oil of at least one kind selected from a mineral oil, fats and oils, and a synthetic oil, (A) a phosphoric ester, (B) a phenol based antioxidant and/or an amine based antioxidant, and (C) an organic acid salt of at least one metal selected from an alkali metal, an alkaline earth metal, zinc, and lead.

Description

Lubricating oil composition for papermaker
Technical field
The present invention relates to a kind of lubricating oil composition for papermaker, relate in more detail and a kind ofly have good anti-residue and have the good non-corrosibility and the lubricating oil composition for papermaker of attrition resistance simultaneously.
Background technology
Utilize paper machine to copy after the paper, through the operation of super-dry paper, it is long that existing paper machine carries out the exsiccant time, and drying temperature also is in low temperature.The paper machine that used in recent years in order to enhance productivity, the time shared on the drying process shortens, and the result makes drying temperature also very high.
Drying temperature one uprises, and the thermal load of lubricating oil is also just corresponding to be increased, and uses the paper machine of existing mineral oil to use lubricating oil because poor heat resistance is easy to generate residue and coking etc. in lubricated portion.When using paper machine to copy paper, use highly acid plain boiled water in addition,, have the corrosive function that prevents from the machinery of these plain boiled waters with lubricating oil so also require to copy paper because this plain boiled water has the tendency of corroding metal.
Like this, require paper machine to have thermotolerance and non-corrosibility 2 big performances with lubricating oil, in order to suppress residue, in case using metal in large quantities is sanitising agent and ashless dispersant, faults such as non-corrosibility reduction, the corrosion of paper machine body then take place sometimes, and the aspect of taking into account these two opposition is very difficult.
Summary of the invention
The object of the present invention is to provide and have the lubricating oil composition for papermaker that good heat resistance has good non-corrosibility and attrition resistance simultaneously.
The present inventor is in order to finish described problem, study repeatedly, found that: use specific lubricant base, again specific compounds being used for this base oil contains it, can obtain having good thermotolerance like this and have the good non-corrosibility and the lubricating oil composition of attrition resistance simultaneously, thereby finish the present invention.
What just the present invention relates to copies the material that the paper lubricating oil composition is a kind of formation as described below, to be selected from least a kind of oil in mineral oil, grease and the synthetic oil as base oil, contain (A) phosphoric acid ester, (B) phenol is that oxidation inhibitor and/or amine are oxidation inhibitor, and (C) be selected from basic metal, at least a metal salts of organic acids in alkaline-earth metal, zinc and the lead.
Embodiment
Explain the present invention below.
In lubricating oil composition of the present invention, use at least a kind of oil that is selected from mineral oil, grease and the synthetic oil as base oil.
Here mineral oil can exemplify as follows: the lubricating oil distillate that obtains for utilizing air distillation and underpressure distillation crude oil, the refining means more than a kind or 2 kinds of solvent being taken off gravel (れ I), solvent extraction, hydrogenation decomposition, solvent dewaxing, catalytic dewaxing, hydrofinishing, sulfuric acid cleaned, clay treatment etc. suitably make up and suitably use, obtain the mineral oil of chain methane series or naphthene series etc.
In addition, grease for example has: tallow, lard, Trisun Oil R 80, soybean oil, rapeseed oil, Rice pollard oil, Oleum Cocois, plam oil, palm kernel oil or its hydrogenation thing etc.
In addition, for example have as synthetic oil: poly-alpha-olefins (ethylene-propylene copolymer, polybutene, 1-octene oligopolymer, the 1-decene oligopolymer, with and hydride etc.), alkylbenzene, alkylnaphthalene, monoesters (butyl stearate, the dodecylic acid monooctyl ester), diester (pentanedioic acid two-tridecyl ester, two-2-ethylhexyl adipic acid ester, the diiso decyl adipic acid ester, two-tridecyl adipic acid ester, sebacic acid two-2-(ethyl hexyl) ester etc.), polyester (trimellitate etc.), polyol ester (trimethylolpropane caprylate, the TriMethylolPropane(TMP) pelargonate, tetramethylolmethane-2-ethylhexanoate, tetramethylolmethane pelargonate etc.), polyether polyols, polyphenylene ether, dialkyl diphenyl ether, phosphoric acid ester (tricresyl alkaliine etc.), fluorochemicals (PFPE, fluorinated polyolefin etc.), silicone oil etc.
The base oil of lubricating oil composition for papermaker of the present invention can use above-mentioned base oil separately, also can be used in combination more than 2 kinds.
In addition, wherein consider the preferred synthetic oil of good heat resistance, especially preferably poly-alpha-olefins, polyol ester as the base oil of lubricating oil composition for papermaker of the present invention.
There is no particular limitation for its viscosity of base oil that the present invention uses, and considers that withstand load is good, and preferred 40 ℃ kinetic viscosity is 30mm 2The material that/s is above, more preferably 50mm 2The material that/s is above.Consider supply in addition, preferred 1500mm to the lubricating oil of lubricant housings 2The material that/s is following, more preferably 1000mm 2The material that/s is following.
In addition, the content of the base oil in the lubricating oil composition of the present invention can be any, and still common full dose with lubricating oil composition for papermaker is more than the preferred 80 quality % of benchmark, more preferably more than the 85 quality %, most preferably more than the 90 quality %.
(A) composition is a phosphoric acid ester in the base oil in the lubricating oil composition of the present invention.
Phosphoric acid ester is preferably used the compound shown in the concrete following general formula (1).
(RO) 3-P＝O (1)
In the described formula (1), R represents that carbon number is 1～24 alkyl.The alkylaryl of the alkyl of for example 1～24 carbon that such alkyl is concrete, the alkenyl of 2～24 carbon, the cycloalkyl of 5～7 carbon, the alkyl-cycloalkyl of 6～24 carbon, the aryl of 6～10 carbon, 7～24 carbon, the arylalkyl of 7～24 carbon etc.
Wherein, consider to have better attrition resistance, the alkylaryl of the aryl of preferred 6～10 carbon, 7～24 carbon, the more preferably alkyl phenyl of phenyl, naphthyl, 7～18 carbon, the most preferably alkyl phenyl of phenyl, 7～10 carbon.
What the alkyl phenyl of 7～10 carbon was concrete for example has: aminomethyl phenyl (the position of substitution of methyl is arbitrarily), 3,5-dimethylphenyl (the position of substitution of methyl is arbitrarily), ethylphenyl (the position of substitution of ethyl is arbitrarily), methylethyl phenyl (the position of substitution of methyl and ethyl is arbitrarily), (propyl group can be that straight chain also can be a side chain to the propyl group phenyl, its the position of substitution is arbitrarily), (propyl group can be that straight chain also can be a side chain to the methyl-propyl phenyl, the position of substitution of methyl and propyl group is arbitrarily), diethyl phenyl (the position of substitution of ethyl is arbitrarily), butyl phenyl propyl group (butyl can be that straight chain also can be a side chain, and its position of substitution is arbitrarily) etc.
In addition, 3 R can be the same or different in a part.
Concrete for example the having of the preferred phosphoric acid ester of (A) of the present invention composition: triphenyl, Tritolyl Phosphate, toluene monooxygenase base diphenyl phosphoester, two-tolyl list phenyl phosphate ester, triphenyl thiophosphatephosphorothioate and described mixture etc., wherein preferred especially triphenyl, tricresyl phosphate-tolyl ester, single phenyl diphenyl phosphoester, two-tolyl list phenyl phosphate ester and composition thereof etc.
The content of (A) composition in the lubricating oil composition for papermaker of the present invention is any, its higher limit is the preferred 10 quality % of benchmark with the composition full dose, more preferably 7 quality %, more preferably 5 quality %, 2 quality % most preferably, its lower value is the preferred 0.01 quality % of benchmark with the composition full dose on the one hand, more preferably 0.02 quality %, more preferably 5 quality %, preferred especially 0.05 quality %, most preferably 0.1 quality %.(A) even the content of composition surpasses 10 quality %, only the various performances that are consistent with content also not necessarily have the effect of raising, stability in storage possible deviation in addition.On the other hand, (A) composition contain quantity not sufficient 0.01 quality % the time, do not have additive effect, the thermotolerance of lubricating oil composition for papermaker, non-corrosibility and attrition resistance may worsen.
(B) composition in the lubricating oil composition of the present invention be (B-1) phenol be oxidation inhibitor and/or (B-2) amine be oxidation inhibitor.
(B-1) phenol is that oxidation inhibitor can use and can be not particularly limited as the based compound of alkylphenol arbitrarily of antioxidant for lubricant oil, for example is selected from the alkylphenol compound more than a kind or 2 kinds in the compound of following general formula (2) or general formula (3) expression.
Figure C0114072700061
R in above-mentioned (2) formula 4The alkyl of 1～4 carbon of expression, R 5The alkyl of expression hydrogen atom or 1～4 carbon, R 6The group of expression hydrogen atom, the alkyl of 1～4 carbon, following general formula (i) expression or the group that following general formula is (ii) represented.
R in above-mentioned (i) formula 7The alkylidene group of 1～6 carbon of expression, R 8The alkyl or alkenyl of 1～24 carbon of expression.
R in the above-mentioned (ii) formula 9The alkylidene group of 1～6 carbon of expression, R 10Alkyl, the R of 1～4 carbon of expression 11The alkyl of expression hydrogen atom or 1～4 carbon.
Figure C0114072700071
R in above-mentioned (3) formula 12And R 16The alkyl of representing 1～4 carbon respectively, R 13And R 17The alkyl, the R that represent hydrogen atom or 1～4 carbon respectively 14And R 15Alkylidene group, the Y that represents 1～6 carbon respectively represents the group shown in the alkylidene group of 1～18 carbon or following general formula are (iii).
-R 18-S～R 19 (iii)
R in the above-mentioned (iii) formula 18And R 19The alkylidene group of representing 1～6 carbon respectively.
In general formula (2), R 4The alkyl of 1～4 carbon of expression.Such alkyl is concrete for example methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl etc., considers oxidative stability preferred tertiary butyl.
R in addition 5The alkyl of expression hydrogen atom or 1～4 carbon.Such alkyl is concrete for example methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl etc., considers oxidative stability preferred tertiary butyl.
In general formula (2), R 6The base of expression hydrogen atom, the alkyl of 1～4 carbon, above-mentioned formula (i) expression and the group that above-mentioned formula is (ii) represented.
R 6The alkyl of 1～4 carbon of expression is concrete for example methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl etc., considers oxidative stability preferable methyl or ethyl.
R in general formula (2) 6Be the occasion of the represented base of (i) formula, (i) R of formula 7The alkylidene group of 1～6 represented carbon can be that straight chain also can be a side chain, concrete example is as methylene radical, methyl methylene radical, ethylidene (dimethylene), ethyl methylene radical, propylidene (methyl ethylene base), trimethylene, the butylidene of straight or branched, the pentylidene of straight or branched, the hexylidene of straight or branched etc.
Consideration is made the compound shown in its formula of (2), R with few reaction process 7The alkylidene group of 1～2 carbon of preferred expression, concrete for example have methylene radical, methyl methylene radical, an ethylidene (dimethylene) etc.
The R of (i) formula on the one hand 8The alkyl or alkenyl of 1～24 represented carbon can be that straight chain also can be a side chain, and concrete example is as alkyl (these alkyl can be that straight chain also can be a side chain) such as methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl; Thiazolinyls (these thiazolinyls can be that straight chain also can be a side chain, and the position of two keys also is arbitrarily) such as vinyl, propenyl, pseudoallyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonene base, decene base, hendecene base, laurylene base, tridecylene base, tetradecene base, ten pentaene bases, hexadecylene base, 17 thiazolinyls, octadecylene base, 18 carbon dialkylenes, 19 thiazolinyls, icosa alkene base, two hendecene bases, docosene base, tricosene base, two tetradecene bases.Consider that wherein the solvability to base oil is good, R 8The alkyl of 4～18 carbon of preferred expression, concrete preference is if any alkyl (these alkyl can be that straight chain also can be a side chain) such as butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyls.The more preferably straight or branched alkyl of 6～12 carbon, the branched-chain alkyl of preferred especially 6～12 carbon.
In the represented phenolic compound of general formula (2), R 6Be the compound of the occasion of the represented base of (i) formula, R in preferred (i) formula 7Be the alkylidene group of 1～6 carbon, R 8Be the material of the straight or branched alkyl of 6～12 carbon, more preferably R in (i) formula 7Be the alkylidene group of 1～2 carbon, R 8It is the material of the branched-chain alkyl of 6～12 carbon.
R in the general formula (2) 6Be the (ii) compound of the occasion of the represented base of formula, (ii) R in the formula 9 expressionsThe alkylidene group of 1～6 carbon.This alkylidene group can be that straight chain also can be a side chain, and concrete example such as front are for R 7Illustrative various alkylidene group.General formula (2) is made in consideration with few operation compound with and raw material be easy to get R 9The alkylidene group of 1～3 carbon of expression, concrete example such as methylene radical, methyl methylene radical, ethylidene (ethylene group), ethyl methylene radical, propylidene (methyl ethylene base), trimethylene etc.
In addition, the (ii) R in the formula 10The alkyl of 1～4 carbon of expression.Concrete for example have methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, a tertiary butyl etc., considers the good preferred tertiary butyl of oxidative stability.R in addition 11The alkyl of expression hydrogen atom or aforesaid 1～4 carbon is considered the good preferred tertiary butyl of oxidative stability.
In general formula (2), aforesaid R 6The base of expression hydrogen atom, the alkyl of 1～4 carbon, above-mentioned formula (i) expression and the base that above-mentioned formula is (ii) represented, the alkyl of wherein preferred 1～4 carbon, more preferably methyl, ethyl.
Contain aforesaid all cpds as the compound shown in the general formula (2), wherein, if enumerate preferred material, as R 6The compound of the occasion of the alkyl of 1～4 carbon of expression for example has: 2, and 6-two-tertiary butyl-p-cresol, 2,6-two-tertiary butyl-4-ethyl phenol etc.; As R 6For the compound of the occasion of the base of general formula (i) expression for example has: (3-methyl-5-tert-butyl-hydroxy phenyl) acetic acid n-hexyl ester, (3-methyl-5-tert-butyl-hydroxy phenyl) acetic acid isohexyl ester, (3-methyl-5-tert-butyl-hydroxy phenyl) acetic acid n-heptyl ester, the different heptyl ester of (3-methyl-5-tert-butyl-hydroxy phenyl) acetic acid, (3-methyl-5-tert-butyl-hydroxy phenyl) acetic acid n-octyl ester, (3-methyl-5-tert-butyl-hydroxy phenyl) acetic acid isooctyl acrylate, (3-methyl-5-tert-butyl-hydroxy phenyl) acetic acid 2-(ethyl hexyl) ester, (3-methyl-5-tert-butyl-hydroxy phenyl) acetic acid n-nonyl ester, the different nonyl ester of (3-methyl-5-tert-butyl-hydroxy phenyl) acetic acid, (3-methyl-5-tert-butyl-hydroxy phenyl) positive decyl ester of acetic acid, (3-methyl-5-tert-butyl-hydroxy phenyl) acetic acid isodecyl ester, (3-methyl-5-tert-butyl-hydroxy phenyl) acetic acid n-undecane base ester, the different undecyl ester of (3-methyl-5-tert-butyl-hydroxy phenyl) acetic acid, (3-methyl-5-tert-butyl-hydroxy phenyl) acetic acid dodecyl ester, (3-methyl-5-tert-butyl-hydroxy phenyl) acetic acid Permethyl 99A. base ester, (3-methyl-5-tert-butyl-hydroxy phenyl) propionic acid n-hexyl ester, (3-methyl-5-tert-butyl-hydroxy phenyl) propionic acid isohexyl ester, (3-methyl-5-tert-butyl-hydroxy phenyl) propionic acid n-heptyl ester, the different heptyl ester of (3-methyl-5-tert-butyl-hydroxy phenyl) propionic acid, (3-methyl-5-tert-butyl-hydroxy phenyl) propionic acid n-octyl ester, (3-methyl-5-tert-butyl-hydroxy phenyl) propionic acid isooctyl acrylate, (3-methyl-5-tert-butyl-hydroxy phenyl) propionic acid 2-(ethyl hexyl) ester, (3-methyl-5-tert-butyl-hydroxy phenyl) propionic acid n-nonyl ester, the different nonyl ester of (3-methyl-5-tert-butyl-hydroxy phenyl) propionic acid, (3-methyl-5-tert-butyl-hydroxy phenyl) positive decyl ester of propionic acid, (3-methyl-5-tert-butyl-hydroxy phenyl) propionic acid isodecyl ester, (3-methyl-5-tert-butyl-hydroxy phenyl) propionic acid n-undecane base ester, the different undecyl ester of (3-methyl-5-tert-butyl-hydroxy phenyl) propionic acid, (3-methyl-5-tert-butyl-hydroxy phenyl) propionic acid dodecyl ester, (3-methyl-5-tert-butyl-hydroxy phenyl) propionic acid Permethyl 99A. base ester, (3,5-two-tert-butyl-hydroxy phenyl) acetic acid n-hexyl ester, (3,5-two-tert-butyl-hydroxy phenyl) acetic acid isohexyl ester, (3,5-two-tert-butyl-hydroxy phenyl) acetic acid n-heptyl ester, (3,5-two-tert-butyl-hydroxy phenyl) the different heptyl ester of acetic acid, (3,5-two-tert-butyl-hydroxy phenyl) acetic acid n-octyl ester, (3,5-two-tert-butyl-hydroxy phenyl) acetic acid isooctyl acrylate, (3,5-two-tert-butyl-hydroxy phenyl) acetic acid 2-(ethyl hexyl) ester, (3,5-two-tert-butyl-hydroxy phenyl) acetic acid n-nonyl ester, (3,5-two-tert-butyl-hydroxy phenyl) the different nonyl ester of acetic acid, (3,5-two-tert-butyl-hydroxy phenyl) the positive decyl ester of acetic acid, (3,5-two-tert-butyl-hydroxy phenyl) acetic acid isodecyl ester, (3,5-two-tert-butyl-hydroxy phenyl) acetic acid n-undecane base ester, (3,5-two-tert-butyl-hydroxy phenyl) the different undecyl ester of acetic acid, (3,5-two-tert-butyl-hydroxy phenyl) acetic acid dodecyl ester, (3,5-two-tert-butyl-hydroxy phenyl) acetic acid Permethyl 99A. base ester, (3,5-two-tert-butyl-hydroxy phenyl) propionic acid n-hexyl ester, (3,5-two-tert-butyl-hydroxy phenyl) propionic acid isohexyl ester, (3,5-two-tert-butyl-hydroxy phenyl) propionic acid n-heptyl ester, (3,5-two-tert-butyl-hydroxy phenyl) the different heptyl ester of propionic acid, (3,5-two-tert-butyl-hydroxy phenyl) propionic acid n-octyl ester, (3,5-two-tert-butyl-hydroxy phenyl) propionic acid isooctyl acrylate, (3,5-two-tert-butyl-hydroxy phenyl) propionic acid 2-(ethyl hexyl) ester, (3,5-two-tert-butyl-hydroxy phenyl) propionic acid n-nonyl ester, (3,5-two-tert-butyl-hydroxy phenyl) the different nonyl ester of propionic acid, (3,5-two-tert-butyl-hydroxy phenyl) the positive decyl ester of propionic acid, (3,5-two-tert-butyl-hydroxy phenyl) propionic acid isodecyl ester, (3,5-two-tert-butyl-hydroxy phenyl) propionic acid n-undecane base ester, (3,5-two-tert-butyl-hydroxy phenyl) the different undecyl ester of propionic acid, (3,5-two-tert-butyl-hydroxy phenyl) propionic acid dodecyl ester, (3,5-two-tert-butyl-hydroxy phenyl) propionic acid Permethyl 99A. base ester etc.; As R 6The compound that is the occasion of the base (ii) represented of formula for example has: two (3,5-two-tert-butyl-hydroxy phenyl) methane, 1,1-two (3,5-two-tert-butyl-hydroxy phenyl) ethane, 1,2-two (3,5-two-tert-butyl-hydroxy phenyl) ethane, 1,1-two (3,5-two-tert-butyl-hydroxy phenyl) propane, 1, two (3, the 5-two-tert-butyl-hydroxy phenyl) ethane, 1 of 2-, 3-two (3,5-two-tert-butyl-hydroxy phenyl) propane, 2, two (3,5-two-tert-butyl-hydroxy phenyl) propane of 2-etc.; And composition thereof etc.
On the one hand in described general formula (3), R 12And R 16The alkyl of representing 1～4 carbon respectively, concrete for example have methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, a tertiary butyl etc., considers well equal preferred tertiary butyl of oxidative stability.
R 13And R 17The alkyl of representing hydrogen atom or 1～4 carbon respectively, such alkyl are considered the oxidative stability well preferable methyl or the tertiary butyl respectively as mentioned above.
In addition in general formula (3), R 14And R 15The alkylidene group of representing 1～6 carbon respectively can be that straight chain also can be a straight chain, and concrete is respectively to R 7Described various alkylidene group.Compound and the raw material of considering to utilize few reaction process to make its formula of (3) expression obtain R easily 14And R 15The alkylidene group of preferred 1～2 carbon of difference, concrete for example methylene radical, methyl methylene radical, ethylidene (dimethylene) etc.
In the general formula (3), Y represents the alkylidene group of 1～18 carbon or the base that described formula is (iii) represented.
Concrete for example the having of alkylidene group of 1～18 carbon of representing as Y: methylene radical, the methyl methylene radical, ethylidene (dimethylene), the ethyl methylene radical, propylidene (methyl ethylene base), 1, the 3-propylidene, butylidene, pentylidene, hexylidene, inferior heptyl, octylene, nonamethylene, inferior decyl, inferior undecyl, inferior dodecyl, inferior tridecyl, inferior tetradecyl, inferior pentadecyl, inferior hexadecyl, inferior heptadecyl, (these alkylidene groups can be that straight chain also can be a side chain) such as inferior octadecyls, consider that raw material such as obtains easily at the alkylidene group of preferred 1～6 carbon, concrete for example methylene radical, the methyl methylene radical, ethylidene (dimethylene), the ethyl methylene radical, propylidene (methyl ethylene base), 1, the 3-propylidene, butylidene, pentylidene, hexylidene (these alkylidene groups can be that straight chain also can be a side chain), preferred especially ethylidene (dimethylene), trimethylene, straight chain butylidene (tetramethylene), straight chain pentylidene (pentamethylene), the straight-chain alkyl-sub-of 2～6 carbon of straight chain hexylidene (hexa-methylene) etc.
Particularly preferred Y is that the compound of occasion of the alkylidene group of 1～18 carbon is the compound shown in following (4) in the alkylphenol of general formula (3) expression.
Figure C0114072700121
Y in general formula (3) is the occasion of the base represented with (iii) formula, the (iii) R in the formula in addition 18And R 19The alkylidene group of 1～6 represented carbon can be that straight chain also can be a straight chain, and concrete is respectively to R as preceding 7Described various alkylidene group.Compound and the raw material of considering to utilize few reaction process to make its formula of (3) expression obtain R easily 18And R 19The alkylidene group of preferred 1～3 carbon of difference, concrete for example methylene radical, methyl methylene radical, ethylidene (dimethylene), ethyl methylene radical, propylidene (methyl ethylene base), trimethylene etc.
In the alkylphenol with general formula (3) expression, particularly preferred Y is that the compound of the (iii) occasion of the base represented of formula is the compound shown in following (5).
Figure C0114072700122
On the other hand, as (B-2) amine is oxidation inhibitor, can use the based compound of aromatic amine arbitrarily as the oxidation inhibitor use of lubricating oil, be not particularly limited, for example can be preferably selected from the p of (N-is to alkyl) phenyl-shown in following general formula (6) or general formula (7) expression, the aromatic amine more than a kind or 2 kinds in p '-dialkyl group diphenylamine.
In above-mentioned (6) formula, R 20The alkyl of expression hydrogen atom or 1～16 carbon.
Figure C0114072700124
R in above-mentioned (7) 21And R 22The alkyl of representing 1～16 carbon respectively.
In described (6) formula, R 20The alkyl of the straight or branched of expression hydrogen atom or 1～16 carbon.Work as R 20Surpass 16 occasion, the ratio of the functional group that occupies in the molecule diminishes, and resistance of oxidation might weaken.
As R 20Concrete for example the having of alkyl: (these alkyl can be that straight chain also can be a side chain) such as methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyls.
Work as R in the compound shown in the general formula (6) 20During for alkyl, consider that himself oxidation products solvability of relative base oil is good, the alkyl of the side chain of preferred 8～16 carbon, the more preferably oligopolymer of the alkene of 3 or 4 carbon branched-chain alkyl of 8～16 carbon obtaining of deriving.For example propylene, 1-butylene, 2-butylene and iso-butylene that the alkene of 3 or 4 carbon described here is concrete consider that himself oxidation resultant solvability of relative base oil is good, preferred propylene or iso-butylene.
As (B-2) of the present invention composition, the occasion of (N-is to alkyl) phenyl-that (6) formula of stating is in the use represented, R 202 aggressiveness of preferred especially hydrogen atom or iso-butylene derive the side chain octyl that obtains, by 3 aggressiveness of propylene derive the side chain nonyl that obtains, by 3 aggressiveness of iso-butylene, 4 aggressiveness of the side chain dodecyl that obtains, the propylene side chain pentadecyl that 5 aggressiveness of the side chain dodecyl that obtains or propylene derive and obtain of deriving of deriving, 2 aggressiveness of preferred especially hydrogen atom or iso-butylene, 3 aggressiveness of the side chain octyl group that obtains, the iso-butylene side chain dodecyl that the tetramer of the side chain dodecyl that obtains or propylene derives and obtain of deriving of deriving.
R in the aromatic amine that (6) formula of use is represented 20The compound that is alkyl also can use commercially available N-to alkylbenzene-Alpha-Naphthyl amine.Can make the olefin oligomer and the phenyl-reaction of alkene or 2～16 carbon of the alkyl halide compound of phenyl-and 1～16 carbon, 2～16 carbon by using Fu-Ke catalyzer in addition, easily synthesize.What at this moment, Fu-Ke catalyzer was concrete for example can use: the metal halide of ammonium chloride, zinc chloride, iron(ic) chloride etc.; An acidic catalyst of sulfuric acid, phosphoric acid, five phosphorus oxide, boron fluoride, acidic white earth, atlapulgite etc. etc.
On the other hand, expression p, R in above-mentioned (7) formula of p '-dialkyl group diphenylamine 21And R 22The alkyl of representing 1～16 carbon respectively.
R 21And R 22Divide that other one or two be the occasion of hydrogen atom, because himself oxidation may be as the residue sedimentation, carbonatoms surpasses 16 occasion on the one hand, and owing to the ratio of functional group shared in the molecule is little, resistance of oxidation may die down.
R 21And R 22Concrete for example has: (these alkyl can be that straight chain also can be a side chain) such as methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyls.Himself the oxidation resultant solvability of wherein considering relative base oil is good, R 21And R 22The derive branched-chain alkyl of 3～16 carbon obtaining of the alkyl of the side chain of preferred 3～16 carbon, the more preferably alkene of 3 or 4 carbon, or its oligopolymer.
For example propylene, 1-butylene, 2-butylene and iso-butylene etc. that the alkene of 3 or 4 carbon described here is concrete consider that himself oxidation resultant solvability of relative base oil is good, preferred propylene or iso-butylene.
State the p that (7) formula is represented in the use as (B-2) of the present invention composition, the occasion of p '-dialkyl group diphenylamine, R 21And R 22The sec.-propyl that preferred especially propylene derived obtains, the tertiary butyl that different propylene derived obtains, the side chain hexyl that 2 aggressiveness of propylene are derived and obtained, the side chain octyl group that 2 polymers of iso-butylene are derived and obtained, the side chain nonyl that the tripolymer of propylene is derived and obtained, the side chain dodecyl of deriving and obtaining by 3 aggressiveness of iso-butylene, 4 aggressiveness of the propylene side chain pentadecyl that 5 aggressiveness of the side chain dodecyl that obtains or propylene are derived and obtained of deriving, the tertiary butyl that preferred especially iso-butylene is derived and obtained, the side chain hexyl that 2 aggressiveness of propylene are derived and obtained, the side chain octyl group that 2 polymers of iso-butylene are derived and obtained, the side chain nonyl that the tripolymer of propylene is derived and obtained, by 3 aggressiveness of iso-butylene derive 4 aggressiveness of the side chain dodecyl that obtains or propylene derive the iso-butylene side chain dodecyl of deriving and obtaining.
(7) p that represents of formula, p '-dialkyl group diphenylamine also can use commercially available product.Identical with the N-shown in the formula (6) in addition to alkyl phenyl-Alpha-Naphthyl amine, can be by using Fu-Ke catalyzer, make alkene or its oligopolymer and the phenyl-reaction of alkene or 2～16 carbon of the alkyl halide compound of diphenylamine and 1～16 carbon, 2～16 carbon, easily synthesize.At this moment, as Fu Ruidi-Ke Lai Ford catalyzer concrete can use the metal halide that alkylbenzene-Alpha-Naphthyl amine exemplified when synthetic as N-and an acidic catalyst etc.
Certainly (B) of the present invention composition also can use separately be selected from phenol be antioxidant and amine be in the antioxidant a kind of compound, and, also can use the compound more than 2 kinds that is selected from above-mentioned with arbitrary proportion blended mixture etc.
The content of (B) composition is arbitrarily in the lubricating oil composition of the present invention, and its higher limit is the preferred 10 quality % of benchmark with the composition full dose, more preferably 7 quality %, preferred especially 5 quality %, 2 quality % most preferably.Content surpasses 10 quality %, does not also observe the raising effect with the corresponding wear resistant of content, in addition also possible deviation of stability in storage.
On the one hand, (B) lower value of the content of composition is the preferred 0.01 quality % of benchmark with the composition full dose, more preferably 0.02 quality %, preferred especially 0.05 quality %, 0.1 quality % most preferably.(B) occasion that contains quantity not sufficient 0.01 quality % of composition does not observe additive effect yet, in addition yet possible deviation of the thermotolerance of lubricating oil composition and wear resistant.
(C) of the present invention composition is a kind of organic acid salt that is selected from least a kind of metal in basic metal, alkaline-earth metal, zinc and the lead.
In described (C) composition, basic metal is sodium and potassium etc. for example, and alkaline-earth metal is magnesium, calcium and barium etc. for example, the preferred alkaline-earth metal that uses among the present invention.
In addition in (C) composition as organic acid salt for example have (B-1) sulfonate, (C-2) phenates, (C-3) salicylate with and composition thereof etc.
For example have as (C-1) sulfonate: molecular weight 100～1500, preferred 200～700 alkyl aromatic compound are carried out sulfonation, the alkyl aryl sulfonate that obtains thus, itself and basic metal, alkaline-earth metal, zinc or plumbous base (oxide compound or oxyhydroxide) are reacted, obtain so-called neutral sulfonate; Neutral sulfonate and superfluous basic metal, alkaline-earth metal, zinc or plumbous salt or base (oxide compound or oxyhydroxide) are heated in the presence of water, obtain alkaline sulfonate; Neutral sulfonate and basic metal, alkaline-earth metal, zinc or plumbous base (oxide compound or oxyhydroxide) are reacted, obtain carbonate parlkaline (hyperalkaline) sulfonate; Neutral sulfonate and basic metal, alkaline-earth metal, zinc or the plumbous base (oxide compound or oxyhydroxide) and the boronic acid compounds of boric acid or boron trioxide etc. are reacted, the boronic acid compounds of carbonate parlkaline (hyperalkaline) sulfonate and boric acid or boron trioxide etc. is reacted, make borate parlkaline (hyperalkaline) sulfonate that obtains; With and composition thereof.
In addition as described alkyl aryl sulfonate, concrete for example have mahogany acid or a synthetic sulfonic acid etc.Mahogany acid described here usually is to use the alkyl aromatic compound with the lubricating oil distillate of mineral oil to carry out the by product sulfonic acid that produced when sulfonated material and whiteruss are made etc.For example can use following sulfonated product as synthetic sulfonic acid in addition, the i.e. by product that produces as the alkylbenzene manufacturing works of detergent raw material, polyolefine is carried out alkylation on benzene, the alkylbenzene of the alkyl with straight or branched that obtains carries out Sulfonated product, and perhaps the alkylnaphthalene with dinonyl naphthalene etc. carries out Sulfonated product.In addition, the sulphonating agent during as these alkyl aromatic compounds of sulfonation is not particularly limited, and uses oleum or anhydrous slufuric acid usually.
As (C-2) phenates the neutral phenates is for example arranged, in the presence of the elementary sulfur or not, make the alkylphenol of alkyl and basic metal, alkaline-earth metal, zinc or plumbous base (oxide compound or oxyhydroxide) react the neutral phenates that obtains with 1～2 4～20 carbon; In the presence of water, make neutral phenates and superfluous basic metal, alkaline-earth metal, zinc or plumbous salt and base (oxide compound or oxyhydroxide) heating react the gained alkalescence phenates that obtains; Neutral phenates and basic metal, alkaline-earth metal, zinc or plumbous base (oxide compound or oxyhydroxide) are reacted, obtain so-called carbonate parlkaline (hyperalkaline) phenates; Neutral phenates and basic metal, alkaline-earth metal, zinc or the plumbous base (oxide compound or oxyhydroxide) and the boronic acid compounds of boric acid or anhydrous boric acid etc. are reacted, the boronic acid compounds of carbonate parlkaline (hyperalkaline) phenates and boric acid or anhydrous boric acid etc. is reacted, make and obtain borate parlkaline (hyperalkaline) phenates; With and composition thereof.
As (C-3) salicylate, the neutral salicylate is for example arranged, in the presence of the elementary sulfur or not, make alkylsalicylate and basic metal, alkaline-earth metal, zinc or the plumbous base (oxide compound or oxyhydroxide) of the alkyl of 4～20 carbon react the neutral salicylate that obtains with 1～2; In the presence of water, make neutral salicylate and superfluous basic metal, alkaline-earth metal, zinc or plumbous salt and base (oxide compound or oxyhydroxide) heating react the so-called alkaline salicylate that obtains; Neutral salicylate and basic metal, alkaline-earth metal, zinc or plumbous base (oxide compound or oxyhydroxide) are reacted, obtain carbonate parlkaline (hyperalkaline) salicylate; Neutral salicylate and basic metal, alkaline-earth metal, zinc or the plumbous base (oxide compound or oxyhydroxide) and the boronic acid compounds of boric acid or anhydrous boric acid etc. are reacted, the boronic acid compounds of carbonate parlkaline (hyperalkaline) salicylic acid metal salt and boric acid or anhydrous boric acid etc. is reacted, make and obtain borate parlkaline (hyperalkaline) salicylate; With and composition thereof.
The full base number of (C) of the present invention composition is arbitrarily, usually as the preferred 0～500mgKOH/g of the full base number of (C) composition, more preferably 0～450mgKOH/g.In addition, full base number of the present invention is meant according to K2501-1992[petroleum product and lubricating oil-neutralization test method] the full base number that obtains of the alkali acid system measured.
Also can use a kind that only is selected from the aforesaid compound as (C) composition among the present invention, also can use the mixture more than 2 kinds.
The content of (C) composition in the lubricating oil composition for papermaker of the present invention is arbitrarily, its higher limit is the preferred 20 quality % of benchmark with the composition full dose, more preferably 10 quality %, more preferably 5 quality %, 3 quality % most preferably, its lower value is the preferred 0.01 quality % of benchmark with the composition full dose on the one hand, more preferably 0.05 quality %, more preferably 0.1 quality %, preferred especially 0.2 quality %, even (C) content of composition surpasses 20 quality %, do not observe the effect of the various performances raisings that are consistent with content, in addition the stability in storage possible deviation yet.On the other hand, (C) composition contain quantity not sufficient 0.01 quality % the time, do not have additive effect, the thermotolerance of lubricating oil composition for papermaker may worsen.
Use specific base oil as base oil among the present invention as mentioned above, contain (A) composition, (B) composition and (C) composition as neccessary composition, can obtain the lubricating oil composition for papermaker that thermotolerance, non-corrosibility and attrition resistance further improve like this.
Lubricating oil composition for papermaker of the present invention also can be used other various additives in order further to improve its good character as required.
Such additive for example has: the metal inerting agent of antiwelding agent, benzotriazole and the alkyl thiadiazoles etc. of the oiliness rising agent of oleic acid and lipid etc., polythioether, olefine sulfide and sulfuration ester etc.; Defoamers such as silicone oil, fluorosilicon oil, polyacrylic ester; The non-emulsifying agent of the condensation resultant of oxyethane, propylene oxide etc.; The yield point depressant of polymethacrylate etc.; The viscosity index rising agent of polymethacrylate, polybutene, polyoxyethylene alkylphenyl ethene, olefin copolymer, vinylbenzene-diene copolymers, styrene-maleic anhydride copolymer etc.; Rust-preventive agent etc.
When cooperating these additives in the lubricating oil composition for papermaker of the present invention, can distinguish separately and use, also can cooperate more than 2 kinds and use.Cooperate under the situation of these general additives, additive is arbitrarily.It is amount below the 15 quality % that the total amount of the additive that these are general is preferably added with composition full dose benchmark.
Lubricating oil composition of the present invention can be for paper machine usefulness, and this lubricating oil group thing also can be suitable as the lubricating oil of for example various mechanical gears, bearing, compressor, oil pressure etc. except that paper machine.
Embodiment
Utilize embodiment and comparative example to illustrate in greater detail content of the present invention below, the invention is not restricted to these embodiment.
Embodiment 1～5 and comparative example 1～7
According to the composition shown in the table 1, what preparation the present invention was correlated with copies paper with lubricating oil composition (embodiment 1～5).In addition, according to the composition shown in the table 2, preparation is used for the composition (comparative example 1～7) of comparison.
In addition, each composition of embodiment and comparative example use is as follows.
Base oil
Basis 1: Dipentaerythritol and branching C 8-10Ester (the kinetic viscosity 150mm that forms of lipid acid 2/ s@40 ℃)
Basis 2:1-decylene oligomer (number-average molecular weight 1650)
(A) composition
A1: Tritolyl Phosphate
A2: di(2-ethylhexyl)phosphate phenyl toluene monooxygenase base ester
(B) composition
B1:2,6-di-t-butyl-p-cresol
B2:p, p '-two-branched octyl pentanoic
(C) composition
C1: lime carbonate parlkaline Whitfield's ointment calcium salt
(full base number (alkali acid system) 160mgKOH/g)
C2: neutral calcium sulfonate salt (full base number (alkali acid system) 0mgKOH/g)
For the composition of these embodiment and comparative example, the test method shown in utilization is following is estimated its thermotolerance, non-corrosibility and attrition resistance.The results are shown in table 1 and the table 2.
Thermostability: thermal stability test
[lubricating oil thermal stability test method] according to the regulation among the JIS K2540, it is the beaker of 50ml that the sample oil of getting 45g places volume, copper and iron catalyst are added wherein, after in 160 ℃ air thermostat layer, placing 10 days, the level of residue in the determination test oil.
In addition, the catalyzer that uses in the turbine oil oxidation stability test (JIS K2514) is cut into 8 volumes (the about 3.5cm of length), uses as copper and iron catalyst.
Non-corrosibility: rust prevention test
The test of stipulating in the JIS K2510 lubricating oil test for rust preventing ability method is improved with the non-corrosibility of lubricating oil in order to estimate paper machine, adopt improved test method to carry out rust prevention test.
Variation point uses distilled water or artificial seawater when estimating common lubricating oil, replace the artificial plain boiled water of above-mentioned use when estimating paper machine with lubricating oil.
Attrition resistance: FALEX abradability test
The trier that the test of FALEX abradability is used ASTM D3233-93 " to measure the extreme pressure character standard test methods (Falex Pin Vee Block Methods) of lubricating oil " and stipulated is measured wear loss.
In addition, bolt (diameter of axle) uses external diameter 6.35mm (1/4 inch), length 31.75mm (1.1/4 inch) steel, uses the steel at 96 degree angles on the V-type section.
Test conditions is: rotation number 1000rpm, Direct Load100lbs, test period are 16 hours.
Table 1
Form (quality %) Thermostability level of residue (mg/45g) Erosion resistance Wear loss (mg)
Base oil (A) composition (B) composition (C) composition
Embodiment 1 Basis 1 (98.8) A1 (0.5) B1 (0.5) C1 (0.2) 5.6 Rustless 4.4
2 Basis 2 (98.8) A1 (0.5) B1 (0.5) C1 (0.2) 4.7 Rustless 3.7
3 Basis 1 (98.8) A2 (0.5) B1 (0.5) C1 (0.2) 3.7 Rustless 7.0
4 Basis 1 (98.8) A1 (0.5) B2 (0.5) C1 (0.2) 6.8 Rustless 4.1
5 Basis 1 (98.8) A1 (0.5) B1 (0.5) C2 (0.2) 7.4 Rustless 7.8
Table 2
Form (quality %) Thermostability level of residue (mg/45g) Erosion resistance Wear loss (mg)
Base oil (A) composition (B) composition (C) composition
Comparative example 1 Basis 1 (99.0) A1 (0.5) B1 (0.5) - 41.7 Rust (severe) is arranged 17.9
2 Basis 2 (99.3) - B1 (0.5) C1 (0.2) 52.9 Rust (severe) is arranged 13.4
3 Basis 1 (99.3) A1 (0.5) - C1 (0.2) 74.1 Rust (severe) is arranged 32.9
4 Basis 1 (100) - - - 229.4 Rust (severe) is arranged 52.9
5 Basis 1 (99.8) - - C1 (0.2) 147.2 Rust (severe) is arranged 68.0
6 Basis 1 (99.8) - B1 (0.5) - 86.3 Rust (severe) is arranged 19.8
7 Basis 1 (99.8) A1 (0.5) - - 73.9 Rust (severe) is arranged 57.3
As can be known, lubricating oil composition for papermaker of the present invention (embodiment 1～5) is compared with the composition of comparative example 1～7, has the good performance of good thermotolerance, non-corrosibility and wear resistant simultaneously from table 1 and table 2.
Lubricating oil composition for papermaker of the present invention is a kind ofly to have good thermotolerance and be suppressed at the generation of the residue in the lubricating oil pipe arrangement, has good non-corrosibility and attrition resistance, can realize the long lubricating oil composition of life-span of machinery.

Claims (1)

1. lubricating oil composition for papermaker, it is characterized in that, to be selected from least a kind of oil in mineral oil, grease and the synthetic oil as base oil, with the total composition is benchmark, contain (A) phosphoesterase 30 .01～10 quality %, (B) phenol is that oxidation inhibitor and/or amine are oxidation inhibitor 0.01～10 quality %, and (C) is selected from least a metal salts of organic acids 0.01～20 quality % in basic metal, alkaline-earth metal, zinc and the lead.
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