CN102695785B - Flame-retardant hydraulic oil composition - Google Patents

Flame-retardant hydraulic oil composition Download PDF

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CN102695785B
CN102695785B CN201080061213.5A CN201080061213A CN102695785B CN 102695785 B CN102695785 B CN 102695785B CN 201080061213 A CN201080061213 A CN 201080061213A CN 102695785 B CN102695785 B CN 102695785B
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acid
ester
composition
oil
quality
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CN102695785A (en
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三本信一
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Eneos Corp
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JX Nippon Oil and Energy Corp
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    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
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Abstract

Disclosed is a flame-retardant hydraulic oil which has a satisfactory antioxidant activity, an excellent inhibitory activity on the elution of zinc and good abrasion resistance, can respond to the increase in pressure and the tendency to be maintainance-free in hydraulic systems in recent years, and has a long service life. Specifically disclosed is a flame-retardant hydraulic oil composition comprising (A) at least one base oil selected from the group consisting of synthetic esters, oils and fats each of which is characterized in that the content ratio of an unsaturated fatty acid in fatty acid in fatty acids that constitute the ester moiety is 20 mol% or more and the acid value of the ester moiety is 1.0 mgKOH/g or less and (B) an alkylthiadizole in an amount of 0.001 to 1.0 mass% relative to the total amount of the composition. Preferably, the composition additionally comprises (C) a bis(4-dialkylaminophenyl)methane in an amount of 0.001 to 5.0 mass% relative to the total amount of the composition and/or (D) at least one triazole compound selected from the group consisting of a triazole derivative, a benzotriazole derivative and a tolutriazole derivative in an amount of 0.0001 to 1.0 mass% relative to the total amount of the composition.

Description

Flame retardant hydraulic oil composition
Technical field
The present invention relates to flame retardant hydraulic oil composition, relate more specifically to such flame retardant hydraulic oil composition, it is suitable for the application of using under the high-temperature and high-pressure conditions of high fire occurrence risk having most, as cast forcing machine or the operation of iron work equipment for aluminum dipping form, and it is applicable to attrition resistance, sludge inhibition and the particularly high-pressure pump of zinc leaching retention excellence, and it can be used for a long time.
Background technology
Conventionally, as under the place thering is high fire occurrence risk, use as the hydraulic efficiency oil using in operation in aluminum dipping form casting forcing machine or iron work equipment, flame retardant resistance hydraulic efficiency oil (liquid) is if water-ethylene glycol or fatty acid ester are for maintaining the security in place.Especially in the place that is limited by fire service law the 4th petroleum-type restriction, mainly use water-ethylene glycol liquid, but have about the loaded down with trivial details storage of waste oil and the shortcoming of attrition resistance.Yet the modification of fire service law in 2002 is got rid of outside fire service law scope the hydraulic efficiency oil with 250 ℃ of above flash-points, cause having the relatively more extensively application of the fatty acid ester of high flash point.As a result, ester oil has just become flame retardant resistance hydraulic efficiency oil jointly.
The character of fatty acid ester forms and changes according to the lipid acid that forms ester.The oxidative stability of the ester of saturated fatty acid is more excellent.Yet saturated fatty acid is produced by the unsaturated fatty acids of synthetic petroleum raw material or hydrogenation source automatic vegetables oil, because of but to the disagreeableness expensive raw material of environment.At present, also used natural synthetic ester or grease, it mainly contains the lipid acid (referring to following patent documentation 1-3) that comprises the unsaturated fatty acids that is derived from vegetable and animals oils favourable on environmentally friendly and cost.
Meanwhile, because nearest hydraulic efficiency system has been used and do not needed more than becoming in the past to safeguard under elevated pressures, therefore, require the hydraulic efficiency oil using in these cases to there is long lifetime property and excellent attrition resistance.The natural synthetic ester of being produced as vegetable and animals oils by natural materials contains the lipid acid mainly consisting of unsaturated fatty acids, thereby to favourable on global environment close friend and cost.Yet it is being extremely poor shortcoming aspect synthetic ester of saturated fatty acid or the oxidative stability of synthetic hydrocarbon oil.
In principle, because ester class hydraulic efficiency oil is understood stripping zinc by remaining lipid acid, so do not use zinc in the oily part of contact as pipeline, valve or joint etc.Yet, under being widely used of ester class flame retardant resistance hydraulic efficiency oil, wherein from the zinc being generally used for the zinc-plated part stripping of the pipeline of hydraulic efficiency system, valve or joint, causing such as the quantity of situation that forms the problem of sludge and increase.Especially, when water-ethylene glycol hydraulic efficiency oil changes ester class hydraulic efficiency oil into, residual water promotes the stripping of zinc, thereby occurs in large quantities such as the problem of filter stoppage etc.By the acid increasing along with oil is deteriorated, also bring the stripping of zinc, thereby for the measurement of zinc stripping, oil oxidation stability also becomes important factor.
For conventional mineral hydraulic efficiency oil or synthin hydraulic efficiency oil, phenols or amine antioxidants or ZnDTP (zinc dialkyl dithiophosphate) have been used.Yet the ester class hydraulic efficiency oil that comprises saturated or unsaturated fatty acids has the problem that is difficult to extend working life, even if this is because add this type of routine phenol or amine antioxidants oxidation-resistance will be also inadequate.
Especially, it is significant that the synthetic ester that this trend is produced at unsaturated fatty acids bad aspect oxidative stability in use or vegetable and animals oils are used as under basic oil condition.Because not yet find the synthetic ester produced by unsaturated fatty acids for this type of or the additive of vegetable and animals oils useful effect, therefore conventionally can only select the synthetic ester (it adversely affects global environment and costliness) of being produced by saturated fatty acid, or the synthetic ester of being produced by unsaturated fatty acids or vegetable and animals oils (its oil change interval is short), and there is no other selection.
For conventional mineral hydraulic efficiency oil, ZnDTP or aromatic phosphoric ester are also used as abrasion resisting additive.Yet, for containing ester, as the hydraulic efficiency oil of base oil, point out following problem, due to the high adsorption activity of ester, therefore with for mineral hydraulic pressure oil condition, compare, additive seldom plays a role.For example, the TCP (Tritolyl Phosphate) as typical Phosphorus abrasion resisting additive can show abrasion resisting effect hardly in fatty acid ester.
Except the problems referred to above, the problem recently producing is the zinc-plated stripping by the acid that exists in ester hydraulic efficiency oil or produce between its usage period that is applied to pipeline or valve in hydraulic efficiency system.Up to now, do not produce the technology that suppresses zinc stripping, and do not use the zinc-plated best measure of thinking.
As mentioned above, in the present circumstance, use the synthetic ester produced by environmentally friendly and relatively cheap natural matter or vegetable and animals oils to develop attrition resistance excellent and can suppress zinc stripping to extend thus the flame retardant resistance hydraulic efficiency oil of working life very difficult.
Reference listing
Patent documentation
Patent documentation 1: Japanese Patent Laid-Open communique 2001-214187
Patent documentation 2: Japanese patent gazette 3548591
Patent documentation 3: Japanese patent gazette 2888747
Summary of the invention
the problem that invention will solve
In synthetic ester, some unreacted lipid acid are remaining and cause the stripping of zinc.When the acid number of lipid acid is too high, the effect that suppresses the additive of zinc stripping weakens.When forming the lipid acid of ester and be saturated fatty acid, it is poorly soluble thereby make metal as the zinc of stripping and deteriorated product easily precipitate (settle), then forms sludge.
Although for suppressing the object of abrasion, add extreme-pressure additive, gentle extreme-pressure additive as phosphoric acid ester in ester, be invalid.Otherwise the extreme-pressure additive with strong activity has disadvantageous effect and often causes zinc stripping oxidative stability and sludge inhibition.
In addition, oxidative stability is also to suppress the material particular of zinc stripping.For the hydraulic efficiency oil containing ester, it is poor as basic oil oxidation stability, and between its usage period, acid number increases, thereby promotes zinc stripping.Yet routine phenol or the amine antioxidants for mineral oil or synthetic hydrocarbon oil can not provide ester oil with sufficient antioxidant effect.
In view of the foregoing carry out the present invention, and object is the flame retardant hydraulic oil composition that provides more lasting, it comprises main containing unsaturated fatty acids and unsaturated fatty acids or the vegetable and animals oils of acid number below particular value, and it has sufficient oxidation-resistance and good zinc leaching retention and attrition resistance the response pressure in hydraulic efficiency system in recent years and increases and non-maintaining trend.
for the scheme of dealing with problems
As the result of investigating further and studying, the present invention is based on completing to the discovery that base oil solves the problems referred to above by adding special metal corrosion inhibitor, and described base oil is synthetic ester and/or the grease below 1.0mgKOH/g for particularly comprising the more than 20 % by mole unsaturated fatty acidss that is derived from natural matter and have acid number in the lipid acid that forms ester.In addition, have the exploitation that the specific amine oxidation retarder of excellent anti-oxidation characteristics and/or the mixing of specific nitrogen based metal deactivators cause ester class flame retardant resistance hydraulic efficiency oil, it has the work-ing life further extending.
" acid number " used herein represents the value of measuring according to JIS K2501 " test method is counted in the neutralization of petroleum products and lubricating oil " (potentiometric titration).
; the present invention relates to flame retardant hydraulic oil composition; it comprises that (A) selects at least one base oil of the group of freely synthesizing ester and composition; described synthetic ester and grease comprise more than 20 % by mole unsaturated fatty acidss and have acid number in the lipid acid that forms ester is below 1.0mgKOH/g; (B) the alkyl thiadiazoles of the amount of 0.001-1.0 quality %, based on composition total mass.
The invention still further relates to aforementioned flame retardant hydraulic oil composition, it further comprises: (C) two (4-dialkylamino phenyl) methane that represented by following formula (1) of the amount of 0.001-5.0 quality %, based on composition total mass:
R wherein 1, R 2, R 3and R 4can be same to each other or different to each other, and independently of one another for thering is the alkyl of 1-6 carbon atom.
The invention still further relates to aforementioned flame retardant hydraulic oil composition, it further comprises: at least one triazole compounds of the group that (D) the free triazole derivative of the choosing of the amount of 0.0001-1.0 quality %, benzotriazole derivatives and tolytriazole derivative form, and based on composition total mass.
the effect of invention
According to the present invention, for mainly comprise unsaturated fatty acids lipid acid ester oil base oil and special metal corrosion inhibitor or further special antioxidants and/or nitrogen based metal deactivators mixes, provide thus not only oxidative stability and attrition resistance is good but also can suppress zinc stripping and in FZG Gear Experimentation, pass through the flame retardant hydraulic oil composition in 10 above stages.
Embodiment
Below the present invention will be described in more detail.
For the base oil of flame retardant resistance oil compositions of the present invention, freely synthesize at least one base oil of the group of ester and composition for choosing, described synthetic ester and grease group each self-contained 20 % by mole of unsaturated fatty acidss of measuring above to have acid number be below 1.0mgKOH/g in the lipid acid that forms ester.The example of this synthetic ester comprises fatty acid ester, polyol ester and complex ester.The example of grease comprises various animal-plant oil.Preferably having kinematic viscosity at 40 ℃ is 10-200mm 2/ s and flash-point are 280 ℃ of above those.
The preferred embodiment of fatty acid ester comprises that unsaturated fatty acids is as Zoomeric acid, oleic acid, vaccenic acid, linolic acid, linolenic acid, eleostearic acid and 8, 11-eicosadienoic acid, with there is saturated fatty acid containing the straight or branched alkyl of 5-19 carbon atom as valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid, capric acid, undeeanoic acid, laurostearic acid, tridecylic acid, TETRADECONIC ACID, pentadecanoic acid, palmitic acid, margaric acid, stearic acid and nonadecanoic acid and there is monohydroxy-alcohol containing the straight or branched alkyl of 1-15 carbon atom as methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, hexanol, enanthol, octanol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, tridecanol, the ester of tetradecyl alcohol and pentadecanol, with its mixture.Concrete preferred example comprises that fatty acid ester is as the ester of the mixed fatty acid of stearic acid and oleic acid and butanols, and the ester of stearic acid and lauric mixed fatty acid and octanol.
Polyol ester preferably has dibasic alcohol or the polyvalent alcohol of 3-20 hydroxyl and has the ester of the lipid acid of 1-24 carbon atom.
The specific examples of dibasic alcohol comprises ethylene glycol, 1,3-PD, propylene glycol, BDO, 1,2-butyleneglycol, 2-methyl isophthalic acid, ammediol, 1,5-PD, neopentyl glycol, 1,6-hexylene glycol, 2-Ethyl-2-Methyl-1,3-PD, 1,7-heptanediol, 2-methyl-2-propyl-1, ammediol, 2,2-diethyl-1,3-PD, 1,8-ethohexadiol, 1,9-nonanediol, decamethylene-glycol, 1,11-undecane glycol and 1,12-dodecanediol.
The specific examples of polyvalent alcohol (polyols) comprises that polyvalent alcohol (polyhydric alcohols) is as trimethylolethane, TriMethylolPropane(TMP), tri hydroxy methyl butane, two-(TriMethylolPropane(TMP)), three-(TriMethylolPropane(TMP)), tetramethylolmethane, two-(tetramethylolmethane), three-(tetramethylolmethane), glycerine, Polyglycerine (dimer to two of glycerine ten aggressiveness (eicosamer)), 1,3,5-, penta triol, Sorbitol Powder, sorbitan, Sorbitol Powder-glycerol condensate, adonitol, arabitol, Xylitol and mannitol; Carbohydrate is as wood sugar, pectinose, ribose, rhamnosyl, glucose, fructose, semi-lactosi, seminose, sorbose, cellobiose, maltose, isomaltose, trehalose, sucrose, raffinose, gentianose and melizitose; The product of its partial ester; And methyl glucoside (glycosides).
In these, preferred polyvalent alcohol be hindered alcohols (hindered alcohols) as neopentyl glycol, trimethylolethane, TriMethylolPropane(TMP), tri hydroxy methyl butane, two-(TriMethylolPropane(TMP)), three-(TriMethylolPropane(TMP)), tetramethylolmethane and two-(tetramethylolmethane), this is because the stability to hydrolysis of their excellences.
The example of the lipid acid of polyol ester comprises about the unsaturated fatty acids of above-mentioned fatty acid ester example and has the saturated fatty acid containing the straight or branched alkyl of 5-19 carbon atom.Particularly preferably use the unsaturated fatty acids about above-mentioned fatty acid ester example.Can also use the eo-acid that alpha-carbon atom is quaternary carbon.The specific examples that props up chain saturated fatty acid comprises isovaleric acid (3 Methylbutanoic acid), 2 methyl caproic acid, 2-ethyl valeric acid, 2 ethyl hexanoic acid and 3,5,5 Trimethylhexanoic acid.
The specific examples of preferred polyol ester comprises the diester of one or more lipid acid and polyvalent alcohol, three esters and four esters, described one or more lipid acid select free unsaturated fatty acids as Zoomeric acid, oleic acid, vaccenic acid, linolic acid, linolenic acid, eleostearic acid and 8, 11-eicosadienoic acid, with there is saturated fatty acid containing the straight or branched alkyl of 5-19 carbon atom as valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid, capric acid, undeeanoic acid, laurostearic acid, tridecylic acid, TETRADECONIC ACID, pentadecanoic acid, palmitic acid, margaric acid, the group that stearic acid and nonadecanoic acid form, and comprise unsaturated fatty acids, described polyvalent alcohol is as neopentyl glycol, trimethylolethane, TriMethylolPropane(TMP), tri hydroxy methyl butane or tetramethylolmethane.
The ester of two or more lipid acid can be the mixture of the ester of two or more a kind of lipid acid and polyvalent alcohol, or the ester of two or more mixed fatty acids and polyvalent alcohol.
In these polyol esters, be preferably as follows the ester of hindered alcohols, described hindered alcohols is as neopentyl glycol, trimethylolethane, TriMethylolPropane(TMP), tri hydroxy methyl butane, two-(TriMethylolPropane(TMP)), three-(TriMethylolPropane(TMP)), tetramethylolmethane, two-(tetramethylolmethane) and three-(tetramethylolmethane), the more preferably ester of neopentyl glycol, trimethylolethane, TriMethylolPropane(TMP), tri hydroxy methyl butane and tetramethylolmethane also, this is because the stability to hydrolysis of their excellences.The ester of TriMethylolPropane(TMP) and tetramethylolmethane most preferably, this is because their excellent especially stability to hydrolysiies.Specific examples comprises oleic acid and sad mixed fatty acid and the ester of TriMethylolPropane(TMP), the mixed fatty acid of oleic acid and n-nonanoic acid and the ester of TriMethylolPropane(TMP), oleic acid and sad mixed fatty acid and the ester of tetramethylolmethane, and the mixed fatty acid of oleic acid and n-nonanoic acid and the ester of tetramethylolmethane.
Polyol ester can keep nonesterified partial ester or whole esterified full esters of hydroxyl wherein for a part of hydroxyl wherein.In addition, polyol ester can be the mixture of partial ester and full ester, but preferably full ester.
Complex ester is the ester of lipid acid and diprotic acid and monohydroxy-alcohol and polyvalent alcohol.Lipid acid, monohydroxy-alcohol and polyvalent alcohol can be for about those of above-mentioned polyol ester example.
The example of diprotic acid comprises the diprotic acid with 5-10 carbon atom, as pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid and sebacic acid.
For ester of the present invention can be have single structure a kind of ester those or there is the mixture of the two or more ester of different structure.
In these synthetic esters, preferred polyol ester, this is because the stability to hydrolysis of their excellences.
Example as the grease of the base oil of flame retardant hydraulic oil composition of the present invention comprises natural animal or Vegetable oil lipoprotein, as rapeseed oil, sunflower oil, soybean oil, Viscotrol C, Oleum Cocois, Semen Maydis oil, Oleum Gossypii semen, sweet oil, Rice pollard oil, plam oil, palm-kernel oil, peanut oil, Yatall MA, butter, lard and its hydrogenated products.In these greases, preferably wherein form the high high oleic-acid vegetables oil of ratio of the unsaturated fatty acids (particularly oleic acid) in the lipid acid of ester, as rapeseed oil, sunflower oil and soybean oil, the high oleic acid grease that more preferably oleic acid ratio further improves.
The base oil of flame retardant hydraulic oil composition of the present invention can be freely one or more of group of above-mentioned synthetic ester and composition of choosing.
In above-mentioned synthetic ester and/or grease, in the lipid acid that forms ester, the ratio of unsaturated fatty acids must be more than 20 % by mole, preferably more than 50 % by mole, more preferably more than 70 % by mole.If the ratio of unsaturated fatty acids is more than 20 % by mole, the lipid acid forming can be selected from saturated fatty acid, unsaturated fatty acids, straight chain fatty acid and branched chain fatty acid, but in view of component (C) is for the effect of the amine antioxidants of two (4-dialkylamino phenyl) methane of being represented by formula (1) preferably comprises relatively large unsaturated fatty acids.
If the ratio of unsaturated fatty acids is lower than 20 % by mole in the lipid acid of formation ester, blend components (C) is suppressing viscosity and acid number effective aspect the starting stage increase of hydraulic efficiency oil use, but use further carry out after, deteriorated product is tending towards becoming rapidly sludge and having problems in hydraulic efficiency system.
In order further to improve the effect that suppresses zinc stripping, the acid number of ester must be below 1.0mgKOH/g.If ester has the acid number that is greater than 1.0mgKOH/g, its constituents for suppressing (B) is that metal corrosion inhibitor (it is alkyl thiadiazoles) and component (D) are the effect of nitrogen based metal deactivators (it is triazole compounds), and accelerating oxidation is deteriorated, thereby composite inhibiting prevent zinc stripping property.
Kinematic viscosity to these base oils is not particularly limited.Yet, the preferred 10-200mm of kinematic viscosity at 40 ℃ 2/ s, more preferably 15-150mm 2/ s, more preferably 20-100mm 2/ s, this is because flame retardant resistance, attrition resistance and the anti-burn (anti-seizure properties) of gained hydraulic composition excellence and less by the power loss of stirring resistance.Viscosity index to base oil is also not particularly limited.Yet in order at high temperature to maintain the object of oil film, viscosity index is preferably more than 80, more preferably more than 100.In addition, pour point is also optional, but from the viewpoint of the startability of winter pump, preferably below-5 ℃, below more preferably-15 ℃.
Flame retardant hydraulic oil composition of the present invention comprises alkyl thiadiazoles, and metal corrosion inhibitor is as component (B).
Alkyl thiadiazoles be preferably by following formula (2), represented 1,3,4-thiadiazoles, by following formula (3), represented 1,2,4-thiadiazoles or the Isosorbide-5-Nitrae being represented by following formula (4), 5-thiadiazoles.Selectively, preferably use their two or more mixture.
R wherein 5and R 6can be same to each other or different to each other, and independently of one another for hydrogen or there is the alkyl of 1-20 carbon atom, and a and b can be same to each other or different to each other, and be the integer of 0-8 independently of one another.
R wherein 7and R 8can be same to each other or different to each other, and independently of one another for hydrogen or there is the alkyl of 1-20 carbon atom, and c and d can be same to each other or different to each other, and be the integer of 0-8 independently of one another.
R wherein 9and R 10can be same to each other or different to each other, and independently of one another for hydrogen or there is the alkyl of 1-20 carbon atom, and e and f can be same to each other or different to each other, and be the integer of 0-8 independently of one another.
The specific examples of this type of thiadiazole compound comprises 2, two (the n-hexyl dithio)-1 of 5-, 3, 4-thiadiazoles, 2, two (the n-octyl dithio)-1 of 5-, 3, 4-thiadiazoles, 2, two (the 2-ethylhexyl dithio)-1 of 5-, 3, 4-thiadiazoles, 2, two (the n-nonyl dithio)-1 of 5-, 3, 4-thiadiazoles, 2, 5-two (1, 1, 3, 3-tetramethyl butyl dithio)-1, 3, 4-thiadiazoles, 3, two (the n-hexyl dithio)-1 of 5-, 2, 4-thiadiazoles, 3, two (the n-octyl dithio)-1 of 5-, 2, 4-thiadiazoles, 3, two (the n-nonyl dithio)-1 of 5-, 2, 4-thiadiazoles, 3, 5-two (1, 1, 3, 3-tetramethyl butyl dithio)-1, 2, 4-thiadiazoles, 4, two (the n-hexyl dithio)-1 of 5-, 2, 3-thiadiazoles, 4, two (the n-octyl dithio)-1 of 5-, 2, 3-thiadiazoles, 4, two (the n-nonyl dithio)-1 of 5-, 2, 3-thiadiazoles and 4, 5-two (1, 1, 3, 3-tetramethyl butyl dithio)-1, 2, 3-thiadiazoles, with and composition thereof.
Flame retardant hydraulic oil composition of the present invention is with more than 0.001 quality %, and preferably more than 0.005 quality %, more preferably amount more than 0.01 quality % comprises alkyl thiadiazoles as component (B), based on composition total mass.As the content of fruit component (B) is less than 0.001 quality %, gained oil compositions can not obtain and prevent zinc stripping property.Flame retardant hydraulic oil composition of the present invention is with below 1.0 quality %, and preferably, below 0.8 quality %, more preferably the amount below 0.6 quality % comprises component (B), based on composition total mass.As the content of fruit component (B) is greater than 1.0 quality %, gained oil compositions is probably because the decomposition of alkyl thiadiazoles becomes sludge.
Flame retardant hydraulic oil composition of the present invention can contain two (the 4-dialkylamino phenyl) methane that represented by formula (1), and it is that amine antioxidants is as component (C).
In formula (1), R 1, R 2, R 3and R 4can be same to each other or different to each other, and independently of one another for thering is the straight or branched alkyl of 1-6 carbon atom.If any R 1, R 2, R 3and R 4the carbon number of group is greater than 6, and in molecule, the ratio of functional group can be little, likely causes the disadvantageous effect to antioxidant effect.By R 1, R 2, R 3and R 4the example of the alkyl representing comprises methyl, ethyl, propyl group, butyl, amyl group and hexyl (all alkyl are straight or branched).
In the amine antioxidants by formula (1) represents, preferred R wherein 1, R 2, R 3and R 4independently of one another for methyl, ethyl or there are those of branched-chain alkyl of 3 or 4 carbon atoms, R wherein most preferably 1, R 2, R 3and R 4be those of methyl or ethyl independently of one another.
Flame retardant hydraulic oil composition of the present invention is with preferably below 5.0 quality %, and more preferably, below 3.0 quality %, more preferably the amount below 1.0 quality % is included as the component (C) of two (4-dialkylamino phenyl) methane, based on composition total mass.The content that is greater than 5.0 quality % is not preferred, and this is because it causes the formation of sludge.
Otherwise oil compositions is with more than 0.001 quality %, more preferably more than 0.005 quality %, more preferably amount more than 0.01 quality % comprises component (C), based on composition total mass.The content that is less than 0.001 quality % is not preferred, and this is because resulting composition can not suppress fully the oxidative degradation of ester thereby can not suppress zinc stripping.
Flame retardant hydraulic oil composition of the present invention can be included as the triazole compounds of nitrogen based metal deactivators as component (D).For the component (D) of triazole compounds is preferably selected from the group being comprised of triazole derivative, benzotriazole derivatives and tolytriazole derivative.The specific examples of benzotriazole derivatives comprises N, two (2-the ethylhexyl)-4-methyl isophthalic acid H-benzotriazole-1-methylamines of N-and N, two (2-the ethylhexyl)-5-methyl isophthalic acid H-benzotriazole-1-methylamines of N-.
Flame retardant hydraulic oil composition is with preferably more than 0.0001 quality %, and more preferably more than 0.0005 quality %, more preferably amount more than 0.001 quality % comprises component (D), based on composition total mass.The content that is less than 0.0001 quality % is not preferred, and this is because resulting composition can not fully suppress zinc stripping.Otherwise oil compositions is with below 1.0 quality %, more preferably, below 0.8 quality %, more preferably the amount below 0.5 quality % comprises component (D), based on composition total mass.The content that is greater than 1.0 quality % is not preferred, because component (D) is difficult to be dissolved in ester base oil, thereby probably due to the deteriorated sludge that becomes of additive.
Flame retardant hydraulic oil composition of the present invention can contain as being selected from (E1) sulfur-bearing phosphoric acid ester, (E2) acid phosphoric acid ester, (E3) acid phosphate amine salt and (E4) component (E) of at least one abrasion resisting additive of phosphorous acid ester, further to improve the performance of composition.
(E1) specific examples of sulfur-bearing phosphoric acid ester comprises that its alkyl has the tri o cresyl thiophosphate alkyl ester of 4-18 carbon atom, tri o cresyl thiophosphate oil base ester, triphenyl-thiophosphate, thiophosphoric acid trimethylbenzene ester, tri o cresyl thiophosphate (dimethylbenzene) ester, thiophosphoric acid tolyl diphenyl ester, thiophosphoric acid dimethylbenzene diphenyl ester (xylenyldiphenyl phosphorothionate), tri o cresyl thiophosphate (n-propyl phenyl) ester, tri o cresyl thiophosphate (isopropyl phenyl) ester, tri o cresyl thiophosphate (n-butylphenyl) ester, tri o cresyl thiophosphate (isobutyl phenenyl) ester, tri o cresyl thiophosphate (secondary butyl phenenyl) ester and tri o cresyl thiophosphate (tert-butyl-phenyl) ester.
(E2) specific examples of acid phosphoric acid ester comprises that its alkyl has dialkyl group acid phosphoric acid ester and two oil base acid phosphoric acid esters (dioleyl acid phosphates) that the alkyl acid phosphoric acid ester of 7-18 carbon atom, its alkyl have 6-18 carbon atom.
(E3) specific examples of acid phosphorous acid ester amine salt comprises the salt of aforementioned acid phosphorous acid ester and following amine: the amine of the alkyl that described amine is the amine with the alkyl of 1-8 carbon atom, have two 1-8 carbon atoms and have the amine of the alkyl of three 1-8 carbon atoms.
(E4) specific examples of phosphorous acid ester comprises dialkyl phosphite, phosphorous acid two oil base esters, diphenyl phosphite, phosphorous acid diformazan phenyl ester, the trialkyl phosphite with the alkyl of three 4-12 carbon atoms, tricresyl phosphite oil base ester, triphenyl phosphite and the tricresyl phosphite of the alkyl with two 4-12 carbon atoms.
Component (E) is preferably any (E1) sulfur-bearing phosphorous acid ester, (E2) acid phosphorous acid ester, (E3) acid phosphorous acid ester amine salt, and this is because their effects good with synthetic ester or grease base oil combination demonstration.
When flame retardant hydraulic oil composition of the present invention and component (E) blend, its content is preferably below 5 quality %, more preferably 2 quality %, and more preferably 1.5 quality %, based on composition total mass.The content that is greater than 5 quality % is not preferred, and this is because the thermostability of resulting composition can be poor, thereby causes that sludge forms.Otherwise, more than the content of component (E) is preferably 0.001 quality %, more preferably more than 0.005 quality %, more preferably more than 0.01 quality %, based on composition total mass.The content that is less than 0.001 quality % is not preferred, and this is because can not expect the improvement of attrition resistance and the anti-burn of resulting composition.
The use of phenol antioxidant can be given good oxidation-resistance and sludge inhibition to flame retardant hydraulic oil composition.Phenol antioxidant is not particularly limited, and this is because can use any alkylphenol compounds with antioxidant as lubricant.Yet the preferred Hinered phenols of phenol antioxidant, as alkylphenol and bis-phenol, preferably comprises those of thioether (sulfide) group and ester bond in molecule.
Flame retardant hydraulic oil composition of the present invention is with preferably below 5 quality %, more preferably 2 quality %, and more preferably the amount of 1.5 quality % comprises phenol antioxidant, based on composition total mass.The content that is greater than 5 quality % is not preferred, and this is because it causes that sludge forms.Otherwise oil compositions is with preferably more than 0.01 quality %, more than 0.05 quality %, more preferably amount more than 0.1 quality % comprises phenol antioxidant, based on composition total mass.The content that is less than 0.01 quality % neither be preferred, and this is because the antioxidant effect of resulting composition can be insufficient.
As mentioned above, in the present invention, at least one base oil that is selected from synthetic ester and grease is only with component (B) with further select free component (C), (D) and (E) more than one additive and phenol antioxidant blend of the group of composition, the flame retardant hydraulic oil composition of production oxidation-resistance thus and attrition resistance excellence.Yet, if necessary, in order further to improve these performances, described oil compositions can with any or suitable combination blend of the various additives of other antioxidant except above-mentioned antioxidant, rust-preventive agent, other metal passivator except above-mentioned metal passivator, other abrasion resisting agent, viscosity index improver, pour point reducer, defoamer, emulsion splitter, anti-demulcent and oiliness improver except above-mentioned abrasion resisting agent.
Except the component as amine antioxidants (C), can also be used in combination other amine antioxidants.The representative instance of amine antioxidants comprises the phenyl-a-naphthylamine being represented by formula (5) and the p being represented by formula (6), p '-dialkyl diphenylamine.
R wherein 11for hydrogen or there is the alkyl of 1-16 carbon atom.
R wherein 12and R 13independently of one another for thering is the straight or branched alkyl of 1-16 carbon atom.
The content of other amine antioxidants except component (C) is preferably 0.001-2.0 quality %, based on composition total mass.
The specific examples of rust-preventive agent comprises amino acid derivative; The partial ester of polyvalent alcohol; Ester is as lanolin fatty acid ester, alkyl succinic acid ester and alkenyl succinic acid ester; Sarkosine; Polyol partial esters is as sorbitan fatty acid esters; Metallic soap is as fatty acid metal salt, lanolin fatty acid metal-salt and oxidized petroleum waves metal-salt; Sulfonate is as calcium sulphonate and barium sulfonate; Oxidized petroleum waves; Amine; Phosphoric acid; And phosphoric acid salt.In these rust-preventive agent, preferably use amino acid derivative, this is because their good rust-proof effects.
The example of above-mentioned amino acid derivative comprises the compound being represented by following formula (7):
In above formula (7), A is the group being represented by formula (8) or (9), and B has the alkyl of 1-12 carbon atom or by the residue of the monocarboxylic ester of following formula (10) expression, R 14for thering is the alkyl of 4-12 carbon atom, and R 15for thering is the alkyl of 1-10 carbon atom:
R 17O-CO-R 16-(8)
R 19O-CO-R 18-CO-(9)
-C-CO-O-R 20(10)
Wherein, R 16for thering is the alkylidene group of 1-12 carbon atom, R 18for thering is the alkylidene group of 1-10 carbon atom, R 17and R 19be hydrogen or the alkyl with 1-10 carbon atom independently of one another, and R 20for thering is the alkyl of 1-10 carbon atom.
In the present invention, hydraulic fluid compositions can have any one or more compound that is selected from these rust-preventive agent with any amount blend.Yet, the preferred 0.001-2.0 quality of its content % conventionally, the total mass based on composition.
The specific examples of other metal passivator except component (D) comprises glyoxaline compound.In the present invention, hydraulic fluid compositions can have any one or more compound that is selected from these metal passivators with any amount blend.Yet its content is preferably 0.0001-1 quality %, the total mass based on composition conventionally.
The specific examples of viscosity index improver comprises overstepping one's bounds powder class viscosity index improver, as one or more are selected from the multipolymer of the monomer of various methacrylic esters or its hydrogenated compound, ethene-alpha-olefin copolymer (alpha-olefin can be propylene, 1-butylene or 1-amylene) or its hydrogenated compound, polyisobutene or its hydrogenated compound; The hydrogenated compound of vinylbenzene-diene and polyoxyethylene alkylphenyl ethene.In the present invention, hydraulic fluid compositions can have any one or more of these viscosity index improvers with any amount blend.Yet its content is preferably 0.01-10 quality %, the total mass based on composition conventionally.
The specific examples of pour point reducer comprises that one or more are selected from the multipolymer of the monomer of various acrylate and methacrylic ester or its hydrogenated compound.In the present invention, hydraulic fluid compositions can have any one or more of these pour point reducers with any amount blend.Yet its content is preferably 0.01-5 quality %, the total mass based on composition conventionally.
The specific examples of defoamer comprises that silicone is as dimethyl silscone and fluorosilicone.In the present invention, hydraulic fluid compositions can have any one or more of these defoamers with any amount blend.Yet its content is preferably 0.001-0.05 quality %, the total mass based on composition conventionally.
The example of emulsion splitter comprises polyether polyols, polyoxyalkylene alkyl ether, polyoxy alkylidene alkylamide and polyoxy alkylidene fatty acid ester etc.
The specific examples of anti-demulcent comprises polyol ester (full ester and partial ester).
The specific examples of oiliness improver comprises lipid acid, ester and alcohol.Conventionally, its content is preferably 0.01-0.5 quality %, the total mass based on hydraulic fluid compositions.
Embodiment
With reference to following examples and comparative example, will describe in more detail the present invention, but the invention is not restricted to this.According to following methods, measure and carry out flash-point and the various test of each composition.
[flash-point]
The flash-point of each composition is measured according to JIS J 2265 " crude oil and petroleum products-flashing test (Cleveland opening agar diffusion method) ".
[four-ball test]
According to ASTM D 2783-88 " lubricating fluid extreme pressure property is measured with standard test methods (four ball methods) ", at revolution, be 1200min -1, load for 294N, oil temperature be at 75 ℃, to carry out this test 1 hour, thereby measure the mean value of polishing scratch (scar) diameter (mm) of three balls of fixing.
[FZG Gear Experimentation]
According to ASTM D 5182, carry out this test.This test is 1500min at revolution -1lower and be to start at 90 ℃ in oil temperature, and make gear load drive 15 minutes by apply the specified weight of regulation in each stage simultaneously.The anti-burn of each oil of Phase Evaluation occurring at burn.The load stage of gear burn is defined as defective.
[wing pump test]
According to ASTM D 2882, carry out wing pump test 100 hours.In the weight of test fore-and-aft survey impeller and ring, thereby measure wear loss (mg).
[dry type TOST test]
In this experimental evidence JIS K 2514, " the TOST oxidation stability test " of regulation carries out.By 300mL sample oil being put into the container of regulation, then coil shape iron and copper catalyst to be put into wherein, oxidation stability test is carried out in the water-bath of then this container being put at the temperature that remains on 95 ℃ for 20 days.Do not make water.At duration of test, bit by bit taking out sample oil increases (mgKOH/g) and sludge amount (mg/50mL) (wherein the sample oil of specified quantitative filters with strainer, and the weight of resistates is scaled to the amount of every 50mL) to measure acid number.
[zinc dissolution test]
The JIS B 2301-1976 that puts into the beaker that comprises 200mL sample oil according to the screw-type of one of them regulation (screwed type) malleable iron pipe fitting is at 120 ℃, to carry out dip test 20 days in temperature.After test, the zinc amount (quality ppm) of stripping in measure sample oil is with the zinc stripping property of each sample oil relatively.
In embodiment and comparative example, component used is as follows.
(A) base oil
A1: the ester (kinematic viscosity at 40 ℃: 47.2mm of the mixed fatty acid of TriMethylolPropane(TMP) and oleic acid, sad and capric acid 2/ s, viscosity index: 180, percent unsaturation: 70 % by mole, acid number: 0.5)
A2: the ester (kinematic viscosity at 40 ℃: 45.2mm of the mixed fatty acid of TriMethylolPropane(TMP) and oleic acid, sad and capric acid 2/ s, viscosity index: 185, percent unsaturation: 90 % by mole, acid number: 2.0)
A3: the ester (kinematic viscosity at 40 ℃: 34.2mm of the mixed fatty acid of TriMethylolPropane(TMP) and oleic acid, sad and capric acid 2/ s, viscosity index: 130, percent unsaturation: 10 % by mole, acid number: 0.3)
A4: the ester (kinematic viscosity at 40 ℃: 66.2mm of the mixed fatty acid of tetramethylolmethane and oleic acid, sad and capric acid 2/ s, viscosity index: 160, percent unsaturation: 70 % by mole, acid number: 1.0)
(B) metal passivator
B1:2, two (the 2-ethylhexyl dithio)-1,3 of 5-, 4-thiadiazoles
B2:2, two (the n-hexyl dithio)-1,3 of 5-, 4-thiadiazoles
(C) antioxidant
C1: two (4-dimethylaminophenyl) methane
C2: alpha-naphthylamine
C3:4,4 '-methylene-bis (2,6 di t butyl phenol)
(D) nitrogen based metal deactivators
D1:N, two (2-the ethylhexyl)-4-methyl isophthalic acid H-benzotriazole-1-methylamines of N-
D2: benzotriazole
(E) abrasion resisting agent
E1:2-ethylhexyl acid phosphoric acid ester
E2: Tritolyl Phosphate
(F) other additive
E3: dehydrated sorbitol mono-fatty acid ester
As described in table 1 and 2, using wherein the ratio of unsaturated fatty acids in the lipid acid that forms ester is the comparative example 4 of the base oil of 10 % by mole, although its acid number is low, compares with embodiment 6, poorer aspect oxidative stability, particularly forms more sludge.
Use the comparative example 1-3 of the base oil A2 that its acid number is 2.0mgKOH/g, although the ratio of unsaturated fatty acids is 90 % by mole (these are high) in the lipid acid that forms ester, compare with 5 with embodiment 2, its zinc stripping quantity is larger.
Table 1
Table 2
utilizability in industry
Flame retardant hydraulic oil composition of the present invention is suitable for the application of using under the high-temperature and high-pressure conditions that fire occurrence risk is high having most, as the application for aluminum dipping form casting forcing machine or the operation of iron work equipment, and it is applicable to high-pressure pump, attrition resistance, sludge inhibition and particularly zinc leaching retention are excellent, make to use for a long time.Thereby said composition is industrial significantly useful.

Claims (3)

1. a flame retardant hydraulic oil composition, it comprises:
(A) by choosing, freely synthesized at least one base oil forming of the group of ester and composition, described synthetic ester and grease comprise more than 70 % by mole unsaturated fatty acidss and have acid number in the lipid acid that forms ester is below 1.0mgKOH/g, and
(B) the alkyl thiadiazoles of the amount of 0.01-0.6 quality %, based on composition total mass,
Wherein, described composition further comprises: (C) two (4-dialkylamino phenyl) methane that represented by following formula (1) of the amount of 0.001-1.0 quality %, based on composition total mass:
R wherein 1, R 2, R 3and R 4independently of one another for thering is the alkyl of 1-6 carbon atom.
2. flame retardant hydraulic oil composition according to claim 1, it further comprises:
(D) at least one triazole compounds of the group that the free triazole derivative of the choosing of the amount of 0.001-0.5 quality %, benzotriazole derivatives and tolytriazole derivative form, based on composition total mass.
3. flame retardant hydraulic oil composition according to claim 1 and 2, wherein said composition is for having the hydraulic efficiency system of zinc-plated pipeline or valve.
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