CN1764712A - Lubricant for water-miscible metal working oil - Google Patents
Lubricant for water-miscible metal working oil Download PDFInfo
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- CN1764712A CN1764712A CN 200480007938 CN200480007938A CN1764712A CN 1764712 A CN1764712 A CN 1764712A CN 200480007938 CN200480007938 CN 200480007938 CN 200480007938 A CN200480007938 A CN 200480007938A CN 1764712 A CN1764712 A CN 1764712A
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Abstract
A lubricant for water-miscible metal-working oils which comprises a polyether which is represented by the following general formula (1) and has an HLB of 6.1 to 16.0 and a weight-average molecular weight of 500 to 10,000; and a water-miscible metal working oil containing the lubricant. They have excellent lubricity in application not only to steel materials but to plastic metals such as aluminum. Even when diluted with water, they are stable and do not separate into phases. R<1>(((OCH2CH2CH2CH2)m/(OA<1>)n)(OA<2>)p-OH]q (1) (In the formula, R<1> represents a C1-24 residue; A<1> and A<2> each represents C2-4 alkylene; m is an integer of 1 or larger; n and p each is an integer of 0 or larger; q is an integer of 1 to 6; and ((OCH2CH2CH2CH2)m/(OA<1>)n) means random bonding when n is an integer of 1 or larger.
Description
Technical field
The present invention relates to lubricant for water-miscible metal working oil.In detail, the present invention relates to lubricant for water-miscible metal working oil, lubricant for water-miscible metal working oil composition and the water system metalworking fluid of polyethers.
Background technology
As machining oil, rolling oil, peel off oil, punching oil, forge oil, aluminium dish and cut off with water system metalworking fluids such as refrigerants with attrition process oil, silicon chip grinding oil, silicon chip, can enumerate solution-type, solvable type, emulsion-type etc.
The desired performance of these water system metalworking fluids be oilness, low whipability, water dilution stability (stability of the diluent during use behind the dilute with water), with other mineral oil be the separating of oil property of treated oil.
As lubricant used in the water system metalworking fluid, used polyethers in the past always.These polyethers are that what is called is known as pluronic type or the oxyethane of contrary pluronic type (counter Pluronic type) and the segmented copolymer (for example No. 4414121 specification sheetss of United States Patent (USP) and No. 4636321 specification sheetss of United States Patent (USP)) or the random copolymers of propylene oxide.
The polyoxyethylene chain that is contained in these polyethers is introduced in order to increase wetting ability and raising water dilution stability, and simultaneously in order to improve oilness, these polyethers have the molecular-weight average more than or equal to 800 usually.
Summary of the invention
The purpose of this invention is to provide a kind of lubricant for water-miscible metal working oil, it is not only to the oilness excellence of steel, and particularly the oilness to plastic metals such as aluminium is also excellent.
Another object of the present invention provides the lubricant for water-miscible metal working oil composition that contains above-mentioned lubricant and other additives and oilness excellence.
Another object of the present invention provides a kind of water system metal working oil, and it contains water and above-mentioned lubricant or above-mentioned lubricant compositions, its oilness, low whipability, water dilution stability and separating of oil property excellence.
According to the present invention, the lubricant for water-miscible metal working oil (following brief note is a lubricant) of the polyethers (E) by containing following general formula (1) expression is reached above-mentioned purpose, and wherein said polyethers has 6.1～16.0 HLB (hydrophilic-lipophilic balance value) and 500～10000 weight-average molecular weight.
R
1[{(OCH
2CH
2CH
2CH
2)
m/(OA
1)
n}(OA
2)
p-OH]
q (1)
In the formula, R
1Be that to have 1～6 hydroxyl and carbonatoms be residue after 1～24 compound is removed at least 1 hydroxyl; A
1Be that carbonatoms except that tetramethylene is 2～4 alkylidene groups; A
2Be that carbonatoms is 2～4 alkylidene group; M is the integer more than or equal to 1, average out to 1～120; N and p are 0 or more than or equal to 1 integer, (n+p) average out to 1～200, and n and p are not 0 simultaneously; Q represents 1～6 integer; N is during more than or equal to 1 integer, { (OCH
2CH
2CH
2CH
2)
m/ (OA
1)
nRepresent random combination.
The invention still further relates to the lubricant for water-miscible metal working oil composition that contains above-mentioned polyethers (E) and other additives.
The invention still further relates to the water system metalworking fluid that contains water and above-mentioned lubricant or above-mentioned lubricant compositions, wherein, described water system metalworking fluid contains the polyethers (E) of the 0.01 weight %～95 weight % that account for above-mentioned metalworking fluid weight.
In the general formula among the present invention (1), R
1Be that to have 1～6 hydroxyl and carbonatoms be that 1～24 compound is removed at least 1 hydroxyl, preferably removed residue behind whole hydroxyls.
As R
1, can enumerate the residue etc. of residue, carbohydrate and the derivative thereof of the residue of the residue of 1～6 yuan of Fatty Alcohol(C12-C14 and C12-C18) of straight chain, branched chain type or ester ring type, 1～6 yuan of phenols, 1～6 yuan of residue that contains aryl alcohols, 2 yuan of alcohol of hetero ring type.
As these pure and mild phenols, can enumerate following (e1)～(e5).
(e1) Fatty Alcohol(C12-C14 and C12-C18)
(e11) 1 yuan of alcohol
(e111) carbonatoms of straight chain or branched chain type is 1～24 the saturated 1 yuan of alcohol of aliphatics: methyl alcohol, ethanol, propyl alcohol (n-propyl alcohol, Virahol etc.), butanols, amylalcohol, hexanol, enanthol, octanol (n-Octanol, 2-Ethylhexyl Alcohol etc.), nonyl alcohol, decyl alcohol, hendecanol, dodecanol, tridecyl alcohol (n-tridecane alcohol, different tridecyl alcohol etc.), tetradecanol, pentadecylic alcohol, cetyl alcohol, heptadecanol, Stearyl alcohol, nonadecanol, eicosanol, heneicosane alcohol, V-1326, tricosanol, Tetracosyl alcohol etc.;
(e112) carbonatoms of straight chain or branched chain type is 3～24 the unsaturated 1 yuan of alcohol of aliphatics: alkenols (1-, 2-or different-vinylcarbinol, butenol, pentenol, hexenol, heptenol, octenol, nonenol, decenol, undecylenic alcohol, lanolin alcohol, tridecylene alcohol, tetradecene alcohol, 15 carbene alcohol, hexadecenol, heptadecene alcohol, oleyl alcohol, 19 carbene alcohol, gadoleyl alcohol, heneicosene alcohol, two lanolin alcohols, tricosene alcohol, tetracosa carbon enol etc.); Alkynyl alcohol (pentyne alcohol etc.).
(e113) carbonatoms of ester ring type is 1 yuan of alcohol of 4～24: cyclopentanol, hexalin etc.
(e12) 2 yuan of alcohol;
(e121) straight chain or branched chain type carbonatoms are 2 yuan of alcohol of aliphatics of 2～24: alkanediol (ethylene glycol, propylene glycol, 1,3-, 1,4-or 1,2-butyleneglycol, neopentyl glycol, 1,6-hexylene glycol, 1,2-or 1,7-heptanediol, 1,2-or 1,8-ethohexadiol, isobutyl glycol, 3-methyl isophthalic acid, 5-pentanediol, 2,2,4-trimethylammonium-1,3-pentanediol, 2,2-butyl-2-ethyl-1, ammediol, 2,5-dimethylhexane-2,5-glycol etc.);
(e122) carbonatoms of ester ring type is 2 yuan of alcohol of 4-18: cycloalkanes support glycol (1,4-cyclohexanediol, 1,4-cyclohexanedimethanol etc.), A Hydrogenated Bisphenol A class (Hydrogenated Bisphenol A, A Hydrogenated Bisphenol A F etc.) etc.;
(e13) 3～6 yuan of alcohol;
(e131) straight chain or branched chain type carbonatoms are 3 yuan of Fatty Alcohol(C12-C14 and C12-C18) of 3～24: glycerine, 1,2,3-trihydroxybutane, 1,2,3-penta triol, 2-methyl isophthalic acid, 2,3-glycerol, 2-methyl-2,3,4-trihydroxybutane, 2-ethyl-1,2,3-trihydroxybutane, 2,3,4-penta triol, 2,3,4-hexanetriol, 4-propyl group-3,4,5-triol in heptan, 2,4-dimethyl-2,3,4-penta triol, pentamethyl-glycerine, 1,2,4-trihydroxybutane, 1,2,4-penta triol, trimethylolethane, TriMethylolPropane(TMP) etc.
(e132) straight chain or branched chain type carbonatoms are 5～24 4～6 yuan of Fatty Alcohol(C12-C14 and C12-C18) and their intramolecularly or intermolecular dehydrate; Tetramethylolmethane, Dipentaerythritol, Sorbitol Powder, N.F,USP MANNITOL, 1,5-, 3,6-or 1,4-anhydro sorbitol, two glycerine etc.
(e2) phenols
(e21) carbonatoms is 1 yuan of phenols of 6～24; Phenol, alkylphenol (adjacent,, right-methylphenol, 2,3-, 2,4-, 2,5-, 3,4-or 3,5-xylenol, 2,6-xylenol, neighbour,, right-ethylphenol, align butylphenol, paraoctyl phenol, to nonylphenol etc.), single styryl phenol, monobenzyl phenol etc.
(e22) carbonatoms is 2～6 yuan of phenols of 6～24; 2 yuan of phenol (pyrocatechol, Resorcinol, Resorcinol etc.), 3～6 yuan of phenol (trihydroxybenzene, tetrahydroxy phenol, hexahydroxybenzene etc.), bisphenols (dihydroxyphenyl propane, Bisphenol F etc.) etc.
(e3) contain aryl alcohols
(e31) carbonatoms is 7～24 aralkyl alcohol; Phenylcarbinol, phenylethyl alcohol etc.
(e32) carbonatoms is 8～24 the substituent aralkyl alcohol of being with; Adjacent,, right-methylbenzyl alcohol, to n-butylbenzene ethanol etc.
(e4) 2 yuan of alcohol of hetero ring type: 1,4,3, the two anhydro sorbitols of 6-etc.
(e5) carbohydrate and derivative thereof; Sucrose, glucose, seminose, fructose, methyl glucoside etc.
Among these, preferably (e1), more preferably (e12), (e13), particularly preferably be carbonatoms in (e12) and be carbonatoms among 2～20 material, (e13) and be 3～18 material, especially preferred be (e121), (e131) and (e132) in carbonatoms be 3～6 material.
As R1, also preferred 2 yuan or 3 yuan of alcohol are removed the residue behind whole hydroxyls.
The carbonatoms of R1 surpasses at 24 o'clock, and wetting ability (E) is insufficient, so with (E) the dilution stability variation as the water system metalworking fluid water described later of lubricant use, produce separation phenomenon after the dilution sometimes.
A in the general formula (1)
1Be that carbonatoms except that tetramethylene is 2～4 alkylidene group, A
2Be that carbonatoms is 2～4 alkylidene group.
A
1And A
2Can be the same or different.A
1Comprise ethylidene, 1,2-or trimethylene, 1,2-or 2, there are a plurality of A in 3-butylidene, isobutylene
1The time, can share more than 2 kinds or 2 kinds of above-mentioned group.In addition, A
2Except comprising A
1In beyond the group enumerated, can also enumerate tetramethylene, have a plurality of A
2The time, also can share above-mentioned group more than 2 kinds or 2 kinds.
A
1And A
2In preferably ethylidene, propylene, 1, the 2-butylidene, more preferably ethylidene, propylene from improving the viewpoint of water dilution stability, particularly preferably are ethylidene.If A
1Or A
2At least its part is an ethylidene, and then the water-soluble of (E) is improved.General formula (1) is A preferably
2It is the compound of ethylidene.
M, n, p and q in the general formula (1) are selected from following ranges, and to make the weight-average molecular weight (following brief note is Mw) of (E) be 500～10000.
In addition, (E) among the present invention has molecular weight distribution usually, so m, n, p and q in the general formula (1) have multiple combination in above-mentioned scope, (E) can be the mixture of these combinations, also can be wherein a kind of.
M be more than or equal to 1, preferred 1～120, more preferably 1～30 integer, and to make on average be 1～120, preferred 1～30, more preferably 1～14.
N and p are 0 or more than or equal to 1, preferred 0 or 1～200, more preferably 0 or 1～40 integer, and make the average out to 1～200, preferred 2～57, more preferably 2～16 of (n+p).
N is 0 o'clock, and p is 1～200; P is 0 o'clock, and n is 1～200; N and p are not 0 simultaneously.
N on average is preferably 0～14, more preferably 2～14.P average preferred 0～44, more preferably 0～12, be preferably 0 especially.Preferred n of general formula (1) or p are 0.
From the viewpoint of water dilution stability, m/n is preferably 0.1～4, and more preferably 0.2～3.
From the viewpoint of water dilution stability, p/ (m+n) is preferably 0～3, is more preferably 0～0.2.
From the viewpoint of water dilution stability, m/ (m+n+p) is preferably 0.05～0.8, is more preferably 0.1～0.7.
Q is 1～6 integer, from the good viewpoint of water dilution stability, is preferably 2～6, more preferably 2～4, be preferably 2～3 especially.If q is greater than 6, oilness variation then.
(E) Mw (according to gel permeation chromatography) is 500～10000, is preferably 700～7000, is more preferably 800～6000, is preferably 1000～5000 especially.(E) Mw was less than 500 o'clock, and oilness is insufficient, and greater than 10000 o'clock, kinetic viscosity was too high, so in the operability variation of processes such as cooperation.
In addition, (the OCH of polyethers (E) Chinese style (1)
2CH
2CH
2CH
2) and (OA
1) must be random combination, not like this, (E) insufficient in cryogenic flowability, the operability variation of lubricant.
(E) HLB is 6.1～16.0, is preferably 6.3～13.8, is more preferably 8～13.HLB was less than 6.1 o'clock, and wetting ability (E) is insufficient, and water dilution stability variation produces sometimes after the dilution and separates.HLB is greater than 16.0 o'clock, the oilness variation.
In addition, HLB among the present invention is the HLB of little field method, can calculate according to the ratio of the value of the value of organic property of compound and inorganic nature, it is to calculate according to the method for calculation of " new surface active agents is crossed the threshold " (1996, Sanyo changes into industry (strain)) 197 pages of records.
Consider that from water dilution stability viewpoint the point covered with clouds of preferred (E) is high, consider that from the oilness viewpoint point covered with clouds (E) is preferably 5 ℃～60 ℃.Point covered with clouds among the present invention be with the 2 weight % aqueous solution of (E) heating and visual detection to the temperature of white casse.
(E) be liquid at normal temperature usually, preferred kinetic viscosity is 5mm at 40 ℃
2/ s～1000mm
2/ s.The mensuration of kinetic viscosity is measured (hereinafter the mensuration of kinetic viscosity is same method therewith) according to JIS K 2283.
Can make (E) by the following method.
Method (i): in the presence of catalyzer, making carbonatoms beyond tetrahydrofuran (THF) (following brief note is THF) and the THF is that 2～4 at least a kind oxirane (following brief note is AO) carries out random addition reaction on above-mentioned (e1)～(e5), then further as required at least a kind of carbonatoms of addition be 2～4 AO.
Method is (ii): the situation that for the n of general formula (1) is 0 polyethers, in the presence of catalyzer, only make the THF homopolymerization on (e1)～(e5), synthetic polyoxy tetramethylene glycol (following brief note is PTMG), then further in the presence of catalyzer at least a kind of carbonatoms of addition be 2～4 AO.
(i) and the addition reaction temperature (ii) be preferably 30 ℃～120 ℃, pressure and be preferably 0MPa～0.6MPa.The AO that uses in the addition reaction can enumerate oxyethane (EO), propylene oxide (PO), 1,2-butylene oxide ring, 2,3-butylene oxide ring, epoxy Trimethylmethane etc.
As catalyzer, can use existing known catalyzer, but the random addition reaction of THF/AO is different with the kind of preferred catalyzer in the AO addition reaction.
As the catalyzer of the random addition reaction of THF/AO, for example can enumerate following substances.
Lewis acid and their complex compound; BF
3, BCl
3, AlCl
3, FeCl
3, SnCl
3, BF
3-ether complexes, BF
3(following brief note is BF to-THF complex compound
3-THF) etc.
Protonic acid; H
2SO
4, HClO
4Deng.
Alkali-metal perchlorate; KClO
4, NaClO
4Deng.
The perchlorate of alkaline-earth metal; Ca (ClO
4)
2, Mg (ClO
4)
2Deng.
The perchlorate of the metal outside above-mentioned: Al (ClO
4)
3Deng.
Among these, preferred BF
3-ether complexes, BF
3-THF.
As the catalyzer of AO addition reaction, except that above-mentioned catalyzer, can also enumerate following material.The oxyhydroxide of basic metal or alkaline-earth metal; KOH, NaOH, CsOH, Ca (OH)
2Deng.
The oxide compound of basic metal or alkaline-earth metal; K
2O, CaO, BaO etc.Basic metal with and hydride; Na, K, NaH, KH etc.
Amine; Triethylamine, Trimethylamine 99 etc.
Preferred KOH, NaOH, CsOH, BF among these
3-Ether complexes, BF
3-THF.
Lubricant for water-miscible metal working oil composition of the present invention (hereinafter brief note is lubricant compositions) comprises above-mentioned (E) and other additive.
As other additive, can enumerate that to be selected from by carbonatoms be at least a material in the group formed of 8～22 aliphatic carboxylic acid and/or its salt (F), other polyethers (G), antioxidant (H), extreme-pressure additive (I), rust-preventive agent (J) and defoamer (K).
As (F), can enumerate following compound (F1)～(F3).
(F1) aliphatic monocarboxylic acid
(F11) representative examples of saturated aliphatic monocarboxylic acid, for example eight carbonic acid (sad, isocaprylic acid), n-nonanoic acid, ten carbonic acid (n-capric acid etc.), undecanoic acid, dodecylic acid (lauric acid etc.) etc., preferred eight carbonic acid, n-nonanoic acid, ten carbonic acid are more preferably sad, n-nonanoic acid.
(F12) unsaturated aliphatic monocarboxylic acid for example can be enumerated dodecenoic acid, tetradecenoic acid, Oleomyristic acid, palmitin oleic acid, oleic acid, erucic acid etc., preferred oleic acid.
(F2) aliphatic dicarboxylic acid, α for example, alpha, omega-dicarboxylic acid (for example nonane diacid, sebacic acid, dodecanedioic acid etc.), alkenyl succinic (for example octenyl succinic, dodecenyl succinic succsinic acid, 15 carbene base succsinic acids etc.), preference chain alkenyl succinic acid, particularly dodecenyl succinic succsinic acid, 15 carbene base succsinic acids.
(F3) the above-mentioned monocarboxylic acid or the salt of dicarboxylic acid
Can enumerate the salt etc. of the AO adducts of an alkali metal salt, alkaline earth salt, ammonium salt, aliphatics amine salt, fatty amine as salt.
Salt can be enumerated (F1) or (F2) be neutralized corrective after the agent neutralization.
As neutralizing agent, for example can enumerate alkali metal hydroxide (sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide etc.); The oxyhydroxide of alkaline-earth metal (calcium hydroxide, magnesium hydroxide etc.); Ammonia; Fatty amine [carbonatoms is 1～10 or is that the carbonatoms of 3～10 hetero ring type amine (morpholine etc.), silane alcohol base is 2～10 single, two or three silane alcohol base amine (monoethanolamine, trolamine, Yi Bingchunan, N-dimethylaminoethanol amine etc.) more than 10 alkyl or alkenyl amine (lauryl amine, oily enamine etc.), carbonatoms]; The AO adducts of these amine etc., and can use simultaneously among these more than 2 kinds or 2 kinds.
As the AO adducts of above-mentioned amine, the carbonatoms that for example can enumerate alkyl is 1～10 or more than the AO adducts of 10 alkylamine (methylamine, ethamine, diethylamine, propylamine, butylamine, hexahydroaniline, octylame etc.); The carbonatoms of alkylidene group is 2～18 or more than the AO adducts of 18 alkylene diamine (quadrol, propylene diamine, hexanediamine, octamethylenediamine, decamethylene diamine, dodecane diamines etc.); Total carbon atom number be 4～18 or more than 18, the carbonatoms of alkylidene group be 2～6 and the amine number be preferably AO adducts of 3～7 polyalkylene polyamine (many second polyamines such as Diethylenetriamine, three second tetramines, tetraethylene-pentamine, five second hexamines, six second, seven amine etc.) etc.The carbonatoms of AO is 2～4, for example can enumerate EO and PO (being preferably PO); The N atom of relative each amine, the adduction mole number of AO is preferably 0.5～2 mole, is more preferably 1～2 mole.0.5 in the time of～2 moles, the separating of oil property of water system metalworking fluid is good.
In the neutralizing agent, preferably fatty amine and AO adducts thereof, be more preferably the AO adducts, particularly preferably be the adducts of trolamine, 2～8 moles of PO of quadrol adduction, the adducts of the particularly adducts of 4 moles of adductions, the adducts of 3～8 moles of PO of Diethylenetriamine adduction, particularly 5 moles of adductions.
In addition, dicarboxylate also comprises single salt of dicarboxylic acid.
Lubricant compositions of the present invention contains (F), thus in the metalworking fluid bubble appears when having suppressed dilute with water, so lubricant compositions of the present invention is an ideal.
If carbonatoms (F) is more than or equal to 8, then lubricant compositions phenomenon that metal is got rusty easily is few, and, if carbonatoms smaller or equal to 22, the also less bubble that occurs during dilute with water then.
Consider from the viewpoint of oilness, monocarboxylic acid (salt) (hereinafter carboxylic acid (salt) expression carboxylic acid and/or its salt) and dicarboxylic acid (salt) are when being used simultaneously, the weight ratio of the two is preferably monocarboxylic acid (salt)/dicarboxylic acid (salt)=100～5/0～95, is more preferably 100～10/0～90.
In the mixture of carboxylic acid and carboxylate salt, the equivalence ratio of carboxylic acid/carboxylate salt is preferably 0～50/50～100, is more preferably 0～30/70～100.
Can directly add carboxylate salt when using carboxylate salt, also can add carboxylic acid and neutralizing agent respectively, in married operation, form carboxylate salt then.Preferably in married operation, carry out the neutral method.
As neutralizing agent, use be fatty amine or its AO adducts the time, the equivalence ratio of carboxylic acid/neutralizing agent is preferably 1/0.8～3, is more preferably 1/0.9～2; When carboxylic acid was excessive, excessive carboxylic acid not only had the effect of control foaming usually, also had the function of oiliness improver composition.
On the contrary, when neutralizing agent was excessive, excess fats family amine or its AO adducts had the function as the rust-preventive agent composition in the lubricant compositions, and neutralizing agent belongs to the content of rust-preventive agent described later (J) not in the content of (F).
In addition, when carrying out in the neutral method generating a small amount of neutralization in the married operation and generating water [preferably be less than (E) weight 5%], the water of generation also belongs to the composition of lubricant compositions of the present invention.
(F) content ratio of (E) is generally 0.03～10 in weight ratio relatively, is preferably 0.03～5.0, is more preferably 0.06～1.2, is preferably 0.1～1.0 especially.
(F) ratio was more than or equal to 0.03 o'clock, and processed metal is difficult for getting rusty, and oilness is improved.In addition, if ratio (F) smaller or equal to 5, then the separating of oil property of water system metalworking fluid is good.
In addition, do not contain the carboxylic acid that contains sulphur and/or nitrogen-atoms (salt) that uses as extreme-pressure additive described later among (F) among the present invention.
Other polyethers (G) makes the polyethers outside (E) of the present invention, can enumerate in the past the Mw that uses as lubricant and be 500～30000 polyethers.
As (G), comprise nonionic polyethers (G1) and ionic ether (G2).
As (G1); EO adducts, the carbonatoms that for example can enumerate polyoxyethylene glycol, carbonatoms and be 1～4 yuan of alcohol of 1～24 is the random or block adducts of the EO/PO of 1～4 yuan of alcohol of 1～24, EO/PO/EO segmented copolymer (for example, the what is called of putting down in writing in No. 4414121 specification sheetss of United States Patent (USP) and No. 4636321 specification sheetss of United States Patent (USP) " pluronic "), PO/EO/PO segmented copolymer (so-called " contrary pluronic "), these polyethers or (E) terminal alkoxide or terminal acylate etc.
As (G2), can enumerate the anionites of above-mentioned (G1), for example the phosphoric acid ester (material of putting down in writing in No. 3945930 specification sheets of United States Patent (USP)) of the sulfuric ester of polyepoxide (material of putting down in writing in No. 3950258 specification sheets of United States Patent (USP)), polyepoxide, the carboxyl etherate of polyepoxide etc.
About the addition of (G), preferably, be more preferably smaller or equal to 60%, especially preferably smaller or equal to 30% smaller or equal to 90% (hereinafter do not have when special instruction, % represents weight %) of (E) weight in the lubricant compositions.
As antioxidant (H), can enumerate phenol and be antioxidant (for example 2,4 dimethyl 6 tert butyl phenol, 4,4-fourth fork base two (6-tertiary butyl cresols) etc.); Aromatic amine is antioxidant (for example phenyl-, a phenyl-etc.); Dialkyl group (carbonatoms is 1～36) zinc dithiophosphate; Diallyl (carbonatoms is 2～36) zinc dithiophosphate; Organic sulfide; Organic selenide etc.About the addition of antioxidant (H), preferably, be more preferably 0.0001%～1% smaller or equal to 2% of polyethers in the lubricant compositions (E) weight.
As extreme-pressure additive (I), can enumerate lead soap (lead naphthenate etc.); Sulfide (sulfide aliphatic acid such as sulfuration oleic acid etc., sulfide aliphatic acid ester, sulfuration Sperm whale oil, sulfuration terpenes, dibenzyl disulfide, carbonatoms are that the amine salt of 8～24 alkylthio propionic acid or an alkali metal salt, carbonatoms are the amine salt of 8～24 alkyl thiol oxyacetic acid or an alkali metal salt etc.); Muriate (chlorination stearic acid, clorafin, xanthogenic acid chloro petroleum naphtha etc.); Phosphide (Tritolyl Phosphate, tributyl phosphate, tricresyl phosphite, normal-butyl n-octyl phosphonic acid ester, di-n-butyl DHP dihexylphosphoric acid ester, di-n-butyl phenyl phosphate ester, phosphoramidic acid dibutylester, amine dibutylphosphoric acid ester etc.).The addition of extreme-pressure additive (I) preferably is less than or equal to 10% of polyethers in the lubricant compositions (E) weight, is more preferably smaller or equal to 5%.
As rust-preventive agent (J), for example can enumerate carbonatoms and be 14～36 aliphatic amide (palmitin acid amides, palmitic amide, oleylamide etc.); Carbonatoms is 6～36 alkenyl succinic diamide (octenyl succinic diamide, decene base succinic diamide, 15 carbene base succinic diamides, octenyl succinic diamide etc.); The nitrous acid cyclo-hexylamine; Benzotriazole; Sulfydryl phenylpropyl alcohol thiazole; N, N '-two salicylidenes-1; Alizarin; The aliphatic amide of enumerating as above-mentioned neutralizing agent with and AO adducts etc.
(J) preferred fat amine AO adducts in particularly preferably is the adducts of the adducts of thanomin, 2～8 moles of PO of quadrol adduction, particularly 4 moles of adductions, the adducts of 3～8 moles of PO of Diethylenetriamine adduction, particularly the adducts of 5 moles of adductions.
In addition, carbonatoms is that 14～36 aliphatics carboxylic acid amides and carbonatoms are that 6～36 alkenyl succinic diamide also has the function as the oiliness activator.
The addition of rust-preventive agent (J) preferably smaller or equal to 50% of polyethers in the lubricant compositions (E) weight, is more preferably 1%～40%; (J) also comprise aforementioned excess fats family amine in the amount.
As defoamer (K), can enumerate organopolysiloxane (for example polydimethylsiloxane etc.) etc.The addition of disappearance infusion (K) preferably smaller or equal to the 1000ppm of polyethers in the lubricant compositions (E) weight, is more preferably 10ppm～500ppm.
For lubricant compositions of the present invention, preferably contain carbonatoms and be 8～22 aliphatic carboxylic acid and/or its salt (F) additive as other.In addition, for lubricant compositions of the present invention, preferably contain at least a kind of material being selected from the group of forming by antioxidant, extreme-pressure additive, rust-preventive agent and defoamer as other additives.
Lubricant compositions of the present invention does not preferably contain hydrocarbon system oil (mineral oil and animals and plants wet goods).Because do not contain hydrocarbon system oil, so even add water, it is preserved for a long time as the water system metalworking fluid also seldom has because of the corruption deterioration, so be preferred.
Based on the weight of lubricant compositions of the present invention, percentage (E)/(F)/(G)～(K) (%) normally 10～99/1～90/0～50, preferred 50～90/9～80/1～30, be more preferably 60～90/9～30/1～10.
Water system metalworking fluid of the present invention contains water and above-mentioned lubricant or lubricant compositions, and polyethers (E) be generally the water system metalworking fluid weight 0.01%～95%, preferred 0.2%～90%, be more preferably 10%～85%, preferred especially 30%～60%.
In addition, based on the weight of water system metalworking fluid, water system metalworking fluid of the present invention contains 0.01%～99% usually, and is preferred 0.3%～95%, is more preferably 12%～88%, the lubricant compositions of preferred especially 30%～80% concentration.
During in the carrying of water system metalworking fluid or by keeping, when perhaps oil, punching oil, rolling oil, forge oil use were peeled off in the conduct of water system metalworking fluid, the concentration of (E) was preferably 5%～90% in the water system metalworking fluid, is more preferably 10%～60%.
In addition, the water system metalworking fluid as machining oil, grind and cut oil, aluminium disk and cut off when using with refrigerant with attrition process oil, silicon chip grinding oil and silicon chip, preferred especially water system metalworking fluid not only contains (E), also contain (F), and preferably water dilutes before will using, the weight concentration that makes (E) is 0.5%～3% particularly 1%～2%, and concentration (F) is 0.1%～2%, particularly 0.2～2%.
Water system metalworking fluid of the present invention can be by making above-mentioned lubricant or direct the mixing with water of lubricant compositions, also can adopt additive method, for example respectively each composition of lubricant compositions is mixed with water, and order by merging is not particularly limited.
Water system metalworking fluid of the present invention can be the arbitrary form of solution-type, solvable type or emulsion-type, considers from the viewpoint of the secular appearance stability of water system metalworking fluid, is preferably solution-type or solvable type.
When solution-type of the present invention or solvable shaped metal treated oil use as machining oil, can be by supplying with above-mentioned diluent and use to being cut metal and cutting tool.
Water system metalworking fluid of the present invention is not only to the oilness excellence of steel and iron, and also excellent to the oilness of plastic metals such as aluminium, aluminium alloy.To be water system metalworking fluid of the present invention use with oil as the processing of aluminium, aluminium alloy, iron and/or steel is ideal.
Embodiment
Below, specifically describe the present invention with embodiment, but the present invention is not subjected to the restriction of these embodiment.Hereinafter " part " expression " weight part ".
(1) condition determination of Mw
The LC8120 that determining instrument: Dong Caoshe produces
Elutriant: THF
Flow velocity: 0.6 (ml/ branch)
Post: TSKgel Super H4000, H3000, H2000
Reference material: polyoxyethylene glycol
(2) measuring method of point covered with clouds
With the 2 weight % aqueous solution heating of (E), measure temperature according to the visual finding white casse.Temperature more than point covered with clouds, the aqueous solution is transparent, and point covered with clouds is high more, and the water dilution stability is good more.
(3) method of calculation of HLB
(the method method of calculation that Sanyo in 1996 changes into 197 pages of records of industry (Co., Ltd.) are calculated HLB according to " new surface active agents cross the threshold ".
Embodiment 1～4,7 and comparative example 1
Have heating-cooling device, whipping appts, withstand voltage dropping funnel, nitrogen exchange pipe and wet bulb thermometer and scribbling in the stainless steel autoclave of glass coating, adding Fatty Alcohol(C12-C14 and C12-C18) and the THF and the BF of the umber [in the bracket is mol ratio] of table 1 or table 2 record
3-THF kept 35 ℃～50 ℃, dripped the EO of the umber [expression mol ratio in the bracket] of table 1 and table 2 record from withstand voltage dropping funnel with 10 hours times.Thereafter, 50 ℃ of slakings 5 hours, cooling then.Further add the 48 weight %NaOH aqueous solution of table 1 and table 2 record umber, after this catalyst neutralisation, under the decompression smaller or equal to 30mmHg, removes low volatilization composition with 120 ℃ of distillations.Thereafter, use adsorption treatment agent (" キ ヨ one ワ one De 600 " and " キ ヨ one ワ one De 1000 " that consonance chemical industry society produces), the adsorption treatment catalyst residue, filter then, dehydration under reduced pressure (130 ℃, smaller or equal to 30mmHg, 1 hour, down with) after, obtain polyethers (E1)～(E4) and (E7) and polyethers (E ' 1) relatively, with these lubricants as embodiment 1～7 and comparative example 1.
Embodiment 5,6 and 8
Except that the addition of THF and EO is the amount of table 1 or table 2 record, similarly to Example 1, polyethers is made in random addition reaction by AO, after refining, in autoclave similarly to Example 1, add this polyethers and the potassium hydroxide of the amount of table 1 record, under reduced pressure after the dehydration, with 10 hours time, from the EO of withstand voltage dropping funnel at the umber [being mol ratio in the bracket] of 130 ℃ of dropping tables 1 record.Further 130 ℃ slakings 5 hour, then cool off thereafter.With similarly to Example 1 method make with extra care, obtain polyethers (E5), (E6) and (E8), with these lubricants as embodiment 5,6 and 8 thereafter.
Embodiment 9
Add (1.0 moles of 1000 parts of PTMG; " PTMG1000 " Mitsubishi Chemical society produces; Mw is approximately 1000 PTMG) and 0.4 part of KOH.After decompression is dewatered down,, drip 1012 parts of (23 moles) EO from withstand voltage dropping funnel at 150 ℃ with 10 hours time.Use 10 hours time, to pressure equilibrium, cool off 150 ℃ of slakings thereafter., use with embodiment 1 identical method refining, obtain 23 moles of EO block adductss (E9) of 1950 parts of PTMG-1000, with this lubricant as embodiment 9 thereafter.
Comparative example 2
In autoclave similarly to Example 1, add 76 parts of propylene glycol (1 mole) and 4.0 parts of KOH, after decompression is dewatered down,, drip 1682 parts of PO (29 moles) in 105 ℃ from withstand voltage dropping funnel with 10 hours time.With 8 hour time, 130 ℃ slakings to pressure equilibrium, with 8 hour times from withstand voltage dropping funnel in 130 ℃ drip 1188 part EOs (27 mole) thereafter.Thereafter synthermal slaking 5 hours to pressure equilibrium, cooling.Then, refining with similarly to Example 1 method, obtain 29 moles of PO of 2800 parts of propylene glycol and the block adducts (E ' 2) of 27 moles of EO, with this lubricant of 2 as a comparative example.
(E1)～(E9) and output, Mw, HLB and the point covered with clouds of (E ' 1)～(E ' 2) see Table 1 and table 2.
Table 1
| Embodiment | |||||||
| 1 | 2 | 3 | 4 | 5 | 6 | ||
| The name of an article of polyethers | E1 | E2 | E3 | E4 | E5 | E6 | |
| Random or block AO addition reaction | 1, the 4-butyleneglycol | 90 (1) | 90 (1) | 90 (1) | 90 (1) | 90 (1) | 90 (1) |
| Glycerine | |||||||
| Propylene glycol | |||||||
| THF | 216 (3) | 1008 (14) | 792 (11) | 504 (7) | 1512 (21) | 2016 (28) | |
| EO | 176 (4) | 880 (20) | 1100 (25) | 1408 (32) | 440 (10) | 440 (10) | |
| PO | |||||||
| BF 3-THF | 3.2 | 12.8 | 12.8 | 12.8 | 12.8 | 17.0 | |
| The 48%NaOH aqueous solution | 1.9 | 7.4 | 7.4 | 7.4 | 7.4 | 9.8 | |
| The 2nd stage A O addition reaction | EO | 220 (5) | 220 (5) | ||||
| KOH | 1.2 | 1.4 | |||||
| Output (part) | 460 | 1880 | 1883 | 1902 | 2150 | 2628 | |
| Mw | 500 | 2150 | 2180 | 2200 | 2490 | 3040 | |
| HLB | 11.7 | 9.9 | 11.7 | 14.3 | 7.4 | 6.5 | |
| Point covered with clouds (℃) | 21 | 21 | 34 | 46 | 13 | 10 | |
Table 2
| Embodiment | Comparative example | |||||
| 7 | 8 | 9 | 1 | 2 | ||
| The name of an article of polyethers | E7 | E8 | E9 | E1 | E2 | |
| Random or block AO addition reaction | 1, the 4-butyleneglycol | 90 (1) | 90 (1.0) | |||
| Glycerine | 92 (1) | |||||
| Propylene glycol | 76 (1) | |||||
| THF | 1152 (16) | 1512 (21) | 1000 parts of PTMG-1000 (1) | 1512 (21) | ||
| EO | 1760 (40) | 1760 (40) | 352 (8) | 1188 (27) | ||
| PO | 1682 (29) | |||||
| BF 3-TH F | 19.1 | 12.8 | 12.8 | |||
| The 48%Na OH aqueous solution | 11.0 | 7.4 | 7.4 | |||
| The 2nd stage A O addition reaction | EO | 5720 (130) | 1012 (23) | |||
| KOH | 5.6 | 0.4 | ||||
| Output (part) | 2850 | 8630 | 1950 | 1860 | 2800 | |
| Mw | 3300 | 9990 | 2100 | 2150 | 3240 | |
| HLB | 12.4 | 15.6 | 10.7 | 5.9 | 10.5 | |
| Point covered with clouds (℃) | 39 | ＞70 | 25 | Do not have | 58 | |
Embodiment 10～21, comparative example 3～6
After the composition outside cooperation ratio (part) mixing water shown in the following table 3, mix to obtain lubricating oil composition fully in room temperature.
In addition, trolamine, 4 moles of quadrols (PO), 5 moles of neutralizing agents as carboxylic acid of two quadrols (PO) use, and excessive part is rust-preventive agent (J).
The water that further adds umber shown in the table 3 in these lubricating oil compositions mixes fully and obtains the water system metalworking fluid of embodiment 10～21 and comparative example 3～6 in room temperature.The outward appearance of these metalworking fluids sees Table 3.
The metewand of outward appearance is as follows.
Zero: transparent even
*: be divided into two-layer
Table 3
| Embodiment | Comparative example | ||||||||||||||||
| 10 | 11 | 12 | 13 | 14 | 15 | 16 | 17 | 18 | 19 | 20 | 21 | 3 | 4 | 5 | 6 | ||
| Polyethers (E) | E1 | 40 | |||||||||||||||
| E2 | 40 | 40 | 40 | 40 | |||||||||||||
| E3 | 40 | ||||||||||||||||
| E4 | 40 | ||||||||||||||||
| E5 | 40 | ||||||||||||||||
| E6 | 40 | ||||||||||||||||
| E7 | 40 | ||||||||||||||||
| E8 | 40 | ||||||||||||||||
| E9 | 40 | ||||||||||||||||
| E1 | 40 | 40 | |||||||||||||||
| E2 | 40 | 40 | |||||||||||||||
| (F) + (J) | Sad | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 30 | ||
| Sebacic acid | 4 | 4 | |||||||||||||||
| Trolamine | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | |||
| 4 moles of quadrols (PO) | 10 | ||||||||||||||||
| 5 moles of two quadrols (PO) | 20 | ||||||||||||||||
| Water | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 51 | 45 | 35 | 50 | 50 | 50 | 25 | |
| Outward appearance | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | × | ○ | ○ | ○ | |
By following measuring method the water dilution stability of these water system metalworking fluids and the evaluation result of oilness are seen Table 4.
The modulation of＜experimental liquid 〉
Further water dilutes 20 times with the water system metalworking fluid of embodiment and comparative example, is modulated into experimental liquid.
＜water dilution stability 〉
With pack into the glass band plug graduated cylinder of 100mL of experimental liquid, 25 ℃ place 1 after, look the judgement outward appearance with following standard mesh.
Zero: transparent even
△: muddiness is arranged slightly
*: be divided into two-layer
＜oilness 〉
Use friction abrasion tester (the レ ス カ society production of ball dish-type (ball on disk), Off リ Network シ ヨ Application プ レ one ヤ one FPR-2000), frictional coefficient and the oil film interruption that contacts the experimental liquid under (load 100g) by measuring steel ball with the point of planar steel plate and aluminium sheet estimated.
Test conditions is as follows.
Revolution: 20rpm
The radius of gyration: 15mm
Temperature: 30 ℃
Time: 5 minutes
Frictional coefficient (μ): 5 minutes mean value
In addition, observe the change of the μ in minute, the metewand that oil film is interrupted is judged with the big or small following of the change width of cloth of μ.
Zero: the amplitude of fluctuation of μ＜0.025
The amplitude of fluctuation of △: μ is 0.025～0.040
*: the change width of cloth＞0.040 of μ
Table 4
| The metalworking fluid that uses | The outward appearance of water diluent | Oilness to steel plate | Oilness to aluminium sheet | |||
| Oil film is interrupted | Frictional coefficient | Oil film is interrupted | Frictional coefficient | |||
| Embodiment | 10 | ○ | ○ | 0.105 | ○ | 0.090 |
| 11 | ○ | ○ | 0.093 | ○ | 0.073 | |
| 12 | ○ | ○ | 0.091 | ○ | 0.074 | |
| 13 | ○ | ○ | 0.097 | ○ | 0.080 | |
| 14 | ○ | ○ | 0.100 | ○ | 0.085 | |
| 15 | ○ | ○ | 0.102 | ○ | 0.086 | |
| 16 | ○ | ○ | 0.095 | ○ | 0.075 | |
| 17 | ○ | ○ | 0.120 | ○ | 0.100 | |
| 18 | ○ | ○ | 0.105 | ○ | 0.095 | |
| 19 | ○ | ○ | 0.097 | ○ | 0.065 | |
| 20 | ○ | ○ | 0.091 | ○ | 0.063 | |
| 21 | ○ | ○ | 0.090 | ○ | 0.065 | |
| Comparative example | 3 | × | ○ | 0.130 | ○ | 0.110 |
| 4 | ○ | × | 0.170 | × | 0.136 | |
| 5 | ○ | × | 0.139 | × | 0.175 | |
| 6 | ○ | × | 0.210 | × | 0.160 | |
Utilizability on the industry
Water system metal of the present invention refuels with lubricator as cutting oil, rolling oil, it is very effective to peel off the lubricant that oil, punching oil, forge oil, aluminium dish uses with water system Metalworking fluids such as cooling agents with attrition process oil, silicon chip grinding oil, silicon chip cut-out.
Claims (13)
1. lubricant for water-miscible metal working oil, it contains following general formula (1) expression polyethers: R
1[{ (OCH
2CH
2CH
2CH
2)
m/ (OA
1)
n(OA
2)
p-OH]
q(1) in the formula, R
1Be that to have 1～6 hydroxyl and carbonatoms be residue after 1～24 compound is removed at least 1 hydroxyl; A
1Be that carbonatoms except that tetramethylene is 2～4 alkylidene group; A
2Be that carbonatoms is 2～4 alkylidene group; M is the integer more than or equal to 1, average out to 1～120; N and p are 0 or more than or equal to 1 integer, (n+p) average out to 1～200, and n and p are not 0 simultaneously; Q represents 1～6 integer; N is during more than or equal to 1 integer, { (OCH
2CH
2CH
2CH
2)
m/ (OA
1)
nRepresent random combination; Described polyethers has 6.1～16.0 HLB and 500～10000 weight-average molecular weight.
2. lubricant as claimed in claim 1, wherein, n or p in the general formula (1) are 0.
3. lubricant as claimed in claim 1 or 2, wherein, R in the general formula (1)
1It is the residue after 2 yuan or 3 yuan of alcohol are removed whole hydroxyls.
4. as each described lubricant of claim 1～3, wherein, A in the general formula (1)
2It is ethylidene.
5. as each described lubricant of claim 1～4, wherein, in the general formula (1), m/ (m+n+p) is 0.05～0.8.
6. lubricant for water-miscible metal working oil composition, it contains polyethers (E) and other additive of claim 1～5 described in each.
7. lubricant compositions as claimed in claim 6, wherein, described other additives are that carbonatoms is 8～22 aliphatic carboxylic acid and/or its salt (F).
8. lubricant compositions as claimed in claim 7 wherein, (F)/(E) counts 0.03～5.0 with weight ratio.
9. as each described lubricant compositions of claim 6～8, wherein, contain be selected from the group of forming by antioxidant, extreme-pressure additive, rust-preventive agent and defoamer at least a additive as other additives.
10. as each described lubricant compositions of claim 6～9, wherein, do not contain hydrocarbon system oil as other additives.
11. water system metalworking fluid, it contains water, each described lubricant of claim 1～5, perhaps contain each described lubricant compositions of water and claim 6～10, wherein, contain the polyethers (E) of the 0.01 weight %～95 weight % that account for described metalworking fluid.
12. water system metalworking fluid as claimed in claim 11, it is the water system metalworking fluid of solution-type or solvable type.
13. as claim 11 or 12 described water system metalworking fluids, it is used for the processing of aluminium, aluminium alloy, iron and/or steel.
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| JP080194/2003 | 2003-03-24 | ||
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| JP397504/2003 | 2003-11-27 |
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| CN102348788A (en) * | 2009-03-11 | 2012-02-08 | 出光兴产株式会社 | Metalworking fluid |
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| CN1057478A (en) * | 1990-06-22 | 1992-01-01 | 薛志纯 | Metal working fluid |
| CN1019814B (en) * | 1990-07-25 | 1992-12-30 | 齐齐哈尔轻工学院有机合成研究所 | A kind of metal cool-press lubricating agent |
| US5494596A (en) * | 1995-01-13 | 1996-02-27 | Minnesota Mining And Manufacturing Company | Data storage device with improved roller lubricant characterized by stable viscosity over wide range of temperatures |
| JP3953793B2 (en) * | 2000-11-30 | 2007-08-08 | 三洋化成工業株式会社 | lubricant |
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