CN104927982A - Emulsified cutting liquid composition - Google Patents
Emulsified cutting liquid composition Download PDFInfo
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Abstract
The invention provides an emulsified cutting liquid composition, a method for improving the stability of hard-water-resistant performance of the emulsified cutting liquid composition, and a method for improving the antirust property of the emulsified cutting liquid composition. The emulsified cutting liquid composition comprises a Mannich base, an emulsifier, water, and the balance being lubricant base oil; wherein the Mannich base is prepared by the following steps: (1) in the presence of an alkylation reaction catalyst, reacting phenol and/or mono-o-alkyl phenol with polyolefin, and collecting the alkylation products; (2) carrying out Mannich reactions among the alkylation products obtained in the step (1), polyethylene-polyamine, and aldehyde to obtain an intermediate; (3) carrying out secondary Mannich reactions among the intermediate obtained in the step (2), p-hydroxyl diphenylamine derivatives and aldehyde, and collecting the finally-obtained Mannich base. The provided emulsified cutting liquid composition has an excellent stable hard-water-resistant property and antirust performance, and can be used in the areas where the water hardness is high.
Description
Technical field
The present invention relates to a kind of emulsion cutting fluid composite, particularly relate to the emulsion cutting fluid composite of anti-hard water stability and high rust resistance.
Background technology
The performance of cutting fluid directly affects the quality of machining, efficiency and cost.Aqueous cutting fluid came out the forties in 20th century, and up to the present, water base fluid has had tremendous development in the application in the field of cutting.In water-base cutting fluid, emulsion cutting fluid has good oilness and cooling, is the maximum and ideal metal working fluid of current consumption.In metal cutting process, cutting fluid mainly plays lubrication and cooling effect, takes into account antirust, cleaning and antimicrobial properties etc. simultaneously.When using at the scene, emulsion cutting fluid needs the water with more than 90% to dilute usually.If the hardness of diluent use water water quality is comparatively large, easily causes diluent visibility to be deteriorated, can react with the functional additive of system time serious, make it separate out, condense and precipitate.
Numerous reports and patent documentation is had both at home and abroad about water-base cutting fluid composition.Patent CN101104831A reports a kind of microemulsified stainless steel coolant.This cutting fluid is made up of the additives such as alkylphenol polyoxyethylene or fatty alcohol-polyoxyethylene ether nonionogenic tenside, clorafin, oleic acid, trolamine and base oil, water, is exclusively used in the processing of stainless cutting fluid.Patent CN101560430A reports a kind of fully synthetic cutting fluid, adopts tensio-active agent, polyoxyethylene glycol, borax, sterilant, pH value regulator and balance deionized water to be in harmonious proportion and forms, solve the problem that existing fully synthetic cutting fluid cobalt element leaches.Patent JP2007186537 discloses a kind of processing cast iron and non-discoloring high-performance water base cutting fluid, is made up of saturated fatty acid, unsaturated fatty acids, di-carboxylic acid, fatty acid metal salt etc.Patent CN102876439A discloses a kind of cutting fluid, is made up of diethanolamine, monoethanolamine, succinic acid, borate, glycerine, emulsifying agent, rust-preventive agent etc.US5725612 reports a kind of Mannich base and manufacture method thereof, and the alkyl ortho-cresol that this Mannich base is replaced by alkyl and aldehyde, amine react manufacture and obtains, and can suppress the generation of engine deposits.
Water-base cutting fluid is in an increasingly wide range of applications at current mechanical processing industry.Cutting fluid is as a kind of special mechanical processing process medium, and due to the impact of self compositing characteristic and extraneous factor, it in use may occur some common problems, such as anti-hard water or soap rendezvous problem.Having a large amount of calcium ions and magnesium ions in water-base cutting fluid one side water, is mostly can add lipid acid in Method of Emulsified Cutting Fluid on the other hand, and the two is easy to form fatty acid soaps.The formation of fatty acid soaps can't have bad impact to the performance of cutting fluid, and the gathering of soap is only the key issue needing to solve.Under hard water situation, especially long-time moisturizing can form a large amount of soaps, and fatty acid soaps occurs to assemble and then can produce certain negative impact to cutting fluid and mechanical processing process, likely causes emulsion instability, causes concentrated solution consumption to increase.When soap is bonded together with foam, metal-powder, assorted wet goods composition in lathe or in central liquid supply system, when forming scum silica frost or even thick substances, the problem brought can be more, they are floating or be deposited in working fluid, not only filtering system is impacted, cause blocking, the consumption of filter paper increases, on-site sanitation situation is poor, and remain in cutter, measurer and transmission system and can cause working accuracy problem.These problems are all had higher requirement to the anti-hard water stability of emulsion cutting fluid self.
Summary of the invention
The invention provides a kind of emulsion cutting fluid composite and improve the method for the anti-hard water stability of emulsion cutting fluid, the method for raising emulsion cutting fluid rustless property.
Emulsion cutting fluid composite of the present invention comprises the lubricant base of Mannich base, emulsifying agent, water and surplus, and the preparation method of wherein said Mannich base comprises:
(1) under catalyst for alkylation reaction exists, phenol and/or single ortho alkyl phenol and polyolefine are reacted, collect alkylate;
(2) alkylate step (1) obtained and polyamines polyene, aldehyde generation Mannich reaction, obtain intermediate product;
(3) intermediate product of step (2) and p-hydroxydiphenylamine derivative, aldehyde be there is second time Mannich reaction, collect and obtain final Mannich base.
In step (1), described polyolefine is by ethene, propylene, C
4-C
10alpha-olefin is polymerized separately or copolymerization and the polyolefine obtained, described C
4-C
10alpha-olefin can select in n-butene, iso-butylene, positive amylene, n-hexylene, positive octene and positive decene one or more, preferred polyisobutene, described polyolefinic number-average molecular weight is 300-3000, preferred 500-2000, more preferably 500-1500.
Described single ortho alkyl phenol preferred alkyl carbonatoms is single ortho alkyl phenol of 1-6, most preferably ortho-cresol.
Described catalyst for alkylation reaction is selected from Lewis acid catalyst, one or more of preferred aluminum chloride, boron trifluoride, tin tetrachloride, titanium tetrabromide, boron trifluoride phenol, boron trifluoride alcohol complex and boron trifluoride ether complex, most preferably boron trifluoride ethyl ether complex and/or boron trifluoride methanol.
Mol ratio between described polyolefine, phenol and/or single ortho alkyl phenol, catalyzer is 1:1-3:0.1-0.5, preferred 1:1.5-3:0.1-0.4, most preferably 1:1.5-3:0.2-0.4.
Reaction times is 0.5h-10h, preferred 1h-8h, most preferably 3h-5h.
Temperature of reaction is 0 DEG C-200 DEG C, preferably 10 DEG C-150 DEG C, most preferably 20 DEG C-100 DEG C.
Need to add solvent in the reaction of step (1), also can add solvent.Described solvent is selected from the hydro carbons of boiling point between 60 DEG C-120 DEG C, such as normal hexane, normal heptane, 60-90 sherwood oil, 90-120 sherwood oil.Described solvent and described polyolefinic mass ratio are 0.5:1-2:1, preferred 0.7:1-1.5:1, most preferably 0.9:1-1.3:1.After step (1) adds solvent participation reaction, by distil process except desolventizing.
In step (2), described polyamines polyene has following general formula:
H
2N(CH
2)
y[(NH(CH
2)
y]
xNH
2
Wherein x is the integer of 0-10, and y is integer 2 or 3.One or more in the preferred diethylenetriamine of described polyamines polyene, triethylene tetramine, tetraethylene pentamine, five ethene hexamines, six ethene seven amine, seven ethene eight amine, eight ethene nine amine, nine ethene ten amine and ten ethene undecylamines, most preferably tetraethylene pentamine.Polyamines polyene can react preparation by ammonia and alkylene dihalide such as dichloro alkanes.
The preferred formaldehyde of described aldehyde, acetaldehyde, C
3-C
7alkanoic, one or more most preferably in paraformaldehyde, paraformaldehyde and formaldehyde.
The alkylate that described step (1) obtains, the mol ratio between described polyamines polyene and described aldehyde are 1:0.3-3:0.1-3.5, preferred 1:0.4-2:0.2-2.5, most preferably 1:0.5-1.5:0.3-2.
The temperature of described Mannich reaction is 50 DEG C-200 DEG C, preferably 60 DEG C-150 DEG C, most preferably 80 DEG C-130 DEG C.
The time of described Mannich reaction is 1h-10h, preferred 2h-8h, most preferably 3h-6h.
Solvent and/or thinner can also be added in the reaction of step (2), described solvent is selected from the hydro carbons of boiling point between 100 DEG C-160 DEG C, such as toluene, dimethylbenzene, No. 150 industrial napthas, the add-on of described solvent is about the 2%-80% of alkylate quality in step (1), preferred 5%-60%, most preferably 5%-30%; Described thinner comprise in mineral lubricating oils, polyolefine, polyethers one or more, the add-on of described thinner is about the 5%-80% of alkylate quality in step (1), preferred 10%-70%, most preferably 10%-60%.
Wherein said mineral lubricating oils can select API I, II, III class mineral lubricant oil base oil, preferably 40 DEG C of viscosity are 20-120 centistoke (cSt), viscosity index at least mineral lubricant oil base oil more than 50, and more preferably 40 DEG C of viscosity are 28-110 centistoke (cSt), the viscosity index mineral lubricant oil base oil at least more than 80.
Described polyolefine is polymerized separately by ethene, propylene, alpha-olefin or copolymerization and the polyolefine obtained, described alpha-olefin comprise in n-butene, iso-butylene, positive amylene, n-hexylene, positive octene and positive decene one or more, preferably 100 DEG C of viscosity is the poly-alpha olefins (PAO) of 2-25 centistoke (cSt), and most preferably 100 DEG C of viscosity are 6-10 centistoke (cSt).Described polyolefinic number-average molecular weight is 500-3000, preferred 700-2500, most preferably 1000-2000.
Described polyethers is the polymkeric substance generated by alcohol and epoxide reaction, and described alcohol is ethylene glycol and/or 1,3-PD, described epoxide is oxyethane and/or propylene oxide, the number-average molecular weight of described polyethers is 500-3000, preferred 700-3000, most preferably 1000-2500.
In step (3), the structure of described p-hydroxydiphenylamine derivative is:
Wherein R
1for H, C1-C8 alkyl, hydroxyl or nitro, preferred H, C1-C4 alkyl or hydroxyl, most preferably H.
In step (3), the preferred formaldehyde of described aldehyde, acetaldehyde, C
3-C
7alkanoic, one or more most preferably in paraformaldehyde, paraformaldehyde and formaldehyde.
The mol ratio of the intermediate product of described step (2), p-hydroxydiphenylamine derivative and described aldehyde is 1:0.3-3:0.1-2, preferred 1:0.3-2:0.1-2, most preferably 1:0.5-1.5:0.3-1.5.
The temperature of described Mannich reaction is 40 DEG C-200 DEG C, preferably 60 DEG C-150 DEG C, most preferably 80 DEG C-130 DEG C.
The time of described Mannich reaction is 1h-10h, preferred 2h-8h, most preferably 3h-6h.
In the compositions of the present invention, described Mannich base accounts for 0.1% ~ 10% of composition total mass, and preferably 0.2% ~ 8%, most preferably 0.3% ~ 5%.
Described emulsifying agent be selected from alkylphenol polyoxyethylene, fatty acid ester and fatty alcohol-polyoxyethylene ether one or more.
The structure of described alkylphenol polyoxyethylene is: CH
3(CH
2)
xc
6h
4(OC
2h
4)
yoH, wherein x is the integer between 5-15, the integer preferably between 6 ~ 12, and y is the integer between 1 ~ 150, the integer preferably between 4 ~ 50.Described alkylphenol polyoxyethylene can select polyoxyethylene octylphenol ether and/or polyoxyethylene nonylphenol ether, trade names can select NP, OP, TX series, such as, can select one or more in NP10, NP15, NP50, OP-4, OP-7 and TX-10.
Described fatty acid ester is the esterification reaction product of lipid acid and C1 ~ C8 alcohol and/or C1 ~ C6 hydramine.
Preferred C10 ~ C20 the lipid acid of described lipid acid, most preferably C12 ~ C18 lipid acid, such as can select in lauric acid, myristic acid, palmitinic acid, stearic acid and oleic acid one or more.
Preferred C2 ~ C6 the alcohol of described C1 ~ C8 alcohol, such as can select in isopropylcarbinol, isooctyl alcohol, ethylene glycol, glycerine, propylene glycol and tetramethylolmethane one or more.
One or more in the preferred monoethanolamine of described C1 ~ C6 hydramine, diethanolamine, trolamine, α-amino isopropyl alcohol, diisopropanolamine (DIPA), tri-isopropanolamine and diethyleneglycolamin, one or more most preferably in trolamine, α-amino isopropyl alcohol and diisopropanolamine (DIPA).
There is the product of esterification in one or more in the preferred C12 ~ C18 lipid acid of described fatty acid ester and glycerine, propylene glycol, isooctyl alcohol and trolamine, such as can select in Zerol, glyceryl monooleate, glyceryl monolaurate, propylene glycol monostearate, propylene glycol mono-oleate, Rikemal PL 100, Ethylhexyl stearate and triethanolamine oleate monoesters one or more, trade names are GMS, GMO, GML, BPMS, BPMO, BPML, EHMS, FM.
The structure of described fatty alcohol-polyoxyethylene ether is: RO-(CH
2cH
2o)
n-H, wherein R is the alkyl of the alkyl of C10 ~ C20, preferred C12 ~ C18, and n is the integer between 1 ~ 20, the integer preferably between 2 ~ 15.The preferred C of described fatty alcohol-polyoxyethylene ether
12h
25o-(CH
2cH
2o)
n-H, n are the integer between 2 ~ 10, and trade names are AEO3, AEO5, AEO7, AEO9.
The mixture of described emulsifying agent preferred alkyl phenol polyethenoxy ether and fatty acid ester, mass ratio is therebetween 40 ~ 80:60 ~ 20, preferably 50 ~ 70:50 ~ 30.
Described emulsifying agent accounts for 1% ~ 40% of present composition total mass, and preferably 3% ~ 35%, most preferably 5% ~ 30%.
Described water accounts for 0.1% ~ 10% of present composition total mass, and preferably 0.2% ~ 9%, most preferably 0.5% ~ 8%.
Described lubricant base be selected from API I, II, III, IV, V class lubricating oil base oil one or more, one or more in preferred API I, II, III class lubricating oil base oil.
Preferably lime soap dispersing agent is added in composition of the present invention, described lime soap dispersing agent is selected from isomeric alcohol polyethenoxy ether, α-glycerol monoalkyl ether α '-sulfonate, alpha-sulfo-fatty acid formate, α-acyl alpha ' alkylsulfonyl two glyceryl ester, acyl N-methyl taurate, lipid acid iso-propionyl sulfuric acid, one or more of alkyl-sulphate and alkylbenzene sulfonate, preferred isomeric alcohol polyethenoxy ether, most preferably isomery ten carbon polyoxyethylenated alcohol, trade names such as can select XP30, XP40, XP50, XP60, XP70, XP80, XP90, XP100, XP140.
Described lime soap dispersing agent accounts for 0.1% ~ 8% of present composition total mass, and preferably 0.2% ~ 5%, most preferably 0.3% ~ 3%.
Preferably rust-preventive agent is added in composition of the present invention, described rust-preventive agent be selected from boric acid ester, borate, hydramine and acid amides one or more, such as can select in tri-isopropanolamine ring boric acid ester, triethanolamine borate, thanomin and triglycolyl amine one or more, preferred boric acid ester, most preferably triethanolamine borate.
Described rust-preventive agent accounts for 0.1% ~ 10% of present composition total mass, and preferably 0.5% ~ 9%, most preferably 1% ~ 8%.
Can also add in extreme pressure agent, oiliness improver, alkaline reserve agent, coupler, sterilant and kilfoam in emulsion cutting fluid composite of the present invention one or more, and its consumption is from the conventional amount used of this area, is not particularly limited.
Present invention also offers a kind of method improving the anti-hard water stability of emulsion cutting fluid, the method is mixed by the lubricant base of above-mentioned Mannich base, emulsifying agent, water and surplus.
Present invention also offers a kind of method improving emulsion cutting fluid rustless property, the method is mixed by the lubricant base of above-mentioned Mannich base, emulsifying agent, water and surplus.
Emulsion cutting fluid composite of the present invention has excellent anti-hard water stability and rustless property, fully can meet the requirement used in the area that water hardness is larger.
Embodiment
Table 1 gives the pharmaceutical chemicals used in embodiment of the present invention.
The specification of table 1 main chemical used and source
| Reagent name | Specification | Index | Source |
| Ortho-cresol | CP | ≥98.0% | Chemical Reagent Co., Ltd., Sinopharm Group |
| HR-PIB | Mn=1000 | Chemical plant, Jilin | |
| Diethylenetriamine | CP | ≥98.0% | Beijing Chemical Plant |
| Triethylene tetramine | CP | ≥95.0% | Chemical Reagent Co., Ltd., Sinopharm Group |
| Tetraethylene pentamine | CP | ≥90.0% | Chemical Reagent Co., Ltd., Sinopharm Group |
| P-hydroxydiphenylamine | Tokyo changes into Industrial Co., Ltd | ||
| 4-hydroxyl-2'-nitrodiphenylamine | Tokyo changes into Industrial Co., Ltd | ||
| 4,4'-diamino biphenol | Tokyo changes into Industrial Co., Ltd |
Embodiment 1 synthesizing polyisobutylene ortho-cresol
In the 500ml four-hole boiling flask that agitator, thermometer, prolong and dropping funnel are housed, add the polyisobutene (Mn=1000) of 34.93g (0.323mol) ortho-cresol, the boron trifluoride diethyl etherate catalyzer of 6.88g (0.048mol), 100ml normal hexane solvent and 161.61g (0.162mol) at 80 DEG C of reaction 2h.After reaction terminates, functional quality mark be the potassium hydroxide solution cleaning reaction mixture of 5% once, and be washed to neutral remove catalyzer with hot water, then underpressure distillation removes desolventizing and unreacted ortho-cresol.The hydroxyl valency of synthetic product polyisobutene ortho-cresol is 53.49mg/g.Hydroxy value measuring is with reference to the acetic anhydride method in GB/T7383-2007.
Example reaction formula is as follows:
Embodiment 2
Polyisobutene ortho-cresol 47.16g (0.045mol) obtained in embodiment 1 is added to 500ml to be under nitrogen protection equipped with in four mouthfuls of beakers of agitator, thermometer and skimmer; then the quadrol of 2.70g (0.045mol), 3.83g (0.047mol) formaldehyde is added; and the toluene adding 47ml is as reaction solvent; after 80 DEG C of reaction 1.5h; be cooled to room temperature; add the p-hydroxydiphenylamine of 4.17g (0.0225mol), 3.83g (0.047mol) formaldehyde, at 70 DEG C of reaction 1h.After question response terminates, underpressure distillation removes a small amount of water of desolventizing and generation, obtains final Mannich base purification agent.Example reaction formula is as follows:
Or it is a small amount of
Embodiment 3
Polyisobutene ortho-cresol 53.37g (0.051mol) obtained in embodiment 1 is added to 500ml to be under nitrogen protection equipped with in four mouthfuls of beakers of agitator, thermometer and skimmer; then the triethylene tetramine of 7.46g (0.051mol), 4.38g (0.054mol) formaldehyde is added; and the dimethylbenzene adding 54ml is as reaction solvent; after 100 DEG C of reaction 1.5h; be cooled to room temperature; add 5.87g (0.0255mol) 4-hydroxyl-2'-nitrodiphenylamine, 4.38g (0.054mol) formaldehyde, at 80 DEG C of reaction 1h.After question response terminates, underpressure distillation removes a small amount of water of desolventizing and generation, obtains final Mannich base purification agent.Example reaction formula reference example 2.
Embodiment 4
Polyisobutene ortho-cresol 58.80g (0.056mol) obtained in embodiment 1 is added to 500ml to be under nitrogen protection equipped with in four mouthfuls of beakers of agitator, thermometer and skimmer; then the diethylenetriamine of 2.89g (0.028mol), 4.78g (0.059mol) formaldehyde is added; and the toluene adding 53ml is as reaction solvent; after 100 DEG C of reaction 1.5h; be cooled to room temperature; add 2.59g (0.014mol) p-hydroxydiphenylamine, 2.39g (0.029mol) formaldehyde, at 80 DEG C of reaction 1h.After question response terminates, underpressure distillation removes a small amount of water of desolventizing and generation, obtains final Mannich base purification agent.Example reaction formula is as follows:
Embodiment 5
Polyisobutene ortho-cresol 40.01g (0.038mol) obtained in embodiment 1 is added to 500ml to be under nitrogen protection equipped with in four mouthfuls of beakers of agitator, thermometer and skimmer; then the tetraethylene pentamine of 3.61g (0.019mol), 3.25g (0.040mol) formaldehyde is added; and the dimethylbenzene adding 38ml is as reaction solvent; after 80 DEG C of reaction 1.5h; be cooled to room temperature; add 4 of 1.91g (0.0095mol); 4'-diamino biphenol, 1.63g (0.020mol) formaldehyde, at 70 DEG C of reaction 1h.After question response terminates, underpressure distillation removes a small amount of water of desolventizing and generation, obtains final Mannich base purification agent.Example reaction formula reference example 4.
The embodiment 6 ~ 9 of emulsion cutting fluid and comparative example 1 ~ 4
The embodiment 6 ~ 13 of emulsion cutting fluid and the formula composition of comparative example 1 ~ 4 are in table 2.Component each in table joined and be in harmonious proportion in container, 50 DEG C of heated and stirred 2 hours, preparation obtained emulsion cutting fluid composite respectively.
Some additives used are as follows:
Contrast Mannich base purification agent, prepares by the embodiment 2 in CN103374085A, is labeled as DQJ-1;
Contrast Mannich base purification agent, prepares by the embodiment 4 in CN103374085A, is labeled as DQJ-2;
Contrast Mannich base purification agent, prepares by the embodiment 5 in CN103374085A, is labeled as DQJ-3;
Contrast Mannich base purification agent, prepares by the embodiment 6 in CN103374085A, is labeled as DQJ-4;
Emulsifying agent, alkylphenol polyoxyethylene, Hai'an, Jiangsu petroleum chemical plant, the trade mark is NP15;
Emulsifying agent, triethanolamine oleate, Hai'an, Jiangsu petroleum chemical plant, the trade mark is FM;
Lime soap dispersing agent, alkyl alcohol ethoxylates, Guangzhou Gong Hua Chemical Co., Ltd., XP30;
Lime soap dispersing agent, alkyl alcohol ethoxylates, Guangzhou Gong Hua Chemical Co., Ltd., XP70;
Rust-preventive agent, triethanolamine borate, Nanxiang Reagent Co., Ltd., Shanghai, is labeled as APE;
Rust-preventive agent, tri-isopropanolamine ring boric acid ester, Shanghai Hai Qu Chemical Co., Ltd., is labeled as TCB;
Lubricant base, 100SN, (40 DEG C of viscosity are 22.29mm
2/ s), Dalian petrochemical industry;
Lubricant base, 150SN, (40 DEG C of viscosity are 29.40mm
2/ s), Dalian petrochemical industry.
These emulsion cutting fluid composites are tested stability of emulsion (see standard SH/T0365 appendix A) and monolithic rustless property (see standard SH/T0365 Appendix B) as test sample in the water quality of 6000ppm, and 6000ppm is with CaCl
2the artificial hard water of configuration, test result is in table 2.
Emulsion cutting fluid stability test is carried out as follows: take composition sample 5g, claim accurate to 0.1g, be placed in tool plug graduated cylinder, then adding hardness is that the water of 6000ppm is to 100mL graticule place, shake up 1min after covering tightly, use pipette, extract 50mL emulsion immediately in 50mL drop-burette, after placing 24h, observe the precipitation volume of soap or oil reservoir, wherein soap is the ester shape thing of one deck white on emulsion, and as above chromatography effluent is that the transparence liquid of brown color is oil reservoir.
Monolithic test for rust preventing ability carries out as follows: in without mouth flat bottom beaker, prepare the diluent 200mL that cutting fluid volumetric concentration is 2% with the water that hardness is 6000ppm, 2min is stirred with round end glass stick, make its whole emulsification, the diluent prepared is dipped with round end glass stick, processed good test piece drips 5, often dripping diameter is 4 ~ 5mm, should maintain a certain distance between each, must not connect, test piece is placed on the porcelain plate in wetting groove, build wetting groove, under 35 ± 2 DEG C of conditions leave standstill, after test expires, carry out test piece visual inspection, dilution drop is wiped, dip in ethanol with cotton again and wipe raffinate gently, observe test piece situation.Wherein 24A represents that 24 hours its rust-preventing characteristics are that A, 18B represent that 18 hours its rust-preventing characteristics are B, and the rest may be inferred.
Table 2
Claims (16)
1. an emulsion cutting fluid composite, comprise the lubricant base of Mannich base, emulsifying agent, water and surplus, the preparation method of wherein said Mannich base comprises: (1) is under catalyst for alkylation reaction exists, phenol and/or single ortho alkyl phenol and polyolefine are reacted, collects alkylate; (2) alkylate step (1) obtained and polyamines polyene, aldehyde generation Mannich reaction, obtain intermediate product; (3) intermediate product of step (2) and p-hydroxydiphenylamine derivative, aldehyde be there is second time Mannich reaction, collect and obtain final Mannich base.
2. according to composition according to claim 1, it is characterized in that, in the step (1) of the described Mannich base of preparation, described polyolefine is by ethene, propylene, C
4-C
10alpha-olefin is polymerized separately or copolymerization and the polyolefine obtained, described single ortho alkyl phenol is selected from single ortho alkyl phenol that atomic number of alkyl carbon is 1-6, described catalyst for alkylation reaction is selected from Lewis acid catalyst, and the mol ratio between described polyolefine, phenol and/or single ortho alkyl phenol, catalyzer is 1:1-3:0.1-0.5.
3. according to composition according to claim 1, it is characterized in that, in the step (2) of the described Mannich base of preparation, described polyamines polyene has following general formula:
H
2N(CH
2)
y[(NH(CH
2)
y]
xNH2
Wherein x is the integer of 0-10, and y is integer 2 or 3, and described aldehyde is formaldehyde, acetaldehyde, C
3-C
7alkanoic, the alkylate that described step (1) obtains, the mol ratio between described polyamines polyene and described aldehyde are 1:0.3-3:0.1-3.5.
4. according to composition according to claim 1, it is characterized in that, in the step (3) of the described Mannich base of preparation, the structure of described p-hydroxydiphenylamine derivative is:
Wherein R
1for H, C1-C8 alkyl, hydroxyl or nitro, described aldehyde is formaldehyde, acetaldehyde, C
3-C
7alkanoic, the mol ratio of the intermediate product of described step (2), p-hydroxydiphenylamine derivative and described aldehyde is 1:0.3-3:0.1-2, and the temperature of described Mannich reaction is 40 DEG C-200 DEG C.
5. according to composition according to claim 1, it is characterized in that, described Mannich base accounts for 0.1% ~ 10% of composition total mass.
6., according to composition according to claim 1, it is characterized in that, described emulsifying agent be selected from alkylphenol polyoxyethylene, fatty acid ester and fatty alcohol-polyoxyethylene ether one or more.
7. according to composition according to claim 6, it is characterized in that, the structure of described alkylphenol polyoxyethylene is: CH
3(CH
2)
xc
6h
4(OC
2h
4)
yoH, wherein x is the integer between 5-15, and y is the integer between 1 ~ 150.
8. according to composition according to claim 6, it is characterized in that, described fatty acid ester is the esterification reaction product of lipid acid and C1 ~ C8 alcohol and/or C1 ~ C6 hydramine.
9. according to composition according to claim 6, it is characterized in that, described fatty acid ester be selected from Zerol, glyceryl monooleate, glyceryl monolaurate, propylene glycol monostearate, propylene glycol mono-oleate, Rikemal PL 100, Ethylhexyl stearate and triethanolamine oleate monoesters one or more.
10. according to composition according to claim 1, it is characterized in that, described emulsifying agent is the mixture of alkylphenol polyoxyethylene and fatty acid ester, and mass ratio is therebetween 40 ~ 80:60 ~ 20.
11., according to composition according to claim 1, is characterized in that, described emulsifying agent accounts for 1% ~ 40% of present composition total mass.
12., according to composition according to claim 1, is characterized in that, described water accounts for 0.1% ~ 10% of present composition total mass.
13. according to the composition one of claim 1-12 Suo Shu; it is characterized in that; lime soap dispersing agent is added in composition of the present invention; described lime soap dispersing agent is selected from isomeric alcohol polyethenoxy ether, α-glycerol monoalkyl ether α '-sulfonate, alpha-sulfo-fatty acid formate, α-acyl alpha ' alkylsulfonyl two glyceryl ester, acyl N-methyl taurate, lipid acid iso-propionyl sulfuric acid, alkyl-sulphate and alkylbenzene sulfonate one or more, described lime soap dispersing agent accounts for 0.1% ~ 8% of present composition total mass.
14. according to the composition one of claim 1-12 Suo Shu, it is characterized in that, add rust-preventive agent in composition of the present invention, described rust-preventive agent be selected from boric acid ester, borate, hydramine and acid amides one or more, described rust-preventive agent accounts for 0.1% ~ 10% of present composition total mass.
15. 1 kinds of methods improving the anti-hard water stability of emulsion cutting fluid, the method is mixed by the lubricant base of the Mannich base described in one of claim 1-12, emulsifying agent, water and surplus.
16. 1 kinds of methods improving emulsion cutting fluid rustless property, the method is mixed by the lubricant base of the Mannich base described in one of claim 1-12, emulsifying agent, water and surplus.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109233939A (en) * | 2018-10-19 | 2019-01-18 | 广州米奇化工有限公司 | Emulsifier and preparation method thereof and water-based metal working fluid |
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| US5725612A (en) * | 1996-06-07 | 1998-03-10 | Ethyl Corporation | Additives for minimizing intake valve deposits, and their use |
| CN103184094A (en) * | 2011-12-29 | 2013-07-03 | 辽宁奥克化学股份有限公司 | Cooling liquid for diamond wire cutting technology |
| CN103374085A (en) * | 2012-04-26 | 2013-10-30 | 中国石油化工股份有限公司 | Mannich base and manufacturing method and application thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US5633326A (en) * | 1989-12-13 | 1997-05-27 | Exxon Chemical Patents Inc. | Polyolefin-substituted amines grafted with poly(aromatic-N-monomers) for oleaginous compositions |
| US5725612A (en) * | 1996-06-07 | 1998-03-10 | Ethyl Corporation | Additives for minimizing intake valve deposits, and their use |
| CN103184094A (en) * | 2011-12-29 | 2013-07-03 | 辽宁奥克化学股份有限公司 | Cooling liquid for diamond wire cutting technology |
| CN103374085A (en) * | 2012-04-26 | 2013-10-30 | 中国石油化工股份有限公司 | Mannich base and manufacturing method and application thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109233939A (en) * | 2018-10-19 | 2019-01-18 | 广州米奇化工有限公司 | Emulsifier and preparation method thereof and water-based metal working fluid |
| CN109233939B (en) * | 2018-10-19 | 2021-10-15 | 广州米奇化工有限公司 | Emulsifier, preparation method thereof and water-based metal working fluid |
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