CN104927982B - Emulsion cutting fluid composite - Google Patents
Emulsion cutting fluid composite Download PDFInfo
- Publication number
- CN104927982B CN104927982B CN201410106202.4A CN201410106202A CN104927982B CN 104927982 B CN104927982 B CN 104927982B CN 201410106202 A CN201410106202 A CN 201410106202A CN 104927982 B CN104927982 B CN 104927982B
- Authority
- CN
- China
- Prior art keywords
- aldehyde
- cutting fluid
- mannich
- mannich base
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Lubricants (AREA)
Abstract
The invention provides a kind of method of emulsion cutting fluid composite and the raising hard water resistance stability of emulsion cutting fluid, the method for improving emulsion cutting fluid rustless property.Emulsion cutting fluid composite of the present invention includes the lube base oil of Mannich base, emulsifying agent, water and surplus, wherein the preparation method of the Mannich base includes：（1）In the presence of catalyst for alkylation reaction, make phenol and/or single ortho alkyl phenol and polyene hydrocarbon reaction, collect alkylate；（2）By step（1）With polyamines polyene, aldehyde Mannich reaction occurs for obtained alkylate, obtains intermediate product；（3）By step（2）Intermediate product and parahydroxydi-phenylamine derivative, aldehyde second of Mannich reaction occurs, collection obtains final Mannich base.The emulsion cutting fluid composite of the present invention has excellent hard water resistance stability and rustless property, can fully meet the requirement used in water hardness larger area.
Description
Technical field
The present invention relates to a kind of emulsion cutting fluid composite, more particularly to hard water resistance stability and high rust resistance
Emulsion cutting fluid composite.
Background technology
The performance of cutting fluid directly affects the quality, efficiency and cost of machining.Aqueous cutting fluid is in 20th century
The forties comes out, and up to the present, application of the water base fluid in cutting field has tremendous development.In water-base cutting fluid, emulsification
Cutting fluid has preferable lubricity and cooling, is the maximum and ideal metalworking fluid of current dosage.Cut in metal
Cut in process, cutting fluid mainly plays lubrication and cooling effect, while takes into account antirust, cleaning and antimicrobial properties
Deng.At the scene in use, emulsion cutting fluid usually requires to be diluted with more than 90% water.If dilution water water quality
Hardness is larger, easily causes dilution observability to be deteriorated, can be reacted when serious with the functional additive of system, make its analysis
Go out, condense and precipitate.
There are numerous report and patent document on water-base cutting fluid composition both at home and abroad.Patent CN101104831A is reported
A kind of microemulsified stainless steel coolant.The cutting fluid is by APES or AEO nonionic table
The additives such as face activating agent, chlorinated paraffin, oleic acid, triethanolamine and base oil, water composition, the cutting fluid for being exclusively used in stainless steel add
Work.Patent CN101560430A reports a kind of fully synthetic cutting fluid, using surfactant, polyethylene glycol, borax, sterilization
Agent, pH value regulator and balance deionized water reconcile and formed, and solve the problems, such as that existing fully synthetic cutting fluid cobalt element leaches.Specially
Sharp JP2007186537 discloses a kind of processing cast iron and non-discolouring high-performance water base cutting fluid, by saturated fatty acid, insatiable hunger
Formed with aliphatic acid, dicarboxylic acids, fatty acid metal salts etc..Patent CN102876439A discloses a kind of cutting fluid, by diethyl
Hydramine, MEA, succinic acid, borate, glycerine, emulsifying agent, antirust agent etc. form.US5725612 reports a kind of Manny
Uncommon alkali and its manufacture method, the alkyl orthoresol that the Mannich base is substituted by alkyl are obtained with aldehyde, amine reaction manufacture, can suppressed
The generation of engine deposits.
Water-base cutting fluid is in an increasingly wide range of applications in current mechanical processing industry.Cutting fluid is used as a kind of
Special mechanical processing process medium, due to the influence of itself compositing characteristic and extraneous factor, it may go out in use
The problem of now some are common, such as hard water resistance or soap rendezvous problem.There are substantial amounts of calcium ions and magnesium ions in water-base cutting fluid one side water,
On the other hand it is that can add aliphatic acid in Method of Emulsified Cutting Fluid mostly, the two is readily formed fatty acid soaps.Fatty acid soaps
Formation can't have bad influence to the performance of cutting fluid, and the aggregation of soap is only the key issue for needing solve.In hard water situation
Under especially long-time moisturizing can form substantial amounts of soap, aggregation occurs for fatty acid soaps can then produce to cutting fluid and mechanical processing process
Raw certain negative effect, it is possible to cause that emulsion is unstable, causes concentrate consumption to increase.When soap in lathe or collects
Be bonded together in middle liquid-supplying system with compositions such as foam, metal dust, miscellaneous oil, formed scum silica frost even thick substances when, band
The problem of coming can be more, and they are floated or are deposited in working solution, and not only filtration system is impacted, and cause blocking, filtering
The consumption of paper increases, on-site sanitation situation is poor, and remaining in cutter, measurer and transmission system can cause machining accuracy to be asked
Topic.These problems all propose higher requirement to the hard water resistance stability of emulsion cutting fluid itself.
The content of the invention
The invention provides a kind of emulsion cutting fluid composite and improve the hard water resistance stability of emulsion cutting fluid method,
The method for improving emulsion cutting fluid rustless property.
Emulsion cutting fluid composite of the present invention includes the lube base of Mannich base, emulsifying agent, water and surplus
Oil, wherein the preparation method of the Mannich base includes：
（1）In the presence of catalyst for alkylation reaction, make phenol and/or single ortho alkyl phenol and polyene hydrocarbon reaction, collect
Alkylate；
（2）By step（1）With polyamines polyene, aldehyde Mannich reaction occurs for obtained alkylate, obtains intermediate product；
（3）By step（2）Intermediate product and parahydroxydi-phenylamine derivative, aldehyde second of Mannich reaction occurs, receive
Collection obtains final Mannich base.
In step（1）In, described polyolefin is by ethene, propylene, C4-C10Alpha-olefin be polymerized alone or combined polymerization and obtain
The polyolefin arrived, the C4-C10Alpha-olefin can select n-butene, isobutene, n-pentene, n-hexylene, positive octene and positive decene
In one or more, preferred polyisobutene, the number-average molecular weight of the polyolefin is 300-3000, preferably 500-2000, more
It is preferred that 500-1500.
Described single preferred atomic number of alkyl carbon of ortho alkyl phenol is 1-6 single ortho alkyl phenol, most preferably orthoresol.
Described catalyst for alkylation reaction is selected from Lewis acid catalysts, preferably alchlor, boron trifluoride, four chlorinations
Tin, titanium tetrabromide, boron trifluoride phenol, the one or more of boron trifluoride alcohol complex and boron trifluoride ether complex, it is optimal
Select boron trifluoride etherate and/or boron trifluoride methanol.
Mol ratio between the polyolefin, phenol and/or single ortho alkyl phenol, catalyst is 1：1-3：0.1-0.5, it is excellent
Select 1：1.5-3：0.1-0.4, most preferably 1：1.5-3：0.2-0.4.
Reaction time is 0.5h-10h, preferably 1h-8h, most preferably 3h-5h.
Reaction temperature is 0 DEG C -200 DEG C, preferably 10 DEG C -150 DEG C, most preferably 20 DEG C -100 DEG C.
In step（1）Reaction in need that solvent can be added without, solvent can also be added.The solvent is selected from boiling point 60
Hydro carbons between DEG C -120 DEG C, such as n-hexane, normal heptane, 60-90 petroleum ethers, 90-120 petroleum ethers.The solvent with
The mass ratio of the polyolefin is 0.5:1-2:1, preferably 0.7:1-1.5:1, most preferably 0.9:1-1.3:1.Step（1）Add
After solvent participates in reaction, solvent is removed by distillation technique.
In step（2）In, described polyamines polyene has below general formula：
H2N(CH2)y[(NH(CH2)y]xNH2
Wherein x is 0-10 integer, and y is integer 2 or 3.The preferred diethylenetriamine of described polyamines polyene, triethylene four
Amine, TEPA, pentaethylene hexamine, the amine of six ethene seven, the amine of seven ethene eight, the amine of eight ethene nine, the amine of nine ethene ten and ten ethene
One or more in undecylamine, most preferably TEPA.Polyamines polyene can be by ammonia and alkylene dihalide such as dichloro alkane
It is prepared by hydrocarbon reaction.
The preferred formaldehyde of described aldehyde, acetaldehyde, C3-C7Fatty aldehyde, most preferably in paraformaldehyde, paraformaldehyde and formaldehyde
It is one or more.
The step（1）Mol ratio between obtained alkylate, the polyamines polyene and the aldehyde is 1:0.3-
3:0.1-3.5, preferably 1:0.4-2:0.2-2.5, most preferably 1:0.5-1.5:0.3-2.
The temperature of the 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 the Mannich reaction is 1h-10h, preferably 2h-8h, most preferably 3h-6h.
In step（2）Reaction in can also add solvent and/or diluent, the solvent be selected from boiling point 100 DEG C-
Hydro carbons between 160 DEG C, such as toluene, dimethylbenzene, No. 150 industrial napthas, the addition of the solvent is about step（1）Middle alkane
The 2%-80% of base product quality, preferably 5%-60%, most preferably 5%-30%；The diluent include mineral lubricating oil, polyolefin,
One or more in polyethers, the addition of the diluent is about step（1）The 5%-80% of middle alkylate quality, preferably
10%-70%, most preferably 10%-60%.
Wherein described mineral lubricating oil can select API I, II, preferably Group III mineral lubricant oil base oil, 40 DEG C of viscosity
For 20-120 centistokes（cSt）, viscosity index (VI) mineral lubricant oil base oil at least more than 50, more preferably 40 DEG C of viscosity are 28-110
Centistoke（cSt）, mineral lubricant oil base oil of the viscosity index (VI) at least more than 80.
The polyolefin be as ethene, propylene, alpha-olefin be polymerized alone or combined polymerization obtained from polyolefin, the α-alkene
Hydrocarbon includes the one or more in n-butene, isobutene, n-pentene, n-hexylene, positive octene and positive decene, preferably 100 DEG C of viscosity
For 2-25 centistokes（cSt）Poly alpha olefin（PAO）, most preferably 100 DEG C of viscosity are 6-10 centistokes（cSt）.The polyolefin
Number-average molecular weight is 500-3000, preferably 700-2500, most preferably 1000-2000.
The polyethers is the polymer generated by alcohol and epoxide reaction, and the alcohol is ethylene glycol and/or 1,3- third
Glycol, described epoxides are oxirane and/or expoxy propane, and the number-average molecular weight of the polyethers is 500-3000, excellent
Select 700-3000, most preferably 1000-2500.
In step（3）In, the structure of the parahydroxydi-phenylamine derivative is：
Wherein R1For H, C1-C8 alkyl, hydroxyl or nitro, preferably H, C1-C4 alkyl or hydroxyl, most preferably H.
In step（3）In, the preferred formaldehyde of described aldehyde, acetaldehyde, C3-C7Fatty aldehyde, most preferably paraformaldehyde, oligomeric first
One or more in aldehyde and formaldehyde.
The step（2）Intermediate product, the mol ratio of parahydroxydi-phenylamine derivative and the aldehyde be 1:0.3-3:
0.1-2, preferably 1:0.3-2:0.1-2, most preferably 1:0.5-1.5:0.3-1.5.
The temperature of the 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 the Mannich reaction is 1h-10h, preferably 2h-8h, most preferably 3h-6h.
In the compositions of the present invention, the Mannich base accounts for the 0.1%~10% of composition gross mass, preferably 0.2%~
8%, most preferably 0.3%~5%.
The one kind or more of the emulsifying agent in APES, fatty acid ester and AEO
Kind.
The structure of the APES is：CH3(CH2)xC6H4(OC2H4)yOH, wherein x are whole between 5-15
Number, the integer between preferably 6~12, y are the integer between 1~150, the integer between preferably 4~50.The alkyl phenol polyoxy
Vinethene can select OPEO and/or NPE, and trade names can select NP, OP, TX
Series, such as the one or more that can be selected in NP10, NP15, NP50, OP-4, OP-7 and TX-10.
The fatty acid ester is aliphatic acid and C1~C8 alcohol and/or the esterification reaction product of C1~C6 hydramine.
Preferred C10~C20 the aliphatic acid of aliphatic acid, most preferably C12~C18 aliphatic acid, for example, can select laurate,
One or more in myristic acid, palmitic acid, stearic acid and oleic acid.
Preferred C2~C6 the alcohol of C1~C8 alcohol, such as isobutanol, isooctanol, ethylene glycol, glycerine, propane diols can be selected
With the one or more in pentaerythrite.
It is the preferred MEA of C1~C6 hydramine, diethanol amine, triethanolamine, isopropanolamine, diisopropanolamine (DIPA), three different
One kind in one or more in Propanolamine and diethyleneglycolamin, most preferably triethanolamine, isopropanolamine and diisopropanolamine (DIPA)
It is or a variety of.
Preferred C12~C18 the aliphatic acid of fatty acid ester and one kind in glycerine, propane diols, isooctanol and triethanolamine
Or a variety of products that esterification occurs, such as glyceryl monostearate, glycerin mono-fatty acid ester, glycerine mono laurate can be selected
Ester, propylene glycol monostearate, propylene glycol mono-oleate, PGML, Ethylhexyl stearate and triethanolamine oil
One or more in acid monoester, product designation GMS, GMO, GML, BPMS, BPMO, BPML, EHMS, FM.
The structure of the AEO is：RO-(CH2CH2O)n- H, wherein R are C10~C20 alkyl, excellent
Select C12~C18 alkyl, n is the integer between 1~20, the integer between preferably 2~15.The AEO
It is preferred that C12H25O-(CH2CH2O)n- H, n be 2~10 between integer, product designation AEO3, AEO5, AEO7, AEO9.
The mixture of the preferred APES of the emulsifying agent and fatty acid ester, mass ratio therebetween is 40
~80：60~20, preferably 50~70：50~30.
The emulsifying agent accounts for the 1%~40% of present composition gross mass, preferably 3%~35%, most preferably 5%~
30%.
The water accounts for the 0.1%~10% of present composition gross mass, preferably 0.2%~9%, most preferably 0.5%~8%.
One or more of the lube base oil in API I, II, III, IV, V class lubricating oil base oil, it is excellent
Select the one or more in API I, II, Group III lube base oil.
Lime soap dispersant is preferably added in the composition of the present invention, the lime soap dispersant is selected from isomeric alcohol polyethenoxy ether
In, α-glycerol monoalkyl ether α '-sulfonate, alpha-sulfo-fatty acid formates, the α-glyceride of acyl alpha ' sulfonyl two, acyl group N- first
Base taurate, aliphatic acid iso-propionyl sulfuric acid, the one or more of alkyl sulfate and alkylbenzenesulfonate, it is preferably different
Structure alcohol APEO, most preferably the carbon alcohol APEO of isomery ten, trade names for example can select XP30, XP40, XP50,
XP60、XP70、XP80、XP90、XP100、XP140。
The lime soap dispersant accounts for the 0.1%~8% of present composition gross mass, preferably 0.2%~5%, most preferably
0.3%~3%.
Antirust agent is preferably added in the composition of the present invention, the antirust agent is selected from borate, borate, hydramine and acid amides
In one or more, such as triisopropanolamine ring borate, triethanolamine borate, monoethanolamine and triglycolyl can be selected
One or more in amine, most preferably preferred boric acid ester, triethanolamine borate.
The antirust agent accounts for the 0.1%~10% of present composition gross mass, preferably 0.5%~9%, most preferably 1%~8%.
The present invention emulsion cutting fluid composite in can also add extreme pressure agent, oiliness improver, alkaline reserve agent, coupling agent,
One or more in bactericide and anti-foaming agent, and its dosage is not particularly limited from the conventional amount used of this area.
Present invention also offers a kind of method for improving the hard water resistance stability of emulsion cutting fluid, this method is will be above-mentioned graceful
Buddhist nun wishes the lube base oil mixing of alkali, emulsifying agent, water and surplus.
Present invention also offers a kind of method for improving emulsion cutting fluid rustless property, this method is by above-mentioned Mannich
The lube base oil mixing of alkali, emulsifying agent, water and surplus.
The emulsion cutting fluid composite of the present invention has excellent hard water resistance stability and rustless property, can fully expire
The requirement that foot uses in the larger area of water hardness.
Embodiment
Table 1 gives the chemicals used in embodiment of the present invention.
The specification of main chemical and source used in table 1
| Reagent name | Specification | Index | Source |
| Orthoresol | CP | ≥98.0% | Chemical Reagent Co., Ltd., Sinopharm Group |
| HR-PIB | Mn=1000 | Jilin chemical plant | |
| Diethylenetriamine | CP | ≥98.0% | Beijing Chemical Plant |
| Triethylene tetramine | CP | ≥95.0% | Chemical Reagent Co., Ltd., Sinopharm Group |
| TEPA | CP | ≥90.0% | Chemical Reagent Co., Ltd., Sinopharm Group |
| Parahydroxydi-phenylamine | Tokyo chemical conversion industry Co., Ltd. | ||
| 4- hydroxyl -2'- nitrodiphenylamines | Tokyo chemical conversion industry Co., Ltd. | ||
| 4,4'- diaminourea biphenols | Tokyo chemical conversion industry Co., Ltd. |
The synthesizing polyisobutylene orthoresol of embodiment 1
In the 500ml four-hole boiling flasks equipped with agitator, thermometer, condenser pipe and dropping funel, 34.93g is added
(0.323mol) orthoresol, 6.88g (0.048mol) BFEE catalyst, 100ml n-hexanes solvent and 161.61g
The polyisobutene of (0.162mol)（Mn=1000）2h is reacted at 80 DEG C.After reaction terminates, use quality fraction is 5% hydroxide
Potassium solution cleaning reactant mixture once, and is washed to neutrality to remove catalyst with hot water, is then evaporated under reduced pressure and removes solvent
And unreacted orthoresol.The hydroxyl valency of synthetic product polyisobutene orthoresol is 53.49mg/g.Hydroxy value measuring refers to GB/
Acetic anhydride method in T7383-2007.
Example reaction equation is as follows：
Embodiment 2
Obtained polyisobutene orthoresol 47.16g (0.045mol) in embodiment 1 is added to 500ml under nitrogen protection
In four mouthfuls of beakers equipped with agitator, thermometer and knockout, 2.70g (0.045mol) ethylenediamine, 3.83g are then added
(0.047mol) formaldehyde, and the toluene for adding 47ml after 80 DEG C are reacted 1.5h, is cooled to room temperature, added as reaction dissolvent
4.17g (0.0225mol) parahydroxydi-phenylamine, 3.83g (0.047mol) formaldehyde, react 1h at 70 DEG C.After question response terminates,
The a small amount of water for removing solvent and generation is evaporated under reduced pressure, obtains final Mannich Base Detergent.Example reaction equation is as follows：
Or a small amount of
Embodiment 3
Obtained polyisobutene orthoresol 53.37g (0.051mol) in embodiment 1 is added to 500ml under nitrogen protection
In four mouthfuls of beakers equipped with agitator, thermometer and knockout, then add 7.46g (0.051mol) triethylene tetramine,
4.38g (0.054mol) formaldehyde, and the dimethylbenzene for adding 54ml after 100 DEG C are reacted 1.5h, is cooled to room as reaction dissolvent
Temperature, 5.87g (0.0255mol) 4- hydroxyl -2'- nitrodiphenylamines, 4.38g (0.054mol) formaldehyde are added, react 1h at 80 DEG C.
After question response terminates, a small amount of water for removing solvent and generation is evaporated under reduced pressure, obtains final Mannich Base Detergent.Example is reacted
Formula reference implementation example 2.
Embodiment 4
Obtained polyisobutene orthoresol 58.80g (0.056mol) in embodiment 1 is added to 500ml under nitrogen protection
In four mouthfuls of beakers equipped with agitator, thermometer and knockout, then add 2.89g (0.028mol) diethylenetriamine,
4.78g (0.059mol) formaldehyde, and the toluene for adding 53ml after 100 DEG C are reacted 1.5h, is cooled to room as reaction dissolvent
Temperature, 2.59g (0.014mol) parahydroxydi-phenylamine, 2.39g (0.029mol) formaldehyde are added, react 1h at 80 DEG C.Question response knot
Shu Hou, a small amount of water for removing solvent and generation is evaporated under reduced pressure, obtains final Mannich Base Detergent.Example reaction equation is as follows：
Embodiment 5
Obtained polyisobutene orthoresol 40.01g (0.038mol) in embodiment 1 is added to 500ml under nitrogen protection
In four mouthfuls of beakers equipped with agitator, thermometer and knockout, then add 3.61g (0.019mol) TEPA,
3.25g (0.040mol) formaldehyde, and the dimethylbenzene for adding 38ml after 80 DEG C are reacted 1.5h, is cooled to room as reaction dissolvent
Temperature, adds 1.91g (0.0095mol) 4,4'- diaminourea biphenol, 1.63g (0.020mol) formaldehyde, reacts 1h at 70 DEG C.
After question response terminates, a small amount of water for removing solvent and generation is evaporated under reduced pressure, obtains final Mannich Base Detergent.Example is reacted
Formula reference implementation example 4.
The embodiment 6~9 and comparative example 1~4 of emulsion cutting fluid
The embodiment 6~13 of emulsion cutting fluid and the formula composition of comparative example 1~4 are shown in Table 2.Each component in table is added
To reconciling in container, in 50 DEG C of heating stirrings 2 hours, prepare obtain emulsion cutting fluid composite respectively.
Some used additives are as follows：
Mannich Base Detergent is contrasted, is prepared by the embodiment 2 in CN103374085A, labeled as DQJ-1；
Mannich Base Detergent is contrasted, is prepared by the embodiment 4 in CN103374085A, labeled as DQJ-2；
Mannich Base Detergent is contrasted, is prepared by the embodiment 5 in CN103374085A, labeled as DQJ-3；
Mannich Base Detergent is contrasted, is prepared by the embodiment 6 in CN103374085A, labeled as DQJ-4；
Emulsifying agent, APES, Jiangsu Hai'an petrochemical plant, trade mark NP15；
Emulsifying agent, triethanolamine oleate, Jiangsu Hai'an petrochemical plant, trade mark FM；
Lime soap dispersant, alkyl alcohol ethoxylates, Guangzhou Gong Hua Chemical Co., Ltd.s, XP30；
Lime soap dispersant, alkyl alcohol ethoxylates, Guangzhou Gong Hua Chemical Co., Ltd.s, XP70；
Antirust agent, triethanolamine borate, Nanxiang Reagent Co., Ltd., Shanghai, labeled as APE；
Antirust agent, triisopropanolamine ring borate, Shanghai Hai Qu Chemical Co., Ltd.s, labeled as TCB；
Lube base oil, 100SN,（40 DEG C of viscosity are 22.29mm2/s）, Dalian petrochemical industry；
Lube base oil, 150SN,（40 DEG C of viscosity are 29.40mm2/s）, Dalian petrochemical industry.
In 6000ppm water quality stability of emulsion is tested using these emulsion cutting fluid composites as test specimen（See
Standard SH/T0365 appendix As）And monolithic rustless property（See standard SH/T0365 Appendix B）, 6000ppm is with CaCl2Configuration
Artificial hard water, test result are shown in Table 2.
Emulsion cutting fluid stability test is carried out as follows：Composition sample 5g is weighed, claims standard to be placed in 0.1g
In tool plug graduated cylinder, then stiffened degree is at 6000ppm water to 100mL graticules, and 1min is shaken up after covering tightly, is inhaled immediately with pipette
50mL emulsions are taken in 50mL burets, place the precipitation volume of observation soap or oil reservoir after 24h, wherein soap is on emulsion
One layer of white ester shape thing in face, as above layer precipitate is oil reservoir for the transparence liquid of brown color.
Monolithic test for rust preventing ability is carried out as follows：The water for being 6000ppm with hardness in without mouth flat bottom beaker
The dilution 200mL that cutting fluid volumetric concentration is 2% is prepared, 2min is stirred with round end glass bar, it is all emulsified, use round end
Glass bar dips the dilution prepared, and 5 drops are dripped in processed good test piece, often drip a diameter of 4~5mm, should be protected between each drop
Hold a certain distance, must not connect, by test piece be placed on wetting groove in porcelain plate on, cover wetting groove, under the conditions of 35 ± 2 DEG C
Stand, after experiment expires, carry out test piece visual examination, dilution drop is wiped, then dip in ethanol with cotton and gently wipe raffinate, see
Examine test piece situation.Wherein 24A represents that 24 hours its rust-preventing characteristics are A, and 18B represents that 18 hours its rust-preventing characteristics are B, and the rest may be inferred.
Table 2
Claims (15)
1. a kind of emulsion cutting fluid composite, including Mannich base, emulsifying agent, the wherein lube base oil of water and surplus, institute
Stating the preparation method of Mannich base includes：(1) in the presence of catalyst for alkylation reaction, phenol and/or single ortho alkyl phenol are made
With polyene hydrocarbon reaction, alkylate is collected；(2) with polyamines polyene, aldehyde Manny occurs for the alkylate for obtaining step (1)
Uncommon reaction, obtains intermediate product；(3) intermediate product of step (2) is occurred with parahydroxydi-phenylamine derivative, aldehyde graceful for the second time
Ni Xi reacts, and collection obtains final Mannich base；The emulsifying agent is selected from APES, fatty acid ester and fat
One or more in alcohol APEO.
2. according to the composition described in claim 1, it is characterised in that described prepare the Mannich base the step of in (1)
Polyolefin be by ethene, propylene, C4-C10Alpha-olefin be polymerized alone or combined polymerization obtained from polyolefin, described single ortho position
Alkyl phenol is selected from single ortho alkyl phenol that atomic number of alkyl carbon is 1-6, and described catalyst for alkylation reaction is urged selected from Lewis acid
Agent, the mol ratio between the polyolefin, phenol and/or single ortho alkyl phenol, catalyst are 1：1-3：0.1-0.5.
3. according to the composition described in claim 1, it is characterised in that described prepare the Mannich base the step of in (2)
Polyamines polyene there is below general formula：
H2N(CH2)y[(NH(CH2)y]xNH2
Wherein x is 0-10 integer, and y is integer 2 or 3, and described aldehyde is formaldehyde, acetaldehyde, C3-C7Fatty aldehyde, the step
(1) mol ratio between the alkylate, the polyamines polyene and the aldehyde that obtain is 1:0.3-3:0.1-3.5.
4. according to the composition described in claim 1, it is characterised in that described prepare the Mannich base the step of in (3)
The structure of parahydroxydi-phenylamine derivative is：
Wherein R1For H, C1-C8 alkyl, hydroxyl or nitro, described aldehyde is formaldehyde, acetaldehyde, C3-C7Fatty aldehyde, the step
(2) mol ratio of intermediate product, parahydroxydi-phenylamine derivative and the aldehyde is 1:0.3-3:0.1-2, the Mannich are anti-
The temperature answered is 40 DEG C -200 DEG C.
5. according to the composition described in claim 1, it is characterised in that the Mannich base accounts for the 0.1% of composition gross mass
~10%.
6. according to the composition described in claim 1, it is characterised in that the structure of the APES is：CH3
(CH2)xC6H4(OC2H4)yThe integer of OH, wherein x between 5-15, y are the integer between 4~150.
7. according to the composition described in claim 1, it is characterised in that the fatty acid ester be aliphatic acid and C1~C8 alcohol and/
Or the esterification reaction product of C1~C6 hydramine.
8. according to the composition described in claim 1, it is characterised in that the fatty acid ester is selected from glyceryl monostearate, sweet
It is oily monoleate, glyceryl monolaurate, propylene glycol monostearate, propylene glycol mono-oleate, PGML, hard
One or more in the different monooctyl ester of resin acid and triethanolamine oleate monoesters.
9. according to the composition described in claim 1, it is characterised in that the emulsifying agent is APES and fat
The mixture of acid esters, mass ratio therebetween is 40~80：60~20.
10. according to the composition described in claim 1, it is characterised in that the emulsifying agent account for composition gross mass 1%~
40%.
11. according to the composition described in claim 1, it is characterised in that the water account for composition gross mass 0.1%~
10%.
12. a kind of emulsion cutting fluid composite, including Mannich base, emulsifying agent, lime soap dispersant, the lubrication oil base of water and surplus
Plinth oil, wherein the preparation method of the Mannich base includes：(1) in the presence of catalyst for alkylation reaction, phenol and/or list are made
Ortho alkyl phenol and polyene hydrocarbon reaction, collect alkylate；(2) alkylate for obtaining step (1) and polyamines polyene,
Mannich reaction occurs for aldehyde, obtains intermediate product；(3) intermediate product of step (2) and parahydroxydi-phenylamine derivative, aldehyde are sent out
Raw second of Mannich reaction, collection obtain final Mannich base；The emulsifying agent is selected from APES, fat
One or more in acid esters and AEO；The lime soap dispersant is selected from isomeric alcohol polyethenoxy ether, α-sweet
Oily monoalky lether α '-sulfonate, alpha-sulfo-fatty acid formates, the glyceride of α-acyl alpha '-sulfonyl two, acyl N-methyl ox sulphur
Hydrochlorate, aliphatic acid iso-propionyl sulfuric acid, the one or more of alkyl sulfate and alkylbenzenesulfonate；The Mannich base
Account for the 0.1%~10% of composition gross mass；The emulsifying agent accounts for the 1%~40% of composition gross mass；The calcium soap disperses
Agent accounts for the 0.1%~8% of composition gross mass；The water accounts for the 0.1%~10% of composition gross mass.
13. a kind of emulsion cutting fluid composite, including Mannich base, emulsifying agent, antirust agent, the lube base of water and surplus
Oil, wherein the preparation method of the Mannich base includes：(1) in the presence of catalyst for alkylation reaction, phenol and/or single neighbour are made
Position alkyl phenol and polyene hydrocarbon reaction, collect alkylate；(2) alkylate for obtaining step (1) and polyamines polyene, aldehyde
Generation Mannich reaction, obtains intermediate product；(3) intermediate product of step (2) and parahydroxydi-phenylamine derivative, aldehyde are occurred
Second of Mannich reaction, collection obtain final Mannich base；The emulsifying agent is selected from APES, aliphatic acid
One or more in ester and AEO；The antirust agent is in borate, borate, hydramine and acid amides
It is one or more；The Mannich base accounts for the 0.1%~10% of composition gross mass；The emulsifying agent accounts for composition gross mass
1%~40%；The antirust agent accounts for the 0.1%~10% of composition gross mass；The water accounts for the 0.1% of composition gross mass
~10%.
14. a kind of method for improving the hard water resistance stability of emulsion cutting fluid, this method is by institute in one of claim 1-11
The lube base oil mixing of Mannich base, emulsifying agent, water and the surplus stated.
15. a kind of method for improving emulsion cutting fluid rustless property, this method is will be graceful described in one of claim 1-11
Buddhist nun wishes the lube base oil mixing of alkali, emulsifying agent, water and surplus.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410106202.4A CN104927982B (en) | 2014-03-20 | 2014-03-20 | Emulsion cutting fluid composite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410106202.4A CN104927982B (en) | 2014-03-20 | 2014-03-20 | Emulsion cutting fluid composite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104927982A CN104927982A (en) | 2015-09-23 |
| CN104927982B true CN104927982B (en) | 2017-11-28 |
Family
ID=54115412
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410106202.4A Active CN104927982B (en) | 2014-03-20 | 2014-03-20 | Emulsion cutting fluid composite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104927982B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2014
- 2014-03-20 CN CN201410106202.4A patent/CN104927982B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104927982A (en) | 2015-09-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103374437B (en) | Two-stroke engine oil composition and manufacture method thereof | |
| AU2009260327A1 (en) | Cleaning compositions containing mid-range alkoxylates | |
| CN103113970B (en) | Water-soluble quasi-dry cutting liquid as well as preparation method and use thereof | |
| WO2010072029A1 (en) | Surfactant compositions with wide ph stability | |
| CN104927982B (en) | Emulsion cutting fluid composite | |
| CN107418673B (en) | Cutting fluid of emulsifying system based on polyisobutenyl succinic anhydride and preparation method and application thereof | |
| CN104927997B (en) | Micro-emulsion cutting fluid composition | |
| CN103664655B (en) | Mannich base detergent, preparation method thereof as well as detergent concentrate and fuel oil composition | |
| CN102796592A (en) | Organic molybdenum additive, preparation method thereof and lubricating oil composition containing additive | |
| CN104928003B (en) | Fully synthetic cutting fluid composition | |
| CN104927998B (en) | Micro-emulsion cutting fluid composition | |
| CN104560240B (en) | Wear-resistant cleaning agent composition, Dresel fuel compositions and the method improving the wear-resistant cleansing performance of diesel oil | |
| CN104927981B (en) | Emulsion cutting fluid composite | |
| CN104928002B (en) | Fully synthetic cutting fluid composition | |
| CN104927999B (en) | Micro-emulsion cutting fluid composition | |
| CN104927972B (en) | Anticorrosive oil composition | |
| CN103666563A (en) | Antiscale composition and application thereof | |
| CN104927983B (en) | Emulsion cutting fluid composite | |
| CN104946352B (en) | Lubricant oil composite | |
| EP4165150A1 (en) | Aqueous composition comprising water-soluble glycerin-based polyalkylene glycols and use thereof | |
| WO2009129292A1 (en) | Polyol esters and process for making them | |
| CN104927996B (en) | Fully synthetic cutting fluid composition | |
| CN104946350B (en) | Lubricant oil composite | |
| CN108865395A (en) | A kind of microemulsified rust preventive cutting fluid and preparation method thereof | |
| US20230407205A1 (en) | Compound, precursor compound thereof, surfactant composition, and detergent composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |