CN103601846A - Polyisobutene butane diacid amide and preparation method thereof as well as minimal quantity lubricating oil prepared from polyisobutene butane diacid amide - Google Patents
Polyisobutene butane diacid amide and preparation method thereof as well as minimal quantity lubricating oil prepared from polyisobutene butane diacid amide Download PDFInfo
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Abstract
The invention provides polyisobutene butane diacid amide. The polyisobutene butane diacid amide is characterized in that the molecular structural formula of the polyisobutene butane diacid amide is as shown in specification, and the polyisobutene butane diacid amide provided by the invention has good lubricity, extreme pressure anti-wear property, wear resistance and wear reduction property and can be used for replacing added components such as chlorides, sulfides and phosphides which are harmful for environments in conventional fields. In addition, the polyisobutene butane diacid amide also has good water solubility and enriches the category of conventional lubricating oil additives. Compared with the prior art, minimal quantity lubricating oil prepared by using a method provided by the invention has good lubricity and extreme pressure anti-wear property. A very small quantity of minimal quantity lubricating oil can meet the high-end requirements of metal processing; the damage to environments and workers is reduced; the pollution to environments is minimized. The minimal quantity lubricating oil is particularly applied to a minimal quantity lubrication system and has an obvious effect when being used in ferrous metal processing.
Description
Technical field
The present invention relates to lubrication technical field, specifically polyisobutene butylene diamide and preparation method thereof and prepare micro lubricating agent with this acid amides.
Background technology
The lubricant usage quantitys such as the machining oil of traditional metal processing and lubrication and cooling use, refrigerant, emulsion are large, and traditional machining oil is all that employing mineral oil is base oil, in physical environment, be difficult for decomposing, additive used is mostly harmful to human body and environment, not only waste resource, also can cause the huge pollution of processing site and environment.In recent years the research of micro cutting technology is obtained to very large progress, reduced the harm that the discharge of a large amount of cutting fluid causes environment, but in order to solve micro cutting problem, often in machining oil, add the extreme pressure anti-wear additives such as excessive environmentally harmful muriate, sulfide, phosphide to solve the lubrication and cooling problem in micro cutting.
As the publication number Chinese patent that is CN101376863, disclose a kind of micro quantity lubrication system aluminum alloy cutting fluid and its production and use, adopted weight percent raw material to be prepared from: base oil 30%, sulfide isobutene 5～20%, clorafin 5～20%, thiophosphatephosphorothioate 5～20%, potassium borate 5～20%, tensio-active agent 10%, rust-preventive agent 5%.Although this cutting fluid has good lubrication performance,, the use sulfide of larger proportion, muriate, phosphide etc., can bring larger pressure to environment.
Summary of the invention
In view of above defect, the object of the invention is to overcome the deficiencies in the prior art, can all or part of replacement sulfide, the polyisobutene butylene diamide of muriate, phosphide be applied to micro lubricating agent.
For achieving the above object, polyisobutene butylene diamide provided by the invention is characterised in that to have following molecular structural formula:
Wherein, the integer that n is 20-500.
In addition, the present invention also provides the preparation method of above-claimed cpd, adopts first polymerization, rear amidated method, synthetic route is: after butene dioic acid or maleic acid anhydride and isobutene reaction generation polyisobutene butene dioic acid, carry out amidate action and obtain polyisobutene butylene diamide.
Concrete synthetic route is:
Wherein, the integer that n is 20-500.
The concrete technology step of above-mentioned polyisobutene butylene diamide synthetic route is as follows:
Step 1, low-carbon alcohol and butene dioic acid or maleic acid anhydride are dropped into respectively in polymeric kettle, be stirred well to completely and dissolve.
In above-mentioned steps one, low-carbon alcohol is that carbonatoms is the monohydroxy-alcohol of 2 to 6, thereby when can effectively dissolve butene dioic acid or maleic acid anhydride, plays the effect of solvent, and be easy to decompression steam.The lower alcohol compound of carbon atom quantity because of its high polarity, can play better solvency action when as solvent thus.Therefore, to be preferably carbonatoms be the monohydroxy-alcohol of 2 to 4 to low-carbon alcohol in the present invention, ethanol more preferably, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol.
In addition, in the present invention, butene dioic acid is selected from maleic acid or FUMARIC ACID TECH GRADE.
In addition, the mol ratio of low-carbon alcohol and butene dioic acid or maleic acid anhydride is preferably (2～3) in the present invention: 1.When this ratio is too high, can makes reactant concn too low, thereby cause the reaction times to extend, react the unfavorable factor such as incomplete; When this ratio is too low, can cause reaction density too high, when polymerization reaction take place, easily produce agglomeration, cause by product too much, the productive rate of principal product reduces, and aftertreatment difficulty.
Step 2: initiator is dropped in polymeric kettle.
In the present invention, conventional initiator may be used to polyreaction of the present invention, as superoxide: dibenzoyl peroxide, lauroyl peroxide, isopropyl benzene hydroperoxide, tertbutyl peroxide, di-t-butyl peroxide, dicumyl peroxide, peroxidized t-butyl perbenzoate, peroxidation trimethylacetic acid tertiary butyl ester, methylethyl ketone peroxide, cyclohexanone peroxide, di-isopropyl peroxydicarbonate, di-cyclohexylperoxy dicarbonate, peroxy dicarbonate ethylhexyl etc.; Azo-compound: Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) etc.
In addition, to account for the mass percent of the gross weight of iso-butylene and butene dioic acid or maleic acid anhydride be 0.1～0.3% to initiator usage quantity.
Step 3: be filled with nitrogen and discharge the air in polymeric kettle.
The present invention also can use other means, as: be filled with the rare gas elementes such as helium, argon gas, coordinate the mode vacuumizing, discharge air in still.
Step 4: warming while stirring is to 70-80 ℃.
Step 5: be filled with isobutene gas in the mixed solution in polymeric kettle, keep constant temperature to stir.
When the gas being filled with is other alkene, during as the derivative of iso-butylene, be also applicable to the step in this technique.
In addition, the mol ratio of iso-butylene and butene dioic acid or maleic acid anhydride is preferably 1:0.8～1 in the present invention.Most preferably be 1:1.
Step 6: keep constant temperature to continue to stir 6-18 hour after charging isobutene gas.
According to the difference of reaction raw materials, the reaction times in this step 6 can be adjusted according to actual, and the preferred reaction time is 10-12 hour.When the reaction times is too short, cause the incomplete of reaction; And when the reaction times is long, because reaction almost reaches terminal, productive rate is without obvious raising.
Step 7: add ammoniacal liquor to solution pH value to reach 8～8.5 in polymeric kettle, do not keep constant temperature whipped state before reaching appointment pH value, when pH value no longer changes, be constant at 8～8.5 o'clock, stopped reaction.
Step 8: the ammoniacal liquor of heat up, decompression being removed moisture, low-carbon alcohol and failed to react.
In this step 8, for realizing better water removal effect, also can suitably add the toluene operation that dewaters that reduces pressure.
In addition, the above-mentioned polymkeric substance the present invention relates to is prepared the method for micro lubricating agent, it is characterized in that: in water or Aqueous Solutions of Polyethylene Glycol, adding weight percent is, after 5～30% above-mentioned polymkeric substance, to stir, and obtains a kind of micro lubricating agent.
According to the needs in the applicable function of oil product and field, when application also can with conventional additive, as water-soluble extreme-pressure anti-friction additive is used together.
Effect and the effect of invention
Polyisobutene butylene diamide compound itself provided by the invention just has good oilness, extreme pressure anti-wear, wear-resistant and anti-attrition.Can replace the added ingredients that clorafin in conventional field, sulfide, phosphide etc. are unfavorable for environmental protection.
In addition, polyisobutene butylene diamide compound itself provided by the invention also has good water-soluble, has enriched the category of existing lubricating oil additive.
Use the micro cutting liquid of method manufacture of the present invention compared with prior art, there is good oilness, extreme pressure anti-wear, seldom the micro cutting liquid of amount just can meet the high-end requirement of metal processing, reduced the harm to environment and workman, dropping to minimum to the pollution of environment, particularly apply to lubricating system with trace amount, be used in the processing of ferrous metal effect remarkable.
In the synthetic process of polyisobutene butylene diamide compound of the present invention, owing to adopting first polymerization amidated synthetic route again, be different from conventional synthetic route, avoided the secondary this loaded down with trivial details technique of purifying.
Embodiment
Embodiment 1
The agent of 1# micro lubricating
Step 1: by 148.24kg(2000mol) isopropylcarbinol and 98.06kg (1000mol) maleic anhydride (MALEIC ANHYDRIDE) drops into respectively in polymeric kettle, fully stirs;
Step 2: 0.74kg initiator dibenzoyl peroxide (BPO) is dropped in polymeric kettle;
Step 3: be filled with nitrogen and discharge the air in polymeric kettle;
Step 4: warming while stirring to 80 ℃;
Step 5: be slowly filled with 56.11kg(1000mol in the mixed solution in polymeric kettle) isobutene gas, keeps constant temperature to stir;
Step 6: keep constant temperature to continue to stir 12 hours after charging isobutene gas;
Step 7: add ammoniacal liquor in polymeric kettle;
Step 8: abundant stirring reaction, observe pH value, reach at 8.5 o'clock to solution pH value, stop adding ammoniacal liquor;
Step 9: moisture, isopropylcarbinol, unreacted ammonia are removed in the decompression that heats up, and obtain a kind of polyisobutene toxilic acid acid amides.
Prepared polyisobutene toxilic acid acid amides is to the agent of 1# micro lubricating after polyisobutene toxilic acid acid amides 30% and water 70% mixing and stirring by weight.
Embodiment 2:
The agent of 2# micro lubricating
Step 1: by 138.21kg(3000mol) ethanol and 116.07kg (1000mol) toxilic acid (maleic acid) drops into respectively in polymeric kettle, fully stirs;
Step 2: 0.51kg initiator peroxy dicarbonate ethylhexyl (EHP) is dropped in polymeric kettle;
Step 3: be filled with nitrogen and discharge the air in polymeric kettle;
Step 4: warming while stirring to 70 ℃;
Step 5: be slowly filled with 56.11kg(1000mol in the mixed solution in polymeric kettle) isobutene gas, keeps constant temperature to stir;
Step 6: keep constant temperature to continue to stir 6 hours after charging isobutene gas;
Step 7: add ammoniacal liquor in polymeric kettle;
Step 8: abundant stirring reaction, observe pH value, reach at 8 o'clock to solution pH value, stop adding ammoniacal liquor;
Step 9: moisture, isopropylcarbinol, unreacted ammonia are removed in the decompression that heats up, and obtain a kind of polyisobutene toxilic acid acid amides.
Prepared polyisobutene toxilic acid acid amides is to the agent of 2# micro lubricating after the polyoxyethylene glycol PEG400 mixing and stirring of polyisobutene toxilic acid acid amides 5% and water 60%, 35% by weight.
Embodiment 3:
The agent of 3# micro lubricating
Step 1: by 150.25kg(2500mol) n-propyl alcohol and 116.07kg (1000mol) fumaric acid (FUMARIC ACID TECH GRADE) drops into respectively in polymeric kettle, fully stirs;
Step 2: 0.27kg initiator Diisopropyl azodicarboxylate is dropped in polymeric kettle;
Step 3: be filled with nitrogen and discharge the air in polymeric kettle;
Step 4: warming while stirring to 75 ℃;
Step 5: be slowly filled with 56.11kg(1000mol in the mixed solution in polymeric kettle) isobutene gas, keeps constant temperature to stir;
Step 6: keep constant temperature to continue to stir 18 hours after charging isobutene gas;
Step 7: add ammoniacal liquor in polymeric kettle;
Step 8: abundant stirring reaction, observe pH value, reach at 8.1 o'clock to solution pH value, stop adding ammoniacal liquor;
Step 9: moisture, isopropylcarbinol, unreacted ammonia are removed in the decompression that heats up, and obtain a kind of polyisobutene fumaric acid acid amides.
Prepared polyisobutene fumaric acid acid amides is to the agent of 3# micro lubricating after polyoxyethylene glycol PEG600,1% potassium metaborate, 1% the Potassium tripolyphosphate mixing and stirring of polyisobutene fumaric acid acid amides 10% and water 70%, 18% by weight.
The agent of 1#～3# micro lubricating is carried out to physical and chemical index test, and result is as follows:
| Test subject | 1# | 2# | 3# | Test method |
| Kinematic viscosity (40 ℃ of@) mm 2/s | 10.56 | 5.43 | 8.11 | GB/T?265 |
| PH value | 8.3 | 8.0 | 8.2 | SH/T?0578 |
| Copper corrosion (50 ℃ of@) 3 hours | 1a | 1a | 1a | GB/T?5096 |
| 0 grade, damp and hot experiment monolithic cast iron | 96 hours | 24 hours | 72 hours | GB/T?2361 |
| Four ball milling spot diameter mm | 0.48 | 0.52 | 0.46 | GB/T?12583 |
Embodiment 4:
The agent of 4# micro lubricating
Step 1: by 192.71kg(2600mol) propyl carbinol and 116.07kg (1000mol) toxilic acid drops into respectively in polymeric kettle, fully stirs;
Step 2: 0.62kg initiator dibenzoyl peroxide (BPO) is dropped in polymeric kettle;
Step 3: be filled with nitrogen and discharge the air in polymeric kettle;
Step 4: warming while stirring to 76 ℃;
Step 5: be slowly filled with 56.11kg(1000mol in the mixed solution in polymeric kettle) isobutene gas, keeps constant temperature to stir;
Step 6: keep constant temperature to continue to stir 10 hours after charging isobutene gas;
Step 7: add ammoniacal liquor in polymeric kettle;
Step 8: abundant stirring reaction, observe pH value, reach at 8.3 o'clock to solution pH value, stop adding ammoniacal liquor;
Step 9: moisture, isopropylcarbinol, unreacted ammonia are removed in the decompression that heats up, and obtain a kind of polyisobutene toxilic acid acid amides.
Prepared polyisobutene toxilic acid acid amides is to the agent of 4# micro lubricating after the polyoxyethylene glycol PEG200 mixing and stirring of polyisobutene toxilic acid acid amides 20% and water 70%, 10% by weight.
The agent of 4# micro lubricating is applied to KS-2106 transformation ZB5212 multi-hole drill (4 hole), attacks diameter 2.5mm, the stainless steel of the blind hole of degree of depth 5mm.The machining oil that originally uses 20% clorafin, 70% rapeseed oil, 10% kerosene modulation to form carries out craft brushing processing, and the rotten tooth fraction defective of tapping is up to 10-20%.Work in 8 hours, measured result is as follows:
Claims (11)
1. a polyisobutene butylene diamide, is characterized in that, has following molecular structural formula:
Wherein, the integer that n is 20-500.
2. a preparation method for polyisobutene butylene diamide as claimed in claim 1, is characterized in that: after butene dioic acid or maleic acid anhydride and isobutene reaction generation polyisobutene butene dioic acid, amidate action is carried out in ammonification.
3. the preparation method of polyisobutene butylene diamide as claimed in claim 1 or 2, is characterized in that, comprises the following steps:
Step 1, low-carbon alcohol and butene dioic acid or maleic acid anhydride are dropped into respectively in polymeric kettle, be stirred well to completely and dissolve;
Step 2: initiator is dropped in polymeric kettle;
Step 3: be filled with nitrogen and discharge the air in polymeric kettle;
Step 4: warming while stirring to 70～80 ℃;
Step 5: be filled with isobutene gas in the mixed solution in polymeric kettle, keep constant temperature to stir;
Step 6: keep constant temperature to continue to stir 6～18 hours after charging isobutene gas;
Step 7: add ammoniacal liquor to reach 8～8.5 to solution pH value, stopped reaction in polymeric kettle;
Step 8: moisture, low-carbon alcohol and unreacted ammoniacal liquor are removed in decompression.
4. the preparation method of polyisobutene butylene diamide as claimed in claim 3, is characterized in that: the mol ratio of described low-carbon alcohol and butene dioic acid or maleic acid anhydride is 2～3:1.
5. the preparation method of polyisobutene butylene diamide as claimed in claim 3, is characterized in that: the mol ratio of described iso-butylene and butene dioic acid or maleic acid anhydride is 1:0.8～1.
6. the preparation method of polyisobutene butylene diamide as claimed in claim 3, it is characterized in that: described initiator is selected from dibenzoyl peroxide, lauroyl peroxide, isopropyl benzene hydroperoxide, tertbutyl peroxide, di-t-butyl peroxide, dicumyl peroxide, peroxidized t-butyl perbenzoate, peroxidation trimethylacetic acid tertiary butyl ester, methylethyl ketone peroxide, cyclohexanone peroxide, di-isopropyl peroxydicarbonate, di-cyclohexylperoxy dicarbonate, peroxy dicarbonate ethylhexyl, Diisopropyl azodicarboxylate, the mixture of one or more in 2,2'-Azobis(2,4-dimethylvaleronitrile).
7. the preparation method of polyisobutene butylene diamide as claimed in claim 3, is characterized in that: the mass percent that described initiator usage quantity accounts for the gross weight of iso-butylene and butene dioic acid or maleic acid anhydride is 0.1～0.3%.
8. the preparation method of polyisobutene butylene diamide as claimed in claim 3, is characterized in that: described low-carbon alcohol is that carbonatoms is the monohydroxy-alcohol of 2 to 6.
9. the preparation method of polyisobutene butylene diamide as claimed in claim 3, is characterized in that: described low-carbon alcohol is preferably ethanol, n-propyl alcohol, Virahol, propyl carbinol or isopropylcarbinol.
10. a micro lubricating agent of preparing with polyisobutene butylene diamide claimed in claim 1, is characterized in that: the polyisobutene dibutene acid amides that is 5～30% by weight percent and 70～95% water or Aqueous Solutions of Polyethylene Glycol and additive form,
Wherein, described additive is one or more in water-soluble extreme-pressure anti-friction additive.
The preparation method of micro lubricating agent prepared by 11. 1 kinds of polyisobutene butylene diamide as claimed in claim 10, it is characterized in that: in water or Aqueous Solutions of Polyethylene Glycol and additive, adding weight percent is after 5～30% polyisobutene dibutene acid amides, stir, obtain a kind of micro lubricating agent.
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Effective date of registration: 20200414 Address after: 300280 No.34, Nanmen commercial building, Tongsheng East District, Dagang Oilfield, Binhai New Area, Tianjin Patentee after: Tianjin Binhai New Area Dagang Fangyuan drilling and production technical service Co.,Ltd. Address before: 200062, room second, building 1006, 414 Jinsha River Road, Shanghai, Putuo District Patentee before: SHANGHAI JINZHAO ENERGY SAVING TECHNOLOGY Co.,Ltd. |
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