CN103601846B - Polyisobutene butylene diamide and preparation method thereof and prepare micro lubricating agent with this acid amides - Google Patents
Polyisobutene butylene diamide and preparation method thereof and prepare micro lubricating agent with this acid amides Download PDFInfo
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- CN103601846B CN103601846B CN201310539711.1A CN201310539711A CN103601846B CN 103601846 B CN103601846 B CN 103601846B CN 201310539711 A CN201310539711 A CN 201310539711A CN 103601846 B CN103601846 B CN 103601846B
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Abstract
The feature of polyisobutene butylene diamide provided by the invention is to have following molecular structure:
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 quantity such as machining oil, refrigerant, emulsion of conventional metals processing and lubrication and cooling is large, and traditional machining oil is all adopt oil based on mineral oil, not easily decompose in physical environment, additive used is mostly to human body and bad environmental, not only waste resource, also can cause the huge pollution of processing site and environment.In recent years very large progress is obtained to the research of micro cutting technology, decrease the harm that a large amount of discharge of cutting fluid causes environment, but in order to solve micro cutting problem, in machining oil, often adding the excessive extreme pressure anti-wear additives such as environmentally harmful muriate, sulfide, phosphide solve lubrication and cooling problem in micro cutting.
If publication number is the Chinese patent of CN101376863, disclose a kind of micro quantity lubrication system aluminum alloy cutting fluid and its production and use, adopt 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, muriate, phosphide etc. of larger proportion, 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, muriate, phosphide polyisobutene butylene diamide and be applied to micro lubricating agent.
For achieving the above object, the feature of polyisobutene butylene diamide provided by the invention is to have following molecular structure:
Wherein, n is the integer of 20-500.
In addition, present invention also offers the preparation method of above-claimed cpd, adopt and be first polymerized, rear amidated method, synthetic route is: after generating polyisobutene butene dioic acid by butene dioic acid or maleic acid anhydride and isobutene reaction, carry out amidate action and obtain polyisobutene butylene diamide.
Concrete synthetic route is:
Wherein, n is the integer of 20-500.
The concrete technology step of above-mentioned polyisobutene butylene diamide synthetic route is as follows:
Step one, low-carbon alcohol and butene dioic acid or maleic acid anhydride to be dropped in polymeric kettle respectively, be stirred well to and dissolve completely.
In above-mentioned steps one, low-carbon alcohol to be carbonatoms the be monohydroxy-alcohol of 2 to 6, thus while effectively dissolving butene dioic acid or maleic acid anhydride, play the effect of solvent, and be easy to decompression and steam.The alcohol compound that carbon atom quantity is lower thus, because of its high polarity, can play better solvency action as during solvent.Therefore, low-carbon alcohol is preferably the monohydroxy-alcohol that carbonatoms is 2 to 4 in the present invention, is more preferably ethanol, 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, reactant concn can be made too low, thus cause the reaction times to extend, react the unfavorable factor such as incomplete; When this ratio is too low, reaction density can be caused too high, when polymerization reaction take place, easily produce agglomeration, cause by product too much, the productive rate of principal product reduces, and aftertreatment is difficult.
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, initiator usage quantity accounts for the mass percent of the gross weight of iso-butylene and butene dioic acid or maleic acid anhydride is 0.1 ~ 0.3%.
Step 3: be filled with the air in nitrogen discharge polymeric kettle.
The present invention also can use other means, as: be filled with the rare gas element such as helium, argon gas, coordinate the mode vacuumized, discharge air in still.
Step 4: warming while stirring is to 70-80 DEG C.
Step 5: be filled with isobutene gas in the mixed solution in polymeric kettle, keeps constant temperature to stir.
When the gas be filled with is other alkene, during derivative as 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 adjust according to actual, and the preferred reaction time is 10-12 hour.Time too short when reacted, cause the incomplete of reaction; And when the reaction time is too long, because reaction almost reaches terminal, productive rate is without significantly improving.
Step 7: add ammoniacal liquor and reach 8 ~ 8.5 to solution pH value in polymeric kettle, kept constant temperature whipped state before not reaching appointment pH value, when pH value no longer changes, when being constant at 8 ~ 8.5, and stopped reaction.
Step 8: heat up, reduce pressure the ammoniacal liquor removing moisture, low-carbon alcohol and fail to react.
In this step 8, for realizing better water removal effect, also suitably can add toluene and carrying out decompression and to dewater operation.
In addition, the above-mentioned polymkeric substance that the present invention relates to prepares the method for micro lubricating agent, it is characterized in that: in water or Aqueous Solutions of Polyethylene Glycol, add weight percent is after the above-mentioned polymkeric substance of 5 ~ 30%, stirs, obtains a kind of micro lubricating agent.
The needs in function and field are suitable for according to oil product, also can with conventional additive when applying, as water-soluble extreme-pressure anti-friction additive uses together.
The effect of invention and effect
Polyisobutene butylene diamide compound provided by the invention inherently has good oilness, extreme pressure anti-wear, wear-resistant and anti-attrition.The added ingredients that the clorafin in general field, sulfide, phosphide etc. are unfavorable for environmental protection can be replaced.
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.
The micro cutting liquid using method of the present invention to manufacture compared with prior art, there is good oilness, extreme pressure anti-wear, the micro cutting liquid of little amount just can meet the high-end requirement of intermetallic composite coating, decrease 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 Be very effective in the processing of ferrous metal.
In the process of polyisobutene butylene diamide compound of the present invention synthesis, be first polymerized again amidated synthetic route owing to adopting, be different from general synthetic routes, avoid this loaded down with trivial details technique of secondary purification.
Embodiment
Embodiment 1
The agent of 1# micro lubricating
Step one: by 148.24kg(2000mol) isopropylcarbinol and 98.06kg (1000mol) maleic anhydride (MALEIC ANHYDRIDE) drop in polymeric kettle respectively, fully stir;
Step 2: 0.74kg initiator dibenzoyl peroxide (BPO) is dropped in polymeric kettle;
Step 3: be filled with the air in nitrogen discharge polymeric kettle;
Step 4: warming while stirring to 80 DEG C;
Step 5: be slowly filled with 56.11kg(1000mol in the mixed solution in polymeric kettle) isobutene gas, keep constant temperature to stir;
Step 6: keep constant temperature to continue stirring 12 hours after charging isobutene gas;
Step 7: add ammoniacal liquor in polymeric kettle;
Step 8: fully stirring reaction, observes pH value, when reaching 8.5 to solution pH value, stops adding ammoniacal liquor;
Step 9: heat up decompression removing moisture, isopropylcarbinol, unreacted ammonia, obtains a kind of polyisobutene maleic acid.
The agent of 1# micro lubricating is by after prepared polyisobutene maleic acid by weight polyisobutene maleic acid 30% and water 70% mixing and stirring.
Embodiment 2:
The agent of 2# micro lubricating
Step one: by 138.21kg(3000mol) ethanol and 116.07kg (1000mol) toxilic acid (maleic acid) drop in polymeric kettle respectively, fully stir;
Step 2: 0.51kg initiator peroxy dicarbonate ethylhexyl (EHP) is dropped in polymeric kettle;
Step 3: be filled with the air in nitrogen discharge polymeric kettle;
Step 4: warming while stirring to 70 DEG C;
Step 5: be slowly filled with 56.11kg(1000mol in the mixed solution in polymeric kettle) isobutene gas, keep constant temperature to stir;
Step 6: keep constant temperature to continue stirring 6 hours after charging isobutene gas;
Step 7: add ammoniacal liquor in polymeric kettle;
Step 8: fully stirring reaction, observes pH value, when reaching 8 to solution pH value, stops adding ammoniacal liquor;
Step 9: heat up decompression removing moisture, isopropylcarbinol, unreacted ammonia, obtains a kind of polyisobutene maleic acid.
The agent of 2# micro lubricating is by after the polyoxyethylene glycol PEG400 mixing and stirring of prepared polyisobutene maleic acid polyisobutene maleic acid 5% and water 60%, 35% by weight.
Embodiment 3:
The agent of 3# micro lubricating
Step one: by 150.25kg(2500mol) n-propyl alcohol and 116.07kg (1000mol) fumaric acid (FUMARIC ACID TECH GRADE) drop in polymeric kettle respectively, fully stir;
Step 2: 0.27kg initiator Diisopropyl azodicarboxylate is dropped in polymeric kettle;
Step 3: be filled with the air in nitrogen discharge polymeric kettle;
Step 4: warming while stirring to 75 DEG C;
Step 5: be slowly filled with 56.11kg(1000mol in the mixed solution in polymeric kettle) isobutene gas, keep constant temperature to stir;
Step 6: keep constant temperature to continue stirring 18 hours after charging isobutene gas;
Step 7: add ammoniacal liquor in polymeric kettle;
Step 8: fully stirring reaction, observes pH value, when reaching 8.1 to solution pH value, stops adding ammoniacal liquor;
Step 9: heat up decompression removing moisture, isopropylcarbinol, unreacted ammonia, obtains a kind of polyisobutene amides.
By prepared polyisobutene amides by weight polyisobutene amides 10% and water 70%, 18% polyoxyethylene glycol PEG600,1% potassium metaborate, 1% Potassium tripolyphosphate mixing and stirring after be the agent of 3# micro lubricating.
Physical and chemical index test is carried out in the agent of 1# ~ 3# micro lubricating, and result is as follows:
| Test subject | 1# | 2# | 3# | Test method |
| Kinematic viscosity (40 DEG C) 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 DEG C) 3 hours | 1a | 1a | 1a | GB/T 5096 |
| Damp and hot 0 grade, 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 one: by 192.71kg(2600mol) propyl carbinol and 116.07kg (1000mol) toxilic acid drop into respectively in polymeric kettle, fully stir;
Step 2: 0.62kg initiator dibenzoyl peroxide (BPO) is dropped in polymeric kettle;
Step 3: be filled with the air in nitrogen discharge polymeric kettle;
Step 4: warming while stirring to 76 DEG C;
Step 5: be slowly filled with 56.11kg(1000mol in the mixed solution in polymeric kettle) isobutene gas, keep constant temperature to stir;
Step 6: keep constant temperature to continue stirring 10 hours after charging isobutene gas;
Step 7: add ammoniacal liquor in polymeric kettle;
Step 8: fully stirring reaction, observes pH value, when reaching 8.3 to solution pH value, stops adding ammoniacal liquor;
Step 9: heat up decompression removing moisture, isopropylcarbinol, unreacted ammonia, obtains a kind of polyisobutene maleic acid.
The agent of 4# micro lubricating is by after the polyoxyethylene glycol PEG200 mixing and stirring of prepared polyisobutene maleic acid polyisobutene maleic acid 20% and water 70%, 10% by weight.
The agent of 4# micro lubricating is applied to KS-2106 and transforms ZB5212 multi-hole drill (4 hole), attack diameter 2.5mm, the stainless steel of the blind hole of degree of depth 5mm.The machining oil that originally use 20% clorafin, 70% rapeseed oil, 10% kerosene are modulated carries out craft and brushes processing, and the rotten tooth fraction defective of tapping is up to 10-20%.Work in 8 hours, measured result is as follows:
Claims (10)
1. a micro lubricating agent, is characterized in that, is that the polyisobutene butylene diamide of 5 ~ 30% and the water of 70 ~ 95% and additive or Aqueous Solutions of Polyethylene Glycol and additive form by weight percent,
Wherein, described additive is one or more in water-soluble extreme-pressure anti-friction additive;
Described polyisobutene butylene diamide, has following molecular structure:
Wherein, n is the integer of 20-500.
2. a micro lubricating agent as claimed in claim 1, is characterized in that: after the preparation method of described polyisobutene butylene diamide generates polyisobutene butene dioic acid by butene dioic acid and isobutene reaction, amidate action is carried out in ammonification.
3. micro lubricating agent as claimed in claim 1, it is characterized in that, the preparation method of described polyisobutene butylene diamide, comprises the following steps:
Step one, low-carbon alcohol and butene dioic acid or maleic acid anhydride to be dropped in polymeric kettle respectively, be stirred well to and dissolve completely;
Step 2: initiator is dropped in polymeric kettle;
Step 3: be filled with the air in nitrogen discharge polymeric kettle;
Step 4: warming while stirring to 70 ~ 80 DEG C;
Step 5: be filled with isobutene gas in the mixed solution in polymeric kettle, keeps constant temperature to stir;
Step 6: keep constant temperature to continue stirring 6 ~ 18 hours after charging isobutene gas;
Step 7: add ammoniacal liquor and reach 8 ~ 8.5 to solution ph in polymeric kettle, stopped reaction;
Step 8: decompression removing moisture, low-carbon alcohol and unreacted ammoniacal liquor.
4. micro lubricating agent 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. micro lubricating agent 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. micro lubricating agent as claimed in claim 3, is characterized in that: described initiator is selected from the mixture of one or more in 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, 2,2'-Azobis(2,4-dimethylvaleronitrile).
7. micro lubricating agent 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. micro lubricating agent as claimed in claim 3, is characterized in that: described low-carbon alcohol to be carbonatoms the be monohydroxy-alcohol of 2 to 6.
9. micro lubricating agent as claimed in claim 3, is characterized in that: described low-carbon alcohol is ethanol, n-propyl alcohol, Virahol, propyl carbinol or isopropylcarbinol.
10. as a manufacture method for claim 1 micro lubricating agent, it is characterized in that: in water or Aqueous Solutions of Polyethylene Glycol and additive, add weight percent is after the polyisobutene butylene diamide of 5 ~ 30%, stirs, obtains 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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