CN104263476B - Biodegradable micro lubricating oil and preparation method thereof - Google Patents
Biodegradable micro lubricating oil and preparation method thereof Download PDFInfo
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- CN104263476B CN104263476B CN201410472108.0A CN201410472108A CN104263476B CN 104263476 B CN104263476 B CN 104263476B CN 201410472108 A CN201410472108 A CN 201410472108A CN 104263476 B CN104263476 B CN 104263476B
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- lubricating oil
- acid
- micro lubricating
- biodegradable micro
- borate
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Abstract
The invention provides a kind of biodegradable micro lubricating oil, it is characterised in that: comprising the fatty acyl sarcosines that mass percentage content is 5～10%, wherein, described fatty acyl sarcosines is prepared from by acylation reaction with sarcosine by carboxylic acid.A kind of biodegradable micro lubricating oil that the present invention provides; there is fine biological degradability; good extreme pressure anti-wear and lubricity; minimum quantity lubrication device is coordinated to use; usage amount can reduce to original less than 5%; reaching good lubrication and cooling effect, energy-saving and emission-reduction, environmental protection benefit are notable.
Description
Technical field
The invention belongs to lubrication technical field, in particular it relates to a kind of biodegradable micro lubricating oil and system thereof
Preparation Method.
Background technology
Traditional metal cutting process use mineral oil or vegetable oil or cutting fluid carry out a large amount of shower formula lubrication and
Cooling, the usage amount of lubricant is big, not only wastes resource, causes the huge pollution of processing site and environment,
The most also can have a strong impact on the healthy of operator.Advocating energy-saving and emission-reduction, environmental conservation, green life
The today produced, it is badly in need of a kind of new metal cutting process technique.
Micro cutting technology is the metallic green New Machining Technology grown up in recent years, it is simply that add in metal cutting
Use lubricating system with trace amount that extreme pressure anti-wear, micro lubricating oil that lubricity is good are sprayed on processing during work
Cutter and finished surface are lubricated, cool down, and solve tradition and add that cutting in man-hour oil, liquid usage amount be big, waste
The problems such as leakage rate is big, but in order to reach good lubrication effect, currently used micro lubricating oil
Often contain substantial amounts of chlorine, sulfur etc. and environment is had the additive of certain impact, meanwhile, micro lubricating used
Agent is the most degradable at nature, affects environment.
Summary of the invention
It is contemplated that overcome the deficiencies in the prior art, it is provided that one coordinates be applicable to metal cutting process technique
The biodegradable micro lubricating oil that minimum quantity lubrication device uses, with replace original traditional with mineral oil or
Vegetable oil or cutting fluid are as machining of metals oil/liquid with containing a large amount of chlorine, the micro lubricating oil of sulphur compound.
The invention provides a kind of biodegradable micro lubricating oil, it is characterised in that: comprise mass percent and contain
Amount is the fatty acyl sarcosines of 5～10%, and wherein, fatty acyl sarcosines is to be passed through acylated by carboxylic acid and sarcosine
Reaction is prepared from.
Preferably employing, carbon number is the saturated of 8-20 or undersaturated fatty acid.
One or more being most preferably in Hamposyl L, N-Oleoylsarcosine, Hamposyl S etc.
Compositions, itself biological degradability is excellent, moreover it is possible to promotes the biodegradation of other organic principles, is simultaneously
Good containing N type extreme pressure anti-wear additives, the best rustless property.
A kind of biodegradable micro lubricating oil that the present invention provides, preferably by following components in percentage by weight group
Become:
The product that above-mentioned dibasic acid esters is dihydroxylic alcohols and monoacid or binary acid and monohydric alcohol esterification generates.
It is the saturated of 2-20 or undersaturated fatty alcohol that above-mentioned monohydric alcohol and dihydroxylic alcohols preferably are selected from carbon number；
It is the saturated of 2-20 or undersaturated fatty acid that above-mentioned monoacid and binary acid preferably are selected from carbon number.
Above-mentioned dibasic acid esters most preferably from, dioctyl adipate, dioctyl azelate, di-n-octyl sebacate, adipic acid
Didecyl, two different decayl esters of azelaic acid, DI(2ETHYLHEXYL)SEBACATE, succinic acid di-isooctyl, succinic acid two isodecyl
The compositions of one or more in ester, ethylene glycol laurate, propylene glycol oleate etc..In the present invention
Dibasic acid esters has good lubricity, and kinematic viscosity is low, and cryogenic property is good, and biodegradability is excellent.
It addition, above-mentioned polyester is to be reacted esterification under catalyst action, the most again by binary acid and dihydroxylic alcohols
Carry out blocking with carboxylic acid or alcohol and be prepared from.
It is the saturated of 2-20 or undersaturated fatty alcohol that above-mentioned dihydroxylic alcohols preferably is selected from carbon number；
It is the saturated of 2-20 or undersaturated fatty acid that above-mentioned binary acid preferably is selected from carbon number.
The preparation method of above-mentioned polyester is: add in polymeric kettle for 1:1 in molar ratio by dihydroxylic alcohols and binary acid,
Add storng-acid cation exchange resin carry out polyreaction as catalyst, reaction temperature at 180～220 DEG C,
Response time is 8～12 hours, is subsequently adding a certain proportion of monocarboxylic acid or monohydric alcohol blocks, subtract
Pressure removes moisture content, after removing storng-acid cation exchange resin, prepares.
Being respectively selected from carbon number for the monocarboxylic acid blocked or monohydric alcohol is the saturated or undersaturated of 2-20
Fatty acid or fatty alcohol.
This polyester is relatively big due to molecular weight, can form the physical protection film of densification in the present invention in metal surface,
There is good lubricity and extreme pressure anti-wear, can completely or partially replace chloride, the extreme-pressure anti-wear of sulfur, phosphorus
Agent uses.
It addition, above-mentioned tall oil acid or tall oil can also be ready denier oil acid, this component has good profit
Slip, its carboxyl-COOH can also form reasonable adhesive force in metal surface simultaneously, has certain rust-preventing characteristic,
Biological degradability is good.
It addition, abovementioned alkyl phosphate ester preferably carbon number be the anionic alkyl of 2-20, alkaryl,
Polyoxyethylated alkyl, poly-diethylene glycol monoesters or dibasic acid esters phosphate ester；Nonionic alkyl, alkaryl, poly-
Oxyethylation alkyl phosphate；The compositions of one or more in amphoteric ion type phosphate ester.
Most preferably from oleyl alcohol phosphate ester, lauryl alcohol phosphate ester, diisooctyl phosphoric acid ester, tributyl phosphate etc.
The compositions of one or more, this component has a good extreme pressure anti-wear, or aluminum and alloy processing is slow
Erosion agent, also possesses preferable biological degradability simultaneously.
It addition, above-mentioned hydramine borate, it is selected from monoethanolamine borate, diethanolamine borate, three ethanol
The compositions of one or more in amine borate etc., this component has excellent rust-preventing characteristic and extreme pressure anti-wear,
It is readily biodegradable simultaneously.
Additionally, present invention also offers the preparation method of a kind of biodegradable micro lubricating oil: i.e., by weight
Percentage ratio weigh described dibasic acid esters, polyester, N-Oleoylsarcosine, tall oil acid or tall oil, alkyl phosphate,
Hydramine borate is separately added in agitator stir about 1 hour at a temperature of 40～60 DEG C, and sampling has been observed
During all-transparent.
Beneficial effects of the present invention:
A kind of biodegradable micro lubricating oil that the present invention provides, has fine biological degradability, good pole
Pressure wear resistence and lubricity, coordinate minimum quantity lubrication device to use, and usage amount can reduce to original less than 5%,
Reaching good lubrication and cooling effect, energy-saving and emission-reduction, environmental protection benefit are notable.
Specifically, have employed N-Oleoylsarcosine in the present invention, it is excellent that this component has biological degradability, moreover it is possible to
Promote the biodegradation of other organic principles, be good containing N type extreme pressure anti-wear additives simultaneously, also have good
Rustless property.
The use of polyester can completely or partially replace the environmentally harmful additives such as chloride, sulfur, to environment more
Close friend, polyester is relatively big due to molecular weight, can coordinate the material of other components in the present invention, in metal surface
Form fine and close physical protection film, there is good lubricity and extreme pressure anti-wear, can completely or partially replace
Extreme pressure anti-wear additives chloride, sulfur, phosphorus uses.
And tall oil acid or tall oil, there is good lubricity, its carboxyl-COOH can also be at metal watch simultaneously
Face forms reasonable adhesive force, has certain rust-preventing characteristic, and biological degradability is good.
Alkyl phosphate then has good extreme pressure anti-wear, or the corrosion inhibiter that aluminum and alloy are processed, the most also
Possesses preferable biological degradability.
Hydramine borate has excellent rust-preventing characteristic and extreme pressure anti-wear simultaneously, is readily biodegradable simultaneously.
It is worthy of note, the compatibility is good, the product of excellent to use the formula proportion of the present invention to be obtained in that.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further detailed explanation:
Embodiment 1:
Weigh 80kg dioctyl adipate, 10kg polyester 1#, 5kg N-Oleoylsarcosine, 2kg tall oil acid,
2kg oleyl alcohol phosphate ester, 1kg monoethanolamine borate are separately added in agitator stir about at a temperature of 40 DEG C
1 hour, sampling was biodegradable micro lubricating oil when observing fully transparent.
The preparation method of above-mentioned polyester 1#: weigh 76.09kg (1000mol) 1,3 propylene glycol and
202.25kg (1000mol) decanedioic acid adds in polymeric kettle, adds 2kg storng-acid cation exchange resin nitrogen
Gas displaces air in still, and in temperature at 220 DEG C, the response time is 8 hours, is subsequently adding a certain proportion of
5kg oleic acid blocks, and decompression removes moisture content, after removing storng-acid cation exchange resin, prepares.
Biodegradable micro lubricating oil prepared by said method, as follows through test physical and chemical index:
| Project | Master data | Experimental technique |
| Outward appearance | Pale yellow transparent | Range estimation |
| 40 DEG C of mm of kinematic viscosity2/s | 15.6 | GB/T265 |
| Pour point DEG C | -27 | GB/T3535 |
| Open flash point DEG C | 158 | GB/T3536 |
| 20 DEG C of kg/m of density3 | 865 | GB/T1884 |
| Copper corrosion level | 1a | GB/T5096 |
| Four ball milling speckle mm | 0.33 | GB/T12583 |
Embodiment 2:
Weighing 60kg dioctyl azelate, 20kg polyester 2#, 10kg Hamposyl L, 5kg tall oil divides
Not Jia Ru in agitator at a temperature of 60 DEG C stir about 1 hour, sampling is biology when observing fully transparent
Degradable micro lubricating oil.
The preparation method of above-mentioned polyester 2#: weigh 90.12kg (1000mol) 1,4 butanediols and
174.19kg (1000mol) decanedioic acid adds in polymeric kettle, adds 1.6kg storng-acid cation exchange resin and uses
Nitrogen displaces air in still, and in temperature at 180 DEG C, the response time is 12 hours, is subsequently adding a definite proportion
The 4kg n-amyl alcohol of example blocks, and decompression removes moisture content, after removing storng-acid cation exchange resin, and system
?.
Embodiment 3:
Weigh 70kg di-n-octyl sebacate, 15kg polyester 2#, 8kg N-Oleoylsarcosine, 5kg lauryl alcohol phosphoric acid
Ester, 2kg diethanolamine borate are separately added in agitator stir about 1 hour at a temperature of 50 DEG C, take
Sample is biodegradable micro lubricating oil when observing fully transparent.
The above-mentioned biodegradable micro lubricating oil preparing above-mentioned preparation is carried out biodegradable experiment:
1. experimental technique: GB/T 21856-2008 chemicals fast degradation carbon dioxide produces test.
2. experiment material:
2.1 fluid: the biodegradable micro lubricating oil of above-described embodiment 3 preparation.
2.2 inoculums: take from soil at different local earth's surface 0-10cm, soil sample, after mixing, remove impurity, is used
Deionized water soaking and stirring takes supernatant.
3. experimental result:
Calculating 28 days biological degradation rates is: 88.32%.
Embodiment 4:
Weigh 75kg two different decayl esters of azelaic acid, 12kg polyester 1#, 7kg N-Oleoylsarcosine, 2kg tall oil,
2kg tributyl phosphate, 2kg diethanolamine borate are separately added in agitator stir about at a temperature of 45 DEG C
1 hour, sampling was biodegradable micro lubricating oil when observing fully transparent.
The biodegradable micro lubricating oil above-mentioned reaction prepared is applied to: gear teeth is processed, gear hobbing type
Number: YK3132；Add work gear title: diameter 100mm, modulus 2.0mm；Hobboing cutter: TiN coating, diameter
75mm, length 70mm.Tradition is processed as 32# machinery oil oil and drenches formula lubrication.
Embodiment 5:
Weigh 73kg DI(2ETHYLHEXYL)SEBACATE, 14kg polyester 1#, 6kg Hamposyl S, 2kg bis-different pungent
It is little that base phosphate ester, 5kg triethanolamine borate are separately added in agitator stir about 1 at a temperature of 52 DEG C
Time, sampling is biodegradable micro lubricating oil when observing fully transparent.
Embodiment 6:
Weigh 67kg DI(2ETHYLHEXYL)SEBACATE, 18kg polyester 3#, 8kg N-Oleoylsarcosine, 4kg tall oil acid,
1.5kg lauryl alcohol phosphate ester, 1.5kg triethanolamine borate are separately added in agitator at a temperature of 55 DEG C
Stir about 1 hour, sampling is biodegradable micro lubricating oil when observing fully transparent.
The preparation method of above-mentioned polyester 3#: by 90.12kg (1000mol) butanediol and 116.07kg (1000mol)
Fumaric acid adds in polymeric kettle, adds 2.5kg storng-acid cation exchange resin (D001 macropore strong acid benzene second
Alkene cation exchanger resin) carry out polyreaction as catalyst, reaction temperature at 200 DEG C, the response time
Being 10 hours, the n-butyl alcohol being subsequently adding 3kg blocks, and decompression removes moisture content, unreacted butanediol,
After removing storng-acid cation exchange resin, obtain a kind of polyester.
Embodiment 7:
Weigh 72kg succinic acid di-isooctyl, 16kg polyester 3#, 6.5kg N-Oleoylsarcosine, 1kg tall oil
Acid, 2.5kg tributyl phosphate, 2kg triethanolamine borate are separately added in agitator at a temperature of 55 DEG C
Stir about 1 hour, sampling is biodegradable micro lubricating oil when observing fully transparent.
The above-mentioned biodegradable micro lubricating oil preparing above-mentioned preparation is carried out biodegradable experiment:
1. experimental technique: GB/T 21856-2008 chemicals fast degradation carbon dioxide produces test.
2. experiment material:
2.1 fluid: the biodegradable micro lubricating oil of above-described embodiment 7 preparation.
2.2 inoculums: take from soil at different local earth's surface 0-10cm, soil sample, after mixing, remove impurity, is used
Deionized water soaking and stirring takes supernatant.
3. experimental result:
Calculating 28 days biological degradation rates is: 87.56%.
Embodiment 8:
Weigh 64kg ethylene glycol laurate, 18kg polyester 3#, 7kg Hamposyl L, 4kg tall oil,
4kg lauryl phosphate, 3kg triethanolamine borate are separately added in agitator stir about at a temperature of 54 DEG C
1 hour, sampling was biodegradable micro lubricating oil when observing fully transparent.
Embodiment 9:
Weigh 63kg propylene glycol oleate, 17kg polyester 3#, 7.5kg Hamposyl S, 4.5kg
Tall oil acid, 4.5kg tributyl phosphate, 3.5kg triethanolamine borate are separately added in agitator at 54 DEG C
At a temperature of stir about 1 hour, sampling is biodegradable micro lubricating oil when observing fully transparent.
Claims (8)
1. a biodegradable micro lubricating oil, it is characterised in that: consist of the following components in percentage by weight:
Described dibasic acid esters is dioctyl adipate, dioctyl azelate, di-n-octyl sebacate, DDA, nonyl
Diacid two isodecyl ester, DI(2ETHYLHEXYL)SEBACATE, succinic acid di-isooctyl, DID Su, ethylene glycol
The mixture of one or more in laurate, propylene glycol oleate.
2. a kind of biodegradable micro lubricating oil as claimed in claim 1, it is characterised in that described fatty acyl
Sarcosine is to be prepared from by acylation reaction with sarcosine by the saturated of C8-C20 or unsaturated carboxylic acid.
3. a kind of biodegradable micro lubricating oil as claimed in claim 1, it is characterised in that:
The product that described dibasic acid esters is dihydroxylic alcohols and monoacid or binary acid and monohydric alcohol esterification generates.
4. a kind of biodegradable micro lubricating oil as claimed in claim 1, it is characterised in that:
The preparation method of described polyester is: dihydroxylic alcohols and binary acid is added in polymeric kettle for 1:1 in molar ratio, adds
Enter storng-acid cation exchange resin and carry out polyreaction as catalyst, reaction temperature at 180～220 DEG C,
Response time is 8～12 hours, is subsequently adding a certain proportion of monocarboxylic acid or monohydric alcohol blocks, subtract
Pressure removes moisture content, after removing storng-acid cation exchange resin, prepares.
5. a kind of biodegradable micro lubricating oil as claimed in claim 1, it is characterised in that:
Described alkyl phosphate is selected from oleyl alcohol phosphate ester, lauryl alcohol phosphate ester, diisooctyl phosphoric acid ester, single lauryl
In phosphate ester, tributyl phosphate, polyoxyethylene monoalkyl phosphoric acid esters, polyoxyethylene bisalkyl phosphate one
Kind or several compositionss.
6. a kind of biodegradable micro lubricating oil as claimed in claim 1, it is characterised in that:
Described hydramine borate is in monoethanolamine borate, diethanolamine borate, triethanolamine borate
The compositions of one or more.
7. a kind of biodegradable micro lubricating oil as described in claim 1-2 is arbitrary, it is characterised in that:
Described fatty acyl sarcosines one in Hamposyl L, N-Oleoylsarcosine, the Hamposyl S or
Several compositionss.
8. the preparation method of a kind of biodegradable micro lubricating oil as described in claim 1-7 is arbitrary, its feature
It is:
Weigh dibasic acid esters, polyester, fatty acyl sarcosines, tall oil acid or tall oil, alkyl phosphoric acid by weight percentage
Ester, hydramine borate, be sequentially added in agitator and stir 1-2 hour at a temperature of 40～60 DEG C, sampling
When observing fully transparent.
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| CN104844747B (en) * | 2015-03-13 | 2016-11-09 | 上海金兆节能科技有限公司 | Butene dioic acid resin and preparation method thereof and by this resin-made for degradable micro lubricating oil |
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| CN106632456B (en) * | 2016-12-20 | 2018-08-14 | 上海金兆节能科技有限公司 | Sweet dew polyol fatty acid phosphate and preparation method thereof and prepare environmentally friendly micro lubricating oil with ester |
| CN109439386B (en) * | 2018-12-02 | 2021-06-25 | 上海金兆节能科技有限公司 | Environment-friendly degradable trace lubricating oil and preparation method thereof |
| CN110510901A (en) * | 2019-08-20 | 2019-11-29 | 江苏博拓新型建筑材料有限公司 | A kind of rust-proof type water-reducing agent and preparation method thereof |
| CN114479997A (en) * | 2021-12-17 | 2022-05-13 | 东莞市耐斯润滑科技有限公司 | Method and process for producing environment-friendly trace lubricating oil based on renewable resource material |
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| CN102220183A (en) * | 2011-05-11 | 2011-10-19 | 广州市联诺化工科技有限公司 | Vegetable oil-based water-soluble cutting fluid |
| CN103113568A (en) * | 2012-12-31 | 2013-05-22 | 上海源育节能环保科技有限公司 | 1,4-butanediol-terminated polybutylene succinate and preparation method thereof, and environment-friendly near-dry cutting oil prepared from polybutylene succinate |
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