CN107417555B - A kind of two-(2- glycine) ester derivative lube oil additive of butanediol and preparation method thereof - Google Patents

A kind of two-(2- glycine) ester derivative lube oil additive of butanediol and preparation method thereof Download PDF

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CN107417555B
CN107417555B CN201710419008.5A CN201710419008A CN107417555B CN 107417555 B CN107417555 B CN 107417555B CN 201710419008 A CN201710419008 A CN 201710419008A CN 107417555 B CN107417555 B CN 107417555B
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butanediol
glycine
ester derivative
lube oil
preparation
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CN107417555A (en
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韩利芬
戴康徐
赵鸿斌
曹华
鲁浩
张文涛
陆建雄
刘文杰
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Boao Zongheng Network Technology Co ltd
Guangzhou Ding Yuan Environmental Protection Technology Co ltd
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Dongguan University of Technology
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C229/06—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton
    • C07C229/10—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
    • C07C229/12—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings to carbon atoms of acyclic carbon skeletons
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C229/06—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton
    • C07C229/10—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
    • C07C229/14—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings to carbon atoms of carbon skeletons containing rings
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/14—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D295/145—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals with the ring nitrogen atoms and the carbon atoms with three bonds to hetero atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
    • C07D295/15—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals with the ring nitrogen atoms and the carbon atoms with three bonds to hetero atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M133/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/38—Heterocyclic nitrogen compounds
    • C10M133/40—Six-membered ring containing nitrogen and carbon only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/221—Six-membered rings containing nitrogen and carbon only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40—Low content or no content compositions
    • C10N2030/41—Chlorine free or low chlorine content compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40—Low content or no content compositions
    • C10N2030/42—Phosphor free or low phosphor content compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40—Low content or no content compositions
    • C10N2030/43—Sulfur free or low sulfur content compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40—Low content or no content compositions
    • C10N2030/45—Ash-less or low ash content
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/64—Environmental friendly compositions

Abstract

The invention discloses a kind of environmentally protective multifunctional additive for lubricating oil butanediol two-(2- glycine) ester derivatives and preparation method thereof.Specifically: first under the effect of the catalyst, butanediol and monoxone obtain monoxone butanediol diester through esterification, then obtain the compound of structure shown in formula I with corresponding amine nucleo philic substitution reaction in the presence of alkali again.Preparation method of the invention is simple, and process conditions are mild, and raw material is easy to get, and synthesis cost is low, and synthetic yield is high.The multifunction additive that this novel no sulphur, without phosphorus, Halogen, ashless butanediol two-(2- glycine) ester derivative can be used as lubricating oil is used alone, it can also be used in combination with other lube oil additives, with good thermal stability, the extreme-pressure anti-wear antifriction performance of base oil can be obviously improved, the corrosion resistance for effectively improving base oil is a kind of environmentally protective biodegradable multifunctional additive for lubricating oil.

Description

A kind of two-(2- glycine) ester derivative lube oil additive of butanediol and its Preparation method
Technical field:
The present invention relates to a kind of two-(2- glycine) ester derivative lube oil additive of butanediol and its preparation sides Method, the analog derivative is especially suitable for lube oil additive technical field.
Background technique:
The rapid development of modern industry accelerates the consumption of the energy, and people are while finding new energy, to energy-saving Technology also conducts in-depth research.Lubricating oil can reduce the friction between mechanical part, reduce mechanical wear, be energy-saving Important technical, and lube oil additive be the key that improve lubricants performance.With the development of industry and environmental requirement Raising, the exploitation of lube oil additive is put forward new requirements, that is, require exploitation green high-efficient multifunctional lubricant add Add agent.
Ester group in esters additive molecule structure is easy to be adsorbed on metal surface and forms firm lubricant film, has good Good friction, lubrication characteristic, combines with alkylamine, can further improve its tribological property；Studies have shown that ester derivative After hydrolysis, biodegradable is CO2And H2O.Therefore, this patent design synthesizes a series of biodegradable butanediols two- (2- glycine) ester derivative is applied in lube base oil, the biodegradable of a kind of function admirable can be obtained Multifunctional additive for lubricating oil.
Summary of the invention:
In view of the deficiencies of the prior art, it is an object of the present invention to provide a kind of two-(2- glycine) esters of butanediol Derivative lube oil additive, sulfur-bearing, phosphorus, chlorine etc. do not have excellent extreme-pressure anti-wear to environment and the harmful element of health Corrosion resistance.
It is a further object to provide butanediol two-(2- glycine) the ester derivative lube oil additives Preparation method.
To achieve the above object, the invention adopts the following technical scheme:
A kind of two-(2- glycine) ester derivative lube oil additive of butanediol, the chemical structure with general formula I:
Wherein,
A kind of preparation method of two-(2- glycine) ester derivative lube oil additive of butanediol, including following step It is rapid:
(1) under the effect of the catalyst, intermediate 1, structure is made through esterification in butanediol and monoxone are as follows:
(2) in the presence of alkali, intermediate 1 and amine nucleo philic substitution reaction, obtain butanediol two-(the 2- amine such as general formula I Guanidine-acetic acid) ester derivative.
As a preferred embodiment of the above technical solution, step (1), reaction described in (2) reaction medium be tetrahydrofuran, chlorine Imitative, hexamethylene, acetone, ethyl acetate or C2-C4The mixing of one or more of fatty alcohol.
As a preferred embodiment of the above technical solution, in step (1), butanediol and chloroacetic molar ratio be 1.0:2.0~ 6.0。
As a preferred embodiment of the above technical solution, in step (2), the molar ratio of intermediate 1 and amine is 1.0:2.0~6.0.
As a preferred embodiment of the above technical solution, step (1), in (2), the amount ratio of reaction substrate and reaction medium is 1mol:(500~5000) mL.
As a preferred embodiment of the above technical solution, step (1), the reaction temperature in (2) are 0~80 DEG C.
As a preferred embodiment of the above technical solution, step (1), the reaction time in (2) are 2~12h.
As a preferred embodiment of the above technical solution, which can be used alone, and be added to mineral oil, synthesis In oil, lubricating oil (rouge), the lubricating oil of excellent extreme-pressure anti-wear and corrosion resistance can be obtained, can also be added with other lubricating oil Add agent to be used in combination, reaches synergistic function.
As a preferred embodiment of the above technical solution, the additive amount of the lube oil additive be lubricating oil 0.1wt%~ 15wt%.
The invention has the following advantages:
Two-(2- glycine) ester derivative of butanediol provided by the invention is used as lube oil additive, has good Heat resistance, excellent extreme-pressure anti-wear antifriction quality and outstanding corrosion resistance, be the outstanding multifunctional lubricating of a kind of comprehensive performance Oil additive；Its preparation process is simple, and reaction condition is mild, raw materials used cheap and easy to get, and synthetic yield is high；Additive " the nothing Sulphur ", " without phosphorus ", " Halogen ", " ashless " are a kind of biodegradable green lubrication oil additives.
Detailed description of the invention:
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of embodiment 1；
Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of embodiment 2；
Fig. 3 is the hydrogen nuclear magnetic resonance spectrogram of embodiment 3；
Fig. 4 is the hydrogen nuclear magnetic resonance spectrogram of embodiment 4；
Fig. 5 is the hydrogen nuclear magnetic resonance spectrogram of embodiment 5；
Fig. 6 is the mass spectrogram of embodiment 1；
Fig. 7 is the mass spectrogram of embodiment 2；
Fig. 8 is the mass spectrogram of embodiment 3；
Fig. 9 is the mass spectrogram of embodiment 4；
Figure 10 is the mass spectrogram of embodiment 5.
Specific embodiment:
In order to better understand the present invention, below by embodiment, the present invention is further described, and embodiment is served only for solving The present invention is released, any restriction will not be constituted to the present invention.
The preparation of intermediate 1:
21.7g monoxone, 9.0g1,4- fourth two are added in the 250mL three-necked flask equipped with water segregator and reflux condensing tube Alcohol, 1.8g ferric chloride hexahydrate and 80mL hexamethylene, temperature rising reflux reaction, after the volume of water in water segregator reaches theoretical value. Stop reaction, vacuum distillation removes hexamethylene, dissolved with methylene chloride, successively uses the Na of 10wt%2CO3Aqueous solution, saturated common salt Water washing, anhydrous magnesium sulfate dry, filter, and rotary evaporation removes solvent, obtain crude product, crude product is tied again with dehydrated alcohol Crystalline substance obtains the intermediate 1 of white needles.
Embodiment 1
9.0g di-n-butylamine, 7.3g intermediate 1,5.9g sodium bicarbonate and 100mL tetrahydro are added in 250mL three-necked flask Furans, temperature rising reflux react 5h.Stop reaction, it is cooling, it is filtered to remove insoluble matter, rotary evaporation removes solvent, uses methylene chloride Dissolution, saturated common salt water washing three times, anhydrous MgSO4It dries, filters, filtrate rotary evaporation removes methylene chloride, obtains yellowish Color liquid 6.6g, yield 85.5%.1H NMR(400MHz,CDCl3, TMS, ppm) and δ: 4.12 (d, J=2.1Hz, 4H), 3.32 (d, J=2.6Hz, 4H), 2.55 (dd, J=10.0,4.7Hz, 8H), 1.71 (d, J=2.5Hz, 4H), 1.48-1.38 (m, 8H),1.36–1.25(m,8H),0.94–0.87(m,12H).MALDI-TOF-MS,m/z:calcd for C24H48N2O4[M+1]+: 429.361,found:429.265。
Embodiment 2
16.9g dioctylamine, 7.3g intermediate 1,5.9g sodium bicarbonate and 100mL tetrahydro are added in 250mL three-necked flask Furans, temperature rising reflux react 5h.Stop reaction, it is cooling, it is filtered to remove insoluble matter, rotary evaporation removes solvent, uses methylene chloride Dissolution, saturated common salt water washing three times, anhydrous MgSO4It dries, filters, filtrate rotary evaporation removes methylene chloride, obtains yellowish Color liquid 6.9g, yield 89.1%.1H NMR(400MHz,CDCl3, TMS, ppm) and δ: 4.14 (d, J=7.1Hz, 4H), 3.27 (s, 4H), 2.53-2.37 (m, 8H), 1.64-1.52 (m, 4H), 1.28 (t, J=7.1Hz, 48H), 0.90 (s, 12H) .MALDI-TOF-MS,m/z:calcd for C40H80N2O4[M+1]+:653.612,found:653.443。
Embodiment 3
6.0g piperidines, 7.3g intermediate 1,5.9g sodium bicarbonate and 100mL tetrahydro furan are added in 250mL three-necked flask It mutters, temperature rising reflux reacts 5h.Stop reaction, it is cooling, it is filtered to remove insoluble matter, rotary evaporation removes solvent, molten with methylene chloride Solution, saturated common salt water washing three times, anhydrous MgSO4It drying, filtering, filtrate rotary evaporation removes methylene chloride, crude product is obtained, It is recrystallized with dehydrated alcohol, obtains buff powder 6.3g, yield 86.3%.1H NMR(400MHz,CDCl3,TMS,ppm)δ: 4.10 (d, J=5.4Hz, 4H), 3.13 (d, J=5.5Hz, 4H), 2.45 (d, J=4.2Hz, 8H), 1.69-1.52 (m, 12H), 1.39 (d, J=5.2Hz, 4H) .MALDI-TOF-MS, m/z:calcd for C18H32N2O4[M+1]+:341.236,found: 341.268。
Embodiment 4
7.0gN- methyl piperazine, 7.3g intermediate 1,5.9g sodium bicarbonate and 100mL tetra- are added in 250mL three-necked flask Hydrogen furans, temperature rising reflux react 5h.Stop reaction, it is cooling, it is filtered to remove insoluble matter, rotary evaporation removes solvent, uses dichloromethane Alkane dissolution, saturated common salt water washing three times, anhydrous MgSO4It dries, filters, filtrate rotary evaporation removes methylene chloride, obtains thick Product is recrystallized with dehydrated alcohol, obtains buff powder 6.2g, yield 88.5%.1H NMR(400MHz,CDCl3,TMS, Ppm) δ: 4.15 (s, 4H), 3.22 (s, 4H), 2.61-2.50 (m, 16H), 2.30 (s, 6H), 1.71 (t, J=2.8Hz, 4H) .MALDI-TOF-MS,m/z:calcd for C18H34N4O4[M+1]+:371.258,found:371.287。
Embodiment 5
11.3g dibenzylamine, 7.3g intermediate 1,5.9g sodium bicarbonate and 100mL tetrahydro are added in 250mL three-necked flask Furans, temperature rising reflux react 5h.Stop reaction, it is cooling, it is filtered to remove insoluble matter, rotary evaporation removes solvent, uses methylene chloride Dissolution, saturated common salt water washing three times, anhydrous MgSO4It dries, filters, filtrate rotary evaporation removes methylene chloride, is slightly produced Product are recrystallized with dehydrated alcohol, obtain white solid 6.4g, yield 87.7%.1H NMR(400MHz,CDCl3,TMS,ppm)δ: 7.38-7.23 (m, 20H), 4.09 (t, J=8.9Hz, 4H), 3.80 (s, 8H), 3.29 (d, J=3.4Hz, 4H), 1.69 (d, J =15.6Hz, 4H) .MALDI-TOF-MS, m/z:calcd for C36H40N2O4[M+1]+:565.299,found:565.246。
Lube oil additive made from embodiment 1-5 is tested for the property below.
1, tribological property is tested:
Referring to GB-3142-82, by the butanediol two-prepared in Examples 1 to 5 (2- glycine) ester derivative point It is dispersed in atoleine, lubricating oil is evaluated using the MS-10A type four-ball friction and wear test machine of Xiamen nature's mystery testing machine factory production Maximum nonseizure load (PBValue).Test II grade of GCr15 steel ball of standard that steel ball used is Shanghai Steel Ball Plant's production, diameter 12.7mm, hardness 59-61RC.Experimental condition is room temperature (25 DEG C), revolving speed 1450r/min, time 10s.PBValue is as shown in table 1.
1 maximum nonseizure load (P of tableBValue)
The results show that such butanediol two-(2- glycine) ester derivant additive is added in atoleine, liquid The P of paraffinBValue is significantly improved.Show the film strength when additive of Examples 1 to 5 can be improved lubricating oil work.
Referring to GB-3142-82, using the sintering load (P of MS-10A type four-ball friction and wear test machine evaluation lubricating oilD Value).Experimental condition is room temperature (25 DEG C), revolving speed 1450r/min, time 10s.PDValue is as shown in table 2.
2 sintering load (P of tableDValue)
The results show that such butanediol two-(2- glycine) ester derivant additive is added in atoleine, liquid The P of paraffinDValue is significantly improved.Show that the additive of Examples 1 to 5 can be improved the maximal work ability of lubricating oil.
Use the measurement of MS-10A type four-ball friction and wear test machine in additive amount for 1.0wt%, load 392N, revolving speed is 1450r/min, the wear scar diameter (WSD) of steel ball when the time is 30min, the results are shown in Table 3, and corresponding average friction coefficient is such as Table 4.
3 steel ball mill spot diameter (WSD) of table
The result shows that such butanediol two-(2- glycine) ester derivant is added in atoleine, atoleine WSD value is substantially reduced.Show that the additive of Examples 1 to 5 can be obviously improved the abrasion resistance of lubricating oil.
4 average friction coefficient of table
The result shows that such butanediol two-(2- glycine) ester derivant is added in atoleine, atoleine Average friction coefficient is substantially reduced.Show that the additive of Examples 1 to 5 can be improved the antifriction performance of lubricating oil.
2, heat stability testing:
The thermal stability of synthesized additive is investigated using 209 type thermogravimetric analyzers (TGA).Test condition are as follows: Ar Atmosphere, 10 DEG C/min of heating rate.The results are shown in Table 5.
The TGA decomposition temperature of 5 additive of table
The results show that the starting thermal decomposition temperature of additive synthesized by Examples 1 to 5 is 161 DEG C~268 DEG C, the second heat Decomposition temperature is 295 DEG C~354 DEG C, has good thermal stability.
3, corrosion resistance is tested:
Referring to GB/T 5096-1985, additive synthesized in Examples 1 to 5 is added with the additive amount of 1.0wt% Into atoleine, oil sample is made, carries out corrosion test.Test copper sheet used is put into oil sample after polishing, and is placed in 100 DEG C baking oven, constant temperature place 3.0h, after the test, take out copper sheet, are cleaned up with petroleum ether, compare Corrosion standards colour table, obtain The corrosion level of synthesized additive out.Test result is as shown in table 6.
6 copper strip test result of table
The results show that the corrosion level of the oil sample containing additive 1~5 is 1a, it is excellent to illustrate that additive 1~5 has Corrosion resistance.
Detailed synthetic method of the invention that the present invention is explained by the above embodiments, but the invention is not limited to above-mentioned Method does not mean that the present invention must rely on above-mentioned reaction condition and could implement.Person of ordinary skill in the field should It is illustrated, any improvement in the present invention, the change of equivalence replacement and reaction actual conditions to reaction dissolvent catalyst of the present invention Deng all of which fall within the scope of protection and disclosure of the present invention.

Claims (10)

1. a kind of two-(2- glycine) ester derivative lube oil additive of butanediol, which is characterized in that with general formula I Chemical structure:
Wherein,
2. a kind of preparation of two-(2- glycine) ester derivative lube oil additive of butanediol as described in claim 1 Method, which comprises the following steps:
(1) under the effect of the catalyst, intermediate 1, structure is made through esterification in butanediol and monoxone are as follows:
(2) in the presence of alkali, intermediate 1 and amine nucleo philic substitution reaction, obtain butanediol two-(the 2- amido second such as general formula I Acid) ester derivative.
3. a kind of preparation of two-(2- glycine) ester derivative lube oil additive of butanediol as claimed in claim 2 Method, which is characterized in that the reaction medium reacted in step (1), (2) is tetrahydrofuran, chloroform, hexamethylene, acetone, acetic acid second Ester or C2-C4The mixing of one or more of fatty alcohol.
4. a kind of preparation of two-(2- glycine) ester derivative lube oil additive of butanediol as claimed in claim 2 Method, which is characterized in that in step (1), butanediol and chloroacetic molar ratio are 1.0:2.0~6.0.
5. a kind of preparation of two-(2- glycine) ester derivative lube oil additive of butanediol as claimed in claim 2 Method, which is characterized in that in step (2), the molar ratio of intermediate 1 and amine is 1.0:2.0~6.0.
6. a kind of preparation of two-(2- glycine) ester derivative lube oil additive of butanediol as claimed in claim 2 Method, which is characterized in that in step (1), (2), the amount ratio of reaction substrate and reaction medium is 1mol:(500~5000) mL.
7. a kind of preparation of two-(2- glycine) ester derivative lube oil additive of butanediol as claimed in claim 2 Method, which is characterized in that the reaction temperature in step (1), (2) is 0~80 DEG C.
8. a kind of preparation of two-(2- glycine) ester derivative lube oil additive of butanediol as claimed in claim 2 Method, which is characterized in that the reaction time in step (1), (2) is 2~12h.
9. a kind of two-(2- glycine) ester derivative lube oil additive of butanediol as described in claim 1, feature It is, which can be used as the exclusive use of lubricating grease multiple function additive, can also be with other lube oil additives It is used in combination.
10. a kind of two-(2- glycine) ester derivative lube oil additive of butanediol as claimed in claim 9, special Sign is that the additive amount of the lube oil additive is 0.1wt%~15wt% of lubricating oil.
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Title
79086-01-4，444082-28-4,;ACS STN;《ACS STN》;20020816
Mono- and Diesters of N-Benzoylaminoacetic Acid as Antiwear Additives to Synthetic Oils;A. A. Makhmudova et al.;《 Russian Journal of Applied Chemistry》;20111231;第84卷(第4期);732-734
含氮、硫润滑油添加剂的合成、表征和润滑性能研究;焦叶叶;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20120415;全文
新型含氮、硫润滑油添加剂的合成、表征与性能研究;邓碧云;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20111215;全文

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