CN109181812A - A kind of C60Inclusion compound and its preparation method and application - Google Patents

A kind of C60Inclusion compound and its preparation method and application Download PDF

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Publication number
CN109181812A
CN109181812A CN201811211817.8A CN201811211817A CN109181812A CN 109181812 A CN109181812 A CN 109181812A CN 201811211817 A CN201811211817 A CN 201811211817A CN 109181812 A CN109181812 A CN 109181812A
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China
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inclusion compound
lubricating
cage
toluene
mixed liquor
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CN109181812B (en
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关集俱
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Suzhou Vocational Institute of Industrial Technology
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Suzhou Vocational Institute of Industrial Technology
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    • 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
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/08—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic sulfur-, selenium- or tellurium-containing compound
    • 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
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/02—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic oxygen-containing compound
    • 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
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/10—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic phosphorus-containing compound
    • 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
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/04—Elements
    • C10M2201/041—Carbon; Graphite; Carbon black
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/126—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids monocarboxylic
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/283—Esters of polyhydroxy compounds
    • 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
    • C10M2219/022—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of hydrocarbons, e.g. olefines
    • 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/083—Dibenzyl sulfide
    • 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
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

A kind of C of the invention60Inclusion compound, by the waste of following parts by weight: C60Account for 85~90 parts, lubricating additive account for 10~15 parts；C60Inclusion compound is to be filled into the C through opening cage processing under high pressure, hot conditions by lubricating additive60Cavity in obtained zero-dimension nano carbon composite.Lubricating additive is one of dialkyl pentasulfide, oleic acid, oleic acid glycol ester, sulfide isobutene, curing benzyl and triethyl phosphate.C of the invention60Inclusion compound is with C60Based on molecule, first by C60Cage is opened, C can be improved in opening binding activity chemical group in the process by opening cage60In the dispersion stabilization and dissolubility of lubricating oil.In friction process, C60Inclusion compound penetrates into friction area with lubricating oil, and inclusion compound is extruded and deforms, C of the lubricating additive from rupture60Release, and lubricating film is generated by absorption physically or chemically and plays lubricating action, to improve C60Antifriction, wear-resistant and extreme pressure property.

Description

A kind of C60Inclusion compound and its preparation method and application
Technical field
The present invention relates to technical field of lubricant more particularly to a kind of fullerene-C for filling lubricating additive60Packet Close object and its preparation method and application.
Background technique
Fullerene-C60(C60) Footballene with symmetrical structure being made of 60 carbon atoms, C60Molecule it is straight Diameter is 0.71nm, and spherical surface is by 12 pentagons and the condensed 32 face body of caged constituted of 20 hexagons, each carbon therein Atom passes through sp2.28Hydridization is bonded with neighboring atom.Nanometer C60Hollow cage structure make it have special physics, chemically Can, small-size effect, skin effect possessed by nanoparticle, quantum size effect etc. in addition, so as to C60And its derivative Research be always the research hotspot in the fields such as theoretical chemistry, material devices, biological medicine, and be expected in engineering, machinery, the energy And the fields such as medicine play a role.
Early in 1985, Kroto just predicted C60And its derivative will be a super lubricant.Subsequent C60And its it is derivative The greasy property of object is studied much, and proves C60It can be used as a kind of " molecule microballoon ball " lubricant, play good Antifriction anti-friction effect.But C60When additive as lubricating oil, also have the disadvantages that
(1)C60There is no dissolubility in common base oil, can only use the methods of mechanical stirring, ultrasound, solid abrasive will It is scattered in lubricating fluid, but since it belongs to multiphase dispersion in lubricant medium, has huge interface energy, intermolecular to draw Power keeps nanoparticle accumulation agglomerating, and the particle of reunion can reach micron order again, leads to the reduction of its greasy property, it is difficult to realize ideal " molecule ball " imagine.
(2)C60Surface does not have active chemical group or element, can not generate chemistry with metal under violent friction condition Adsorbed film plays lubricating action, causes its bearing capacity under high speed, heavily loaded friction condition not strong.
Existing technology generallys use the method for chemical modification to change the physicochemical properties of C60, to improve C60 in base Surface charge can, be eliminated in dissolubility in plinth oil, the surface for reducing C60.Basic skills used by the chemical modification of C60 be Its surface introduces such as copolymer, rouge, carboxylic acid isoreactivity chemical group, to increase dissolubility, dispersion stabilization and the lubrication of C60 Property, but using effect is still undesirable at present.
Currently, there is no the report for filling lubricating additive in the cavity of C60.The present invention first carries out out cage processing to C60, Active chemical group is introduced while opening cage, is added while improving its dispersibility, dissolubility and lubricity, then by lubrication Agent molecule is filled into the cage of C60, can further improve the greasy property of C60.It finally realizes a kind of " interior to fill, dispatch workers to do on-site repairs The C60 inclusion compound of decorations " type.
Summary of the invention
The object of the present invention is to provide a kind of C60The preparation method and C of inclusion compound60Inclusion compound and its application, to solve Problems of the prior art.
To achieve the goals above, the present invention provides a kind of C60Inclusion compound and its preparation method and application.
A kind of first aspect: C60Inclusion compound
A kind of C60Inclusion compound, it is characterised in that: by the waste of following parts by weight: C60Account for 85~90 parts, lubrication addition Agent accounts for 10~15 parts；The C60Inclusion compound is to be filled into be opened cage processing under high pressure, hot conditions by the lubricating additive C60Cavity in obtained zero-dimension nano carbon composite.
Further, the lubricating additive is dialkyl pentasulfide, oleic acid, oleic acid glycol ester, sulfide isobutene (T321), one of curing benzyl and triethyl phosphate.
Second aspect: C60The preparation method of inclusion compound
C60The preparation method of inclusion compound, it is characterised in that: the following steps are included:
(1) utilize miscellaneous nitrogen method by C60It opens cage: first 2, the 3- benzodiazine of 15g being dissolved into 500ml toluene, adds 2g C60；Mixed liquor is flowed back 8h under conditions of being heated to 80 DEG C again, is tracked and is reacted using thin-layer chromatography, until sample spot is not sent out Changing, entire react continue 18-22h.
(2) on a rotary evaporator, the mixed liquor through sufficiently reacting in above-mentioned (1) is evaporated under reduced pressure, heating temperature 120 DEG C, obtain concentrate.
(3) separating-purifying is carried out to the concentrate in above-mentioned (2) using silica gel column chromatography method, is injected to silica gel chromatographic column Eluant, eluent carries out eluting the isolated C for opening cage60Derivative.
(4) cage C will be opened prepared by (3)60Derivative is dissolved in 200ml toluene, and one kind of 20ml 0.5mol/L is added The solution of lubricating additive；Mixed liquor is poured into autoclave, is pressed under conditions of 200 DEG C, 200atm and magnetic agitation 12h is reacted under power.
(5) after reaction to (4), mixed liquor is evaporated under reduced pressure, obtains concentrate, again by obtained concentrate Silica gel chromatographic column chromatography is carried out, is eluted, is isolated and purified with eluant, eluent, can be prepared by C60With a kind of inclusion of lubricating additive Object.
Further, the eluant, eluent in step (3) is the mixed liquor of toluene and petroleum ether, wherein the body of toluene and petroleum ether Product is than being 2: 1.
Further, in step (4) in the solution of lubricating additive, solvent used is dehydrated alcohol or acetone.
Further, the eluant, eluent in step (5) is the mixed liquor of toluene and petroleum ether, wherein the body of toluene and petroleum ether Product is than being 2: 1.
The third aspect: C60The application of inclusion compound
The C of first aspect60Inclusion compound and C by second aspect60The C that the preparation method of inclusion compound is prepared60Inclusion Application of the object in lubricating oil.
The invention has the following beneficial effects:
(1) in C60Carbon cage surface open sizeable notch after, small molecule lubrication addition can be made under certain condition Agent molecule is embedded to form inclusion compound, C60Molecular diameter about 0.71nm, this size with small molecule lubricant molecule is more It coincide, has the condition to form inclusion compound.
(2) C of a kind of embedded lubricating additive proposed by the present invention60Inclusion compound, with C60Based on molecule, pass through miscellaneous nitrogen It chemically reacts C60Cage is opened, while can make to introduce active group on its forelock key, this both increases C60It is steady in the dispersion of base oil Dissolubility that is qualitative, also making it certain in base oil, dissolved C60It is easier to penetrate into friction area, to increase lubrication The lubricant effect of oil.
(3) pure C60With preferable friction-reducing and antiwear action, but under the harsh operating condition compared with big load, speed, C60Profit Sliding effect can reduce.In the present invention, C60When inclusion compound is as lubricating additive, friction area can be penetrated into lubricating oil, rubbed During wiping, inclusion compound is extruded, deforms and ruptures, and lubricating additive can be released, and raw by absorption physically or chemically Lubricating action is played at lubricating film, to improve C60Antifriction, wear resistence and extreme pressure property, as shown in Figure 2.
(4) a kind of lubricating oil prepared by the present invention, the C containing above-mentioned embedded lubricating additive60Inclusion compound is pure with adding The lubricating oil of carbon nanotube is compared, and adds the lubricating oil of inclusion compound under the conditions of identical friction testing, coefficient of friction can lower 5%, wear rate reduces 20%, the maximum nonseizure load (P of lubricating oilBValue) improve 20%.
Detailed description of the invention
Fig. 1 is to make C using benzodiazine60Open the schematic diagram of the chemical reaction process of cage；
Fig. 2 is C60Lubricating action model of the inclusion compound in cutting friction area；
Fig. 3 is to open cage C made from embodiment 160Infrared spectrogram；
Fig. 4 is RC2540 and C made from embodiment 160The infrared spectrogram of inclusion compound；
Fig. 5 is T321 and C made from embodiment 260The infrared spectrogram of inclusion compound；
Fig. 6 is to open cage C made from embodiment 160's1H-NMR nuclear magnetic spectrogram；
Fig. 7 is RC2540 and C made from embodiment 160Inclusion compound1H-NMR nuclear magnetic spectrogram；
Fig. 8 is T321 and C made from embodiment 260Inclusion compound1H-NMR nuclear magnetic spectrogram；
Fig. 9 is C60, T321 and C60The coefficient of friction relational graph of-T321 inclusion compound；
Figure 10 is C60, T321 and C60The wear scar diameter relational graph of-T321 inclusion compound；
Oil, C based on Figure 1160, T321 and C60Maximum nonseizure load (the P of-T321 inclusion compoundBValue) relational graph.
Wherein:
1, the C ruptured60；2, lubricant；3, lubricating film.
Specific embodiment
The present invention will be further described with attached drawing combined with specific embodiments below, to help the contents of the present invention are understood.
Embodiment 1
A kind of C of embedded dialkyl pentasulfide (RC2540) of embodiment 160The preparation method of inclusion compound, including it is following Step:
(1) utilize miscellaneous nitrogen method by C60It opens cage: first 2, the 3- benzodiazine (phthalazines) of 15g being dissolved into 500ml toluene, then The C of 2g is added60；Mixed liquor is flowed back 8h under conditions of being heated to 80 DEG C again, is tracked and is reacted using thin-layer chromatography (TLC), directly It does not change to sample spot, entire react continues 20h, which opens cage reaction process such as Fig. 1.
(2) on a rotary evaporator, the mixed liquor through sufficiently reacting in above-mentioned (1) is evaporated under reduced pressure, heating temperature 120 DEG C, obtain concentrate.
(3) separating-purifying is carried out to the concentrate in above-mentioned (2) using silica gel column chromatography method, using toluene and petroleum ether Mixed liquor as eluant, eluent, wherein the volume ratio of toluene and petroleum ether is 2: 1；When purification, first with eluant, eluent by the silica gel of 50g It is attached to after being impregnated in the chromatographic column that a diameter is 30mm, a length of 300mm.Then the concentrate in (2) is dissolved into 12g elution Preparative separation sample in agent, and be added to the upper layer of silicagel column stationary phase, then cover one layer of absorbent cotton injects toluene and petroleum ether Eluant, eluent is eluted.Unreacted C is isolated first60, next product isolated is out cage C60Derivative finally will Next product eluted is evaporated under reduced pressure, and cage C can be obtained out60Derivative.
(4) cage C will be opened prepared by (3)60Derivative (0.25g) is dissolved in 200ml toluene, and 20ml 0.5mol/ is added The acetone soln of the dialkyl pentasulfide of L；Mixed liquor is poured into autoclave, in 200 DEG C, 200atm and magnetic agitation Under conditions of react 12h under pressure.
(5) after reaction to (4), mixed liquor is evaporated under reduced pressure, obtains concentrate, and with toluene and ethyl acetate Mixed liquor be eluant, eluent, wherein the volume ratio 2: 1 of toluene and ethyl acetate, carries out silica gel chromatograph for obtained concentrate again Column chromatography, can be prepared by C60With the inclusion compound of dialkyl pentasulfide.And it is determined by the quality analysis of different separation samples The yield of inclusion compound.
Embodiment 2
A kind of C of embedded sulfide isobutene (T321) of embodiment 260The preparation method of inclusion compound, comprising the following steps:
(1) utilize miscellaneous nitrogen method by C60It opens cage: first 2, the 3- benzodiazine (phthalazines) of 15g being dissolved into 500ml toluene, then The C of 2g is added60；Mixed liquor is flowed back 8h under conditions of being heated to 80 DEG C again, is tracked and is reacted using thin-layer chromatography (TLC), directly It does not change to sample spot, entire react continues 20h, which opens cage reaction process such as Fig. 1.
(2) on a rotary evaporator, the mixed liquor through sufficiently reacting in above-mentioned (1) is evaporated under reduced pressure, heating temperature 120 DEG C, obtain concentrate.
(3) separating-purifying is carried out to the concentrate in above-mentioned (2) using silica gel column chromatography method, using toluene and petroleum ether Mixed liquor as eluant, eluent, wherein the volume ratio of toluene and petroleum ether is 2: 1；When purification, first with eluant, eluent by the silica gel of 50g It is attached to after being impregnated in the chromatographic column that a diameter is 30mm, a length of 300mm.Then the concentrate in (2) is dissolved into 12g elution Preparative separation sample in agent, and be added to the upper layer of silicagel column stationary phase, then cover one layer of absorbent cotton injects toluene and petroleum ether Eluant, eluent is eluted.Unreacted C is isolated first60, next product isolated is out cage C60Derivative finally will Next product eluted is evaporated under reduced pressure, and cage C can be obtained out60Derivative.
(4) cage C will be opened prepared by (3)60Derivative (0.25g) is dissolved in 200ml toluene, and 20ml 0.5mol/ is added The acetone soln of the sulfide isobutene of L；Mixed liquor is poured into autoclave, in 200 DEG C, the item of 200atm and magnetic agitation 12h is reacted under pressure under part.
(5) after reaction to (4), mixed liquor is evaporated under reduced pressure, obtains concentrate, and with toluene and ethyl acetate Mixed liquor be eluant, eluent, wherein the volume ratio 2: 1 of toluene and ethyl acetate, carries out silica gel chromatograph for obtained concentrate again Column chromatography, can be prepared by C60With inclusion compound, that is, C of sulfide isobutene60- T321 inclusion compound.And pass through the matter of different separation samples Amount analyzes the yield to determine inclusion compound.
Confirmatory experiment 1:
In order to prove C obtained by embodiment 1-260There is the presence of RC2540 and T321 ingredient in inclusion compound, this verifying is real 1 is tested using infrared spectroscopy (IR) analytic approach to C made from embodiment 1-260Inclusion compound is characterized, and opens cage according to filling front and back C60Infrared region absorption peak characteristic differences, to judge whether C60 with lubricating additive has occurred filling effect.
Firstly, to the C by opening cage processing and not being filled60Infrared spectrum analysis is carried out, as shown in Figure 3.Wave in the figure Number is 1429cm-1、1179cm-1、1020cm-1、573cm-1And 527cm-1Strong peak belong to C60.Wave number is 3321cm-1、 2821cm-1、1520cm-1Deng peak should belong to the absorption peak of hydroxyl and carboxyl, this shows the C by opening cage processing60It takes The functional group of hydroxyl and carboxyl.
Secondly, to the C of RC2540 or T321 is filled with60Inclusion compound carries out infrared spectrum analysis, the characteristic absorption of inclusion compound Occur lubricating additive and C in spectrum simultaneously60Characteristic peak, and there is change in the position of peak value, as shown in Figure 4, Figure 5, this card The C of filling lubricating additive is illustrated60Close the formation of object.
Confirmatory experiment 2:
In order to further prove C obtained by embodiment 1-260There is the presence of RC2540 and T321 ingredient in inclusion compound, this The test of the use nuclear magnetic resonance of confirmatory experiment 2 (1H-NMR) spectral method is to C made from embodiment 1-260Inclusion compound is characterized, according to Open cage C in filling front and back60Chemical shift variation, to judge C60Whether with lubricating additive filling effect is had occurred.
Nuclear magnetic resonance test (1H-NMR CS) is used2As solvent, D2O is as capillary internal standard.Cage C is opened shown in Fig. 660's Chemical shift are as follows: 67.2082,6.4247,6.3667,6.1571,6.1214 (s, 1H)；δ 5.7202,5.6907 (s, 2H)；δ 4.7065 (s, D2O)。
Fig. 7, Fig. 8 are respectively the inclusion compound of RC2540 and T3211H H NMR spectroscopy, it is seen that after clathration occurs, nuclear-magnetism spectrum Occurs new chemical shift in figure, these chemical shifts belong to the H in RC2540 and T321 molecule；In addition, original opens cage C60 The mobile trend of chemical shift oriented High-Field, and H proton closer from sulphur atom in RC2540, T321 strand, chemistry The offset of displacement is more obvious, and shows that the S -- S in RC2540, T321 enters C60Cage in, this demonstrate that RC2540, T321 With C60The formation of inclusion compound.
Confirmatory experiment 3
C is measured using x-ray photoelectron spectroscopy (XPS)60, open cage C60With C60Essential element ingredient in inclusion compound and its Content, it can be 80eV, monochromatic AlK alpha ray source, pollution carbon C that electronics is logical when test1sCombination energy 284.8eV make internal standard, about member The results are shown in Table 1 for cellulose content.It can be seen that after opening cage, C60Oxygen content significantly improve, it was demonstrated that introduced while opening cage Other functional groups；Meanwhile the S constituent content of RC2540 inclusion compound and T321 inclusion compound is respectively 19.66% and 18.18%, is filled Divide and demonstrates the presence of lubricating additive ingredient in inclusion compound.
1 C of table60, open cage C60With C60The content (Mass Conc%) of C, O, S element in inclusion compound
Comparison study example 1
This application comparative example 1 is by C made from embodiment 260- T321 inclusion compound is used to prepare lubricating oil, the specific lubricating oil Including being made by following raw material: the C of 98 parts of certain commercial lubricating oil and 2 parts of embodiments 260- T321 inclusion compound.At the same time, it is arranged 1: 100 part of the control group above-mentioned commercial lubricating oil i.e. base oil for not adding any substance；Control group 2: containing 98 parts of above-mentioned commodity profits Lubricating oil and 2 parts of pure T321；Control group 3: contain 98 parts of above-mentioned commercial lubricating oils and 2 parts of untreated C60；Above four groups of lubricating oil Four ball friction tests are carried out, experimental condition: load 245N, room temperature, test speed 1000r/min, time 30min, every group of progress Parallel laboratory test three times, coefficient of friction are averaged, and test result is as shown in Figure 9.Wear scar diameter is measured microscopically with optics, is removed It tries the average value of wear scar diameter, test result is as shown in Figure 10.The P of lubricating oilBValue presses " GB/T12583-1998 lubricant pole Pressure performance measurement method (four ball method) " it is measured, test result is as shown in figure 11.It is obtained by friction test result, in general C60The antifriction of the improvement lubricating oil of-T321 inclusion compound, wear-resistant and extreme pressure property are best.
In the present invention, C60When with the inclusion compound of lubricating additive as lubricating additive, it can penetrate into and rub with basal liquid Region is wiped, in friction process, inclusion compound is extruded and deforms, C of the lubricant 2 from rupture601 release, and by physically or chemically Absorption generate lubricating film 3 play lubricating action, to improve the antifriction of C60, wear resistence and extreme pressure property.
Specific case used herein elaborates inventive concept, the explanation of above example is only intended to Help understands core of the invention thought.It should be pointed out that for those skilled in the art, not departing from this Under the premise of inventive concept, any obvious modification, equivalent replacement or the other improvements made should be included in the present invention Protection scope within.

Claims (7)

1. a kind of C60Inclusion compound, it is characterised in that: by the waste of following parts by weight: C60Account for 85~90 parts, lubricating additive Account for 10~15 parts；The C60Inclusion compound is to be filled into handle through opening cage under high pressure, hot conditions by the lubricating additive C60Cavity in obtained zero-dimension nano carbon composite.
2. C according to claim 160Inclusion compound, it is characterised in that: the lubricating additive be dialkyl pentasulfide, One of oleic acid, oleic acid glycol ester, sulfide isobutene, curing benzyl and triethyl phosphate.
3. a kind of C of any of claims 1 or 260The preparation method of inclusion compound, it is characterised in that: the following steps are included:
(1) utilize miscellaneous nitrogen method by C60It opens cage: first 2, the 3- benzodiazine of 15g being dissolved into 500ml toluene, adds 2g's C60；Mixed liquor is flowed back 8h under conditions of being heated to 80 DEG C again, is tracked and is reacted using thin-layer chromatography, until sample spot does not occur Variation, entire react continue 18-22h；
(2) on a rotary evaporator, the mixed liquor through sufficiently reacting in above-mentioned (1) is evaporated under reduced pressure, heating temperature 120 DEG C, obtain concentrate；
(3) separating-purifying is carried out to the concentrate in above-mentioned (2) using silica gel column chromatography method, injects and elutes to silica gel chromatographic column Agent, which elute, isolated opens cage C60Derivative；
(4) cage C will be opened prepared by (3)60Derivative is dissolved in 200ml toluene, and a kind of lubrication of 20ml 0.5mol/L is added The solution of additive；Mixed liquor is poured into autoclave, under conditions of 200 DEG C, 200atm and magnetic agitation under pressure React 12h；
(5) after reaction to (4), mixed liquor is evaporated under reduced pressure, obtains concentrate, obtained concentrate is carried out again Silica gel chromatographic column chromatography, is eluted with eluant, eluent, is isolated and purified, can be prepared by C60With a kind of inclusion compound of lubricating additive.
4. C as claimed in claim 360The preparation method of inclusion compound, it is characterised in that: eluant, eluent in step (3) be toluene with The mixed liquor of petroleum ether, wherein the volume ratio of toluene and petroleum ether is 2: 1.
5. C as claimed in claim 360The preparation method of inclusion compound, it is characterised in that: the solution of the lubricating additive of step (4), Solvent used is dehydrated alcohol or acetone.
6. C as claimed in claim 360The preparation method of inclusion compound, it is characterised in that: eluant, eluent in step (5) be toluene with The mixed liquor of petroleum ether, wherein the volume ratio of toluene and petroleum ether is 2: 1.
7. a kind of C of any of claims 1 or 260Inclusion compound and any preparation method of claim 3-6 are prepared C60Application of the inclusion compound in lubricating oil.
CN201811211817.8A 2018-10-17 2018-10-17 C60Preparation method and application of inclusion compound Active CN109181812B (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1718538A (en) * 2004-07-08 2006-01-11 北京化工大学 Method of perforating on fullerene ball surface
US20080247930A1 (en) * 2006-03-18 2008-10-09 Robert Hotto Nano-fusion reaction
EP2392555A2 (en) * 2009-01-29 2011-12-07 Korea Research Institute of Chemical Technology (KRICT) Fullerene derivatives and organic electronic device comprising the same
CN102807553A (en) * 2011-05-30 2012-12-05 财团法人工业技术研究院 Fullerene derivative and photoelectric element
WO2013131521A1 (en) * 2012-03-05 2013-09-12 Kyoto University Open-cage fullerenes and a method for preparing the same
CN107353990A (en) * 2017-06-26 2017-11-17 苏州工业职业技术学院 A kind of water-based nano-fluid cutting fluid for adding carbon mano-tube composite and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1718538A (en) * 2004-07-08 2006-01-11 北京化工大学 Method of perforating on fullerene ball surface
US20080247930A1 (en) * 2006-03-18 2008-10-09 Robert Hotto Nano-fusion reaction
EP2392555A2 (en) * 2009-01-29 2011-12-07 Korea Research Institute of Chemical Technology (KRICT) Fullerene derivatives and organic electronic device comprising the same
CN102807553A (en) * 2011-05-30 2012-12-05 财团法人工业技术研究院 Fullerene derivative and photoelectric element
WO2013131521A1 (en) * 2012-03-05 2013-09-12 Kyoto University Open-cage fullerenes and a method for preparing the same
CN107353990A (en) * 2017-06-26 2017-11-17 苏州工业职业技术学院 A kind of water-based nano-fluid cutting fluid for adding carbon mano-tube composite and preparation method thereof

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