CN1173982C - Sulphur-containing organic compound modified metal-chalocogenide nm particles, its prepn. and application - Google Patents

Sulphur-containing organic compound modified metal-chalocogenide nm particles, its prepn. and application Download PDF

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CN1173982C
CN1173982C CNB981180876A CN98118087A CN1173982C CN 1173982 C CN1173982 C CN 1173982C CN B981180876 A CNB981180876 A CN B981180876A CN 98118087 A CN98118087 A CN 98118087A CN 1173982 C CN1173982 C CN 1173982C
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organic compound
nanoparticle
compound
sulfydryl
thiosalt
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CN1221748A (en
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刘维民
陈爽
杨生荣
张治军
薛群基
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Lanzhou Institute of Chemical Physics LICP of CAS
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Abstract

The present invention relates to oil-soluble nano-particles of metal-chalcogen compounds modified by organic compounds containing sulfhydryl or thiosalt and a synthetic method thereof. The compounds of the present invention have a novel general formula (I), wherein R is a straight chain or branched alkyl of C8 to C18, and M is metallic lead or zinc. The present invention also relates to a preparation method for the compounds. The new-type nano-particles can be used as additives of multifunctional lubricating oil (grease), and enables the lubricating oil (grease) to have good abrasion resistance and high carrying capacities.

Description

Organic compounds containing sulfur modified metal one chalcogen compound nanoparticle and its production and use
The present invention relates to a kind of organic compounds containing sulfur modified metal one chalcogen compound nanoparticle, Preparation Method And The Use.
Nano material is owing to its unique physics and chemical property have obtained paying attention to widely.In recent years, the preparation of nanoparticle, performance and applied research have become the forward position research field of multidisciplinary intersection.Inorganic nano-particle has the character of many uniquenesses, yet owing to its non-oil soluble and easily oxidizable make it be very restricted in the application aspect the tribology.
The object of the present invention is to provide a kind of new organic compound modified metal one chalcogen compound nanoparticle.
Further aim of the present invention provides a kind of preparation method who contains sulfydryl or the organic compound modified metal one chalcogen compound nanoparticle of thiosalt.
Another object of the present invention provides the purposes of above-claimed cpd aspect tribology.
The present invention realizes by following measure:
The novel organic compound modified metal that contains sulfydryl or thiosalt one chalcogen compound nanoparticle is found, and its structure is represented with following general formula:
R is C in the formula (I) 8～C 18The straight or branched alkyl, M is metallic lead or zinc.
Most preferably wherein R is formula (I) compound of hexadecyl.
M represents the molecule number of MS in the nanoparticle, is about dozens of; N represents the molecule number of left-half in the nanoparticle formula (I), is about dozens of to hundreds of.
Preparation method of the present invention may further comprise the steps:
A) use and to contain sulfydryl organic compound or thiosalt organic compound as modifier, as vulcanizing agent, with the soluble metal reactant salt, the chain length that wherein contains R in sulfydryl or the thiosalt organic compound is C with ammonium sulfide or alkali metalsulphide 8-C 18The straight or branched alkyl, soluble metallic salt comprises the metal-salt of plumbous and zinc;
B) in the presence of reaction medium;
C) 50-80 ℃ was reacted 0.5-12 hour down;
Contain in the method for sulfydryl or the organic compound modified metal one chalcogen compound nanoparticle of thiosalt in preparation, reaction medium is an acetone, and ethanol separately and the blending agent of water or combination and water;
Preparation contains in the method for sulfydryl or the organic compound modified metal one chalcogen compound nanoparticle of thiosalt the conversion between 0.1～2 ratio of the mol ratio of organic compounds containing sulfur and metal-salt.
Preparation contains in the method for sulfydryl or the organic compound modified metal one chalcogen compound nanoparticle of thiosalt, and the mol ratio of organic compounds containing sulfur and reaction medium is 1: 1000-50000.
The synthesizing of sulfydryl or the organic compound modified metal one chalcogen compound nanoparticle of thiosalt that contain involved in the present invention can be represented with following chemical equation:
Figure C9811808700041
R is that chain length is C in the formula 8-C 18The straight or branched alkyl, M is metallic lead or zinc.
The contriver finds that The compounds of this invention has good dispersiveness in organic solvent and lubricating oil.
Contain the organic compound modified metal of sulfydryl or thiosalt one chalcogen compound nanoparticle and add in the lubricating grease and can obtain good abrasion resistance, also have good supporting capacity simultaneously.
Contain the organic compound modified metal of sulfydryl or thiosalt one chalcogen compound nanoparticle and can be used as a kind of multifunctional lubricant fat additives use.
The addition that contains the organic compound modified metal of sulfydryl or thiosalt one chalcogen compound nanoparticle is 0.025～5.0 (weight percentage).
In order to understand the present invention better, describe by example.
Embodiment 1:
At 100 milliliters of acetone, ethanol adds 0.44 gram (0.67 mmole) double hexadecyl phosphorodithioic acid pyridinium salt in the mixed solvent of water, 60 ℃ of constant temperature, be stirred to complete molten after, add 0.16 gram (0.67 mmole) Na 2S9H 2The O crystal is stirred to whole dissolvings, slowly drips to contain 0.38 gram (1 mmole) Pb (Ac) 23H 2The O crystalline aqueous solution, stirring reaction 1 hour.Filter, wash with hot mixed solvent earlier, the back is washed with hot ethanol, and dry in vacuum drier, promptly gets the brown solid product: double hexadecyl phosphorodithioic acid finishing PbS nanoparticle.
Resulting product is through infrared spectra in the example, x-ray photoelectron spectroscopy, the X-ray powder diffraction, transmission electron microscope and 31The P spectral analysis of the nuclear magnetic resonance is confirmed to be the nanoparticle that will obtain.
1. results of IR
It is to carry out on Bio-Rad FTS-165 infrared spectrometer that IR analyzes.The double hexadecyl phosphorodithioic acid is modified the infrared spectra of PbS nanoparticle and is seen Fig. 1.Find out 2900cm by figure -1, 1465cm -1, 721cm -1With 920～980cm -1Absorption peak illustrated that chain alkyl does not lose in reaction, promptly prove the existence that double hexadecyl phosphorodithioic acid modifier is arranged in the PbS nanoparticle.And in the double hexadecyl phosphorodithioic acid pyridinium salt molecule P=S at 804cm -1The disappearance and the 650cm of the eigen vibration absorption peak at place -1The new spike that the place occurs is considered to because in reaction process, P=S opens with a kind of more stable conjugated structure of Pb effect formation caused.
2.X-ray photoelectron spectroscopic analysis result
The x-ray photoelectron spectroscopy analysis is to carry out on the multi-functional energy spectrometer of PHI-5702.The Pb of finishing and unmodified PbS nanoparticle 4fAnd S 2pThe bound energy of electronics is seen Fig. 2 and Fig. 3.The result shows, because the existence of coating materials has stoped the PbS nanoparticle to PbO and PbSO effectively 4Transformation, i.e. the existence of coating materials has stoped the aerial oxidation of PbS nanoparticle.
3.X-ray powder diffraction analytical results
The analysis of X-ray powder diffraction is to carry out on Rigaku D/max-rB X-ray powder diffraction instrument.Modified the X-ray powder diffraction analysis of PbS nanoparticle by the double hexadecyl phosphorodithioic acid and find out, modify in the PbS nanoparticle, the structure of PbS nanometer nuclear is the PbS of cubic structure.
4. tem study result
Tem study is to carry out on JEM-1200 EX/S type transmission electron microscope.Analytical results shows that modification PbS nanoparticle particle diameter is even, is about 5nm, is the not too near-spherical of rule, and does not have tangible agglomeration.
5. 31P spectral analysis of the nuclear magnetic resonance result
31The p spectral analysis of the nuclear magnetic resonance is to carry out on Bruker AM-400Hz type superconduction magnetic resonance spectroscopy instrument.The chemical shift of modifier double hexadecyl phosphorodithioic acid pyridinium salt is 108.80ppm, and the chemical shift of modifying the PbS nanoparticle is 95.37ppm, 95.31ppm, 95.26ppm and 95.21ppm, prove that reaction has taken place modifier double hexadecyl phosphorodithioic acid pyridinium salt and primitive reaction is complete.
The evaluation of product (1):
Resulting double hexadecyl phosphorodithioic acid pyridinium salt (DDP) finishing PbS nanoparticle in the example is dispersed in the chemical pure whiteruss, at the wear scar diameter of having measured on the four-ball tester under different load.Testing used four-ball tester is the vertical omnipotent friction wear testing machine of MMW-1 type that Jinan trier factory produces, and used steel ball is the secondary standard steel ball (φ 12.7mm, GCr15 bearing steel, HRc are 59-61) that Lanzhou Berings Factory produces.Test is at room temperature carried out, and addition is 0.05wt.%, and rotating speed is 1450 rev/mins, and test period is 30 minutes, the results are shown in Figure 4.The result shows that the DDP that only adds minute quantity modifies the PbS nanoparticle, can effectively improve the supporting capacity and the antiwear property of paraffin oil.
Embodiment 2:
At 100 milliliters of acetone, ethanol adds 1.15 gram (1.75 mmole) double hexadecyl phosphorodithioic acid pyridinium salts in the mixed solvent of water, 55 ℃ of constant temperature, be stirred to complete molten after, add 0.03 gram (0.13 mmole) Na 2S9H 2The O crystal is stirred to whole dissolvings, slowly drips to contain 0.22 gram (1 mmole) Zn (Ac) 22H 2The O crystalline aqueous solution, stirring reaction 1.5 hours.Filter, wash with hot mixed solvent earlier, the back is washed with hot ethanol, and dry in vacuum drier, promptly gets white solid product: double hexadecyl phosphorodithioic acid finishing ZnS nanoparticle.
The evaluation of product:
Resulting double hexadecyl phosphorodithioic acid finishing ZnS nanoparticle is dispersed in the analytically pure tetradecane, in SRV test aircraft measurements its wear scar diameter under different load.Test used SRV trier and produce Optimol SRV micro-moving frictional wear trier for Germany, used steel ball is the secondary standard steel ball (φ 9.525mm, GCr15 bearing steel, HRc are 59-61) that Lanzhou Berings Factory produces.Test is at room temperature carried out, and addition is 0.5wt.%, and frequency is 50Hz, and amplitude is 1mm, and test period is 30 minutes, the results are shown in Figure 5.The result shows that adding DDP modifies the ZnS nanoparticle, can effectively improve the supporting capacity and the antiwear property of the tetradecane.
Investigated the thermostability of this series compound on this external thermal analyzer, show that the decomposition temperature of this series compound is higher than the heat decomposition temperature of its modifier double hexadecyl phosphorodithioic acid pyridinium salt (PyDDP), illustrate that prepared organism decorated nanometer particulate has good thermostability, decomposition temperature is in 270～290 ℃ of scopes.
Embodiment 3:
At 100 milliliters of acetone, ethanol adds 0.48 gram (0.67 mmole) two octadecyl phosphorodithioic acid pyridinium salts in the mixed solvent of water, 60 ℃ of constant temperature, be stirred to complete molten after, add 0.16 gram (0.67 mmole) Na 2S9H 2The O crystal is stirred to whole dissolvings, slowly drips to contain 0.38 gram (1 mmole) Pb (Ac) 23H 2The O crystalline aqueous solution, stirring reaction 1.5 hours.Filter, wash with hot mixed solvent earlier, the back is washed with hot ethanol, and dry in vacuum drier, promptly gets the brown solid product: two octadecyl phosphorodithioic acid finishing PbS nanoparticles.
Embodiment 4:
At 100 milliliters of acetone, ethanol adds 0.37 gram (0.67 mmole) two dodecyl phosphorodithioic acid pyridinium salts in the mixed solvent of water, 60 ℃ of constant temperature, be stirred to complete molten after, add 0.16 gram (0.67 mmole) Na 2S9H 2The O crystal is stirred to whole dissolvings, slowly drips to contain 0.38 gram (1 mmole) Pb (Ac) 23H 2The O crystalline aqueous solution, stirring reaction 1 hour.Filter, wash with hot mixed solvent earlier, the back is washed with hot ethanol, and dry in vacuum drier, promptly gets the brown solid product: two dodecyl phosphorodithioic acid finishing PbS nanoparticles.
Embodiment 5:
At 100 milliliters of acetone, ethanol adds 0.24 gram (0.67 mmole) two iso-octyl phosphorodithioic acid in the mixed solvent of water, 55 ℃ of constant temperature, be stirred to complete molten after, add 0.16 gram (0.67 mmole) Na 2S9H 2The O crystal is stirred to whole dissolvings, slowly drips to contain 0.38 gram (1 mmole) Pb (Ac) 23H 2The O crystalline aqueous solution, stirring reaction 2 hours.Filter, wash with hot mixed solvent earlier, the back is washed with hot ethanol, and dry in vacuum drier, promptly gets the brown solid product: two iso-octyl phosphorodithioic acid finishing PbS nanoparticles.
Embodiment 2, and embodiment 3, and embodiment 4, among the embodiment 5 resulting product through infrared spectra, x-ray photoelectron spectroscopy, the X-ray powder diffraction, transmission electron microscope and 31The P spectral analysis of the nuclear magnetic resonance is confirmed to be the nanoparticle that will obtain.
The evaluation of product:
With embodiment 3, embodiment 4, and the product that obtains among the embodiment 5 is dispersed in the chemical pure whiteruss, at the wear scar diameter of having measured on the four-ball tester under different load.Testing used four-ball tester is the vertical omnipotent friction wear testing machine of MMW-1 type that Jinan trier factory produces, and used steel ball is the secondary standard steel ball (φ 12.7mm, GCr15 bearing steel, HRc are 59-61) that Lanzhou Berings Factory produces.Test is at room temperature carried out, and addition is 0.05wt.%, and rotating speed is 1450 rev/mins, and test period is 30 minutes, the results are shown in Table 1.The result shows that the DDP that only adds minute quantity modifies the PbS nanoparticle, can effectively improve the supporting capacity and the antiwear property of paraffin oil.
The evaluation result of table 1 wear scar diameter (mm)
Additive load (N)
100 200 300 400
Whiteruss 0.521 0.633 0.710 lost efficacy
Example 3 0.504 0.485 0.540 0.651
Example 4 0.451 0.445 0.565 0.662
Example 5 0.449 0.537 0.610 0.689
(four-ball tester, additive concentration are 0.05wt%, 1450r/min, 30min, 25 ℃)

Claims (4)

1. following general formula compound:
R is C in the formula 8-C 18The straight or branched alkyl, M is metallic lead or zinc; M represents the molecule number of MS in the nanoparticle, is dozens of; N represents the molecule number of left-half in the nanoparticle formula (I), for dozens of arrives hundreds of.
2. compound according to claim 1 is characterized in that R is a hexadecyl.
3. the preparation method of compound according to claim 1, this method may further comprise the steps:
A) use contains sulfydryl or thiosalt organic compound and the ratio of soluble metallic salt with mol ratio 0.1～2
Example reaction, with ammonium sulfide or alkali metalsulphide as vulcanizing agent, wherein sulfydryl organic compound or sulphur
For R chain length in the hydrochlorate organic compound is C 8-C 18The straight or branched alkyl, structural formula is
Figure C981180870002C2
Soluble metallic salt is the metal-salt of lead or zinc;
B) in the presence of reaction medium, the mol ratio of sulfydryl or thiosalt organic compound and reaction medium is
1: 1000-50000, wherein reaction medium is an acetone, the mixed solvent of second alcohol and water;
C) reacted 0.5-12 hour down at 50-80 ℃.
4. compound as claimed in claim 1 uses as lubricating oil and grease additive.
CNB981180876A 1998-08-28 1998-08-28 Sulphur-containing organic compound modified metal-chalocogenide nm particles, its prepn. and application Expired - Fee Related CN1173982C (en)

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CN100441340C (en) * 2005-03-02 2008-12-10 河南大学 Phosphorus-containing organic compound modified low-melting-point alloy nano particles and method for preparing same
CN100334187C (en) * 2005-12-15 2007-08-29 北京交通大学 Method for preparing nano lubricating fluid comprising oleophilic metal sulfide
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