WO2015055105A1 - 一种磁性树脂化合物及其制备方法及应用 - Google Patents

一种磁性树脂化合物及其制备方法及应用 Download PDF

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Publication number
WO2015055105A1
WO2015055105A1 PCT/CN2014/088492 CN2014088492W WO2015055105A1 WO 2015055105 A1 WO2015055105 A1 WO 2015055105A1 CN 2014088492 W CN2014088492 W CN 2014088492W WO 2015055105 A1 WO2015055105 A1 WO 2015055105A1
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magnetic
dendrimer
polyamide
sio
compound
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PCT/CN2014/088492
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English (en)
French (fr)
Inventor
鄂红军
朱和菊
隋秀华
廖鹏飞
胡磊磊
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China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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Priority to JP2016548405A priority Critical patent/JP6487453B2/ja
Priority to EP14853911.7A priority patent/EP3059273B1/en
Priority to KR1020157036674A priority patent/KR102172049B1/ko
Priority to BR112015030307-2A priority patent/BR112015030307B1/pt
Priority to US14/896,512 priority patent/US9815948B2/en
Priority to SG11201508525YA priority patent/SG11201508525YA/en
Publication of WO2015055105A1 publication Critical patent/WO2015055105A1/zh
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/002—Dendritic macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/002—Dendritic macromolecules
    • C08G83/003—Dendrimers
    • C08G83/004—After treatment of dendrimers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/028—Polyamidoamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing 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
    • C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
    • C10M125/10—Metal oxides, hydroxides, carbonates or bicarbonates
    • 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
    • C10M139/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing atoms of elements not provided for in groups C10M127/00 - C10M137/00
    • C10M139/04—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing atoms of elements not provided for in groups C10M127/00 - C10M137/00 having a silicon-to-carbon bond, e.g. silanes
    • 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
    • C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
    • C10M149/12—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M149/14—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds a condensation reaction being involved
    • C10M149/22—Polyamines
    • 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
    • C10M155/00—Lubricating compositions characterised by the additive being a macromolecular compound containing atoms of elements not provided for in groups C10M143/00 - C10M153/00
    • C10M155/02—Monomer containing silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/44—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of magnetic liquids, e.g. ferrofluids
    • H01F1/445—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of magnetic liquids, e.g. ferrofluids the magnetic component being a compound, e.g. Fe3O4
    • 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
    • C10M2201/14—Inorganic compounds or elements as ingredients in lubricant compositions inorganic compounds surface treated with organic 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • 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
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/05—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon
    • C10M2229/052—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon containing nitrogen
    • 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
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/14—Group 7
    • 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
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/16—Groups 8, 9, or 10
    • 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
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/075—Dendrimers
    • 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
    • C10N2030/02—Pour-point; Viscosity index
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines

Definitions

  • the present invention relates to a magnetic resin compound, and more particularly to a magnetic resin compound and a preparation method thereof for a magnetic nano antiwear additive which can be used for a lubricant, and more particularly to a magnetic polyamide-amine compound and a preparation method thereof.
  • the traditional lubricating oil anti-wear agents include sulfur anti-wear agents (such as sulfurized olefins, sulfurized esters, sulfurized oils, etc.), phosphorus anti-wear agents (such as phosphates, phosphites, alkylphosphonates, etc.), and halogens.
  • Anti-wear agents such as chlorinated paraffins, chlorinated hydrocarbons, chlorinated fatty acids, etc.
  • organometallics such as lead naphthenate, dialkyl dithiophosphate (ZnDDP), etc.
  • Nanomaterials are new materials developed in the mid-1980s. They have different characteristics than microscopic atoms, molecules, and macroscopic materials. New lubricant materials based on nanomaterials are used as lubricant additives for tribology. The contribution of performance is not achieved by the use of the properties of the nanoparticles themselves, as is the case with conventional lubricant additives that utilize their structural characteristics to achieve their anti-wear and film-reducing effects. Due to the small particle size, the nanoparticles are more likely to enter the friction surface, and a thicker surface film may be formed, so that the surface of the friction pair can be well separated, and the antiwear and antifriction effect is improved.
  • Dendrimers are three-dimensional macromolecules with high branching, have unconventional whole and controllable structures, and have a large number of functional end groups. Since 1978, Vogtle et al. first reported the concept of gradually repeating the synthesis of dendrimers, and then the Tomalia group synthesized the true dendrimers, which has gradually become a hot spot for scientists. Since the molecule itself has a nanometer size and the molecular weight distribution can be monodisperse, the dendrimer surface has an extremely modified amino functional group which is increased in geometric multiples. These structural features make it possible for the branch macromolecules to have good dispersibility in the lubricating oil, satisfying the most basic requirements of the lubricating oil nano-additive. But at present, the branches of macromolecules act as lubricants Antiwear additives have not been reported.
  • Another object of the present invention is to provide a process for the preparation of the novel magnetic dendrimer compound.
  • Still another object of the present invention is to provide the use of the novel magnetic dendrimer compound as a magnetic antiwear additive for lubricating oils.
  • the present invention provides the following technical solutions:
  • ⁇ represents magnetic particles coated with SiO 2 on the surface, and the magnetic particles are surface-modified with a silane coupling agent
  • the (CH 2 ) 3 N (2 n+1 -1) R 1 (2 n +2 -2) is a group having a dendritic structure
  • R 2 (2 n+1 ) is a lipophilic group, and 0 ⁇ n ⁇ 100 .
  • the magnetic particles are magnetic nanoparticles.
  • the magnetic particle contains Fe 3 O 4 , Ni or ⁇ -Fe 2 O 3 At least one of them.
  • the magnetic particle is selected from the core-shell type Fe in which the outer layer is coated with SiO 2 . 3 O 4 & SiO 2 magnetic nanoparticles, and the magnetic particles are surface-modified with a silane coupling agent.
  • the silane coupling agent is 3-aminopropyltriethoxysilane, 3 - glycidyloxypropyltrimethoxysilane or 3-aminopropyltrimethoxysilane.
  • the R 1 is selected from the group consisting of a polyamide having a repeating unit structure represented by the formula II - an amine dendrimer;
  • the R 2 is selected from a branched or linear alkyl group of from 1 to 18 .
  • a magnetic polyamide having a molecular formula represented by Formula III is preferably used.
  • An amine compound, that is, the dendrimer is a polyamide-amine dendrimer compound (PAMAM);
  • ruthenium is a magnetic nanoparticle (having a particle diameter of 1 to 100 nm), 0 ⁇ n ⁇ 10, and 1 ⁇ m ⁇ 18.
  • the magnetic nanoparticle ruthenium contains at least one of Fe 3 O 4 , Ni or ⁇ -Fe 2 O 3 , and the magnetic nanoparticle ruthenium shell layer is coated with SiO 2 , thereby forming a core shell Fe 3 O 4 &SiO 2 magnetic nanoparticles.
  • the core-shell type Fe 3 O 4 &SiO 2 magnetic nanoparticles can also be surface-modified magnetic nanoparticles by a silane coupling agent, and the silane coupling agent is selected from, for example, 3-aminopropyltriethoxysilane. a compound such as 3-glycidoxypropyltrimethoxysilane or 3-aminopropyltrimethoxysilane.
  • step ii) reacting the dendrimer-bonded magnetic particle product obtained in step ii) with a compound having an oleophilic group to obtain the magnetic dendrimer compound.
  • the lipophilic group-containing compound is a halogenated hydrocarbon, preferably a monohaloalkane, more preferably a monoiodoalkane.
  • the magnetic dendrimer compound is contained in the lubricant in an amount of from 100 ppm to 5% by mass.
  • the weight content of Fe and/or Ni is from 0.01 ppm to 0.20%, preferably from 0.01 ppm to 429 ppm.
  • the lubricant of the lubricant is contained in an amount of from 0.01 to 20.1 ppm by weight.
  • the magnetic dendrimer compound is selected from the group consisting of a magnetic polyamide-amine compound represented by Formula III,
  • ⁇ represents magnetic particles coated with SiO 2 on the surface, and the magnetic particles are surface-modified with a silane coupling agent
  • the (CH 2 ) 3 N (2 n+1 -1) R 1 (2 n +2 -2 ) is a group having a dendritic structure
  • the (C m H 2m+1 ) 2 n+1 is a lipophilic group, 0 ⁇ n ⁇ 10, and 1 ⁇ m ⁇ 18.
  • n is selected from an integer of 5 to 9
  • m is selected from an integer of 9 to 13.
  • Magnetic branches molecular compounds do not because of the increased molecular compound such branches magnetically weakened by vibrating sample magnetic meter (VSM) of the Fe 3 O 4 magnetic nanoparticles, and magnetic Fe 3 O 4 nano-level branches of the magnetic molecule compound After the regression line analysis, the saturation magnetization of the two did not decrease significantly. It can be seen that the prepared magnetic dendrimer compound has strong magnetic properties.
  • the oil containing the magnetic dendrimer compound of the present invention can reach the friction and wear site accurately and quickly, and forms a special protective oil film on the surface of the friction pair. Therefore, magnetic dendrimer compounds have wear targeting effects.
  • a magnetic dendrimer compound is prepared by surface modification of core-shell Fe 3 O 4 &SiO 2 magnetic nanoparticles. Since both the core (Fe 3 O 4 & SiO 2 ) and the surface modification (dendritic molecular compound) have a nanometer size (1 to 100 nm), the prepared magnetic particle dendrimer compound should also be nanoscale.
  • the particle size analysis of the 5G magnetic dendrimer compound is carried out by transmission electron microscopy, and the particle size of the nano-sized dendrimer compound is preferably about 30 nm.
  • the oil containing the nano-branched molecular compound of the present invention has a repairing effect on the surface of the worn friction pair.
  • the magnetic dendrimer compound of the invention has good solubility in the base oil and can dissolve I, II, III and IV.
  • Base oil or synthetic oil This is because the end of the dendrimer compound of the present invention is provided with a lipophilic group such as a long-chain alkyl group.
  • the addition of the magnetic dendrimer compound of the present invention as an antiwear agent to a lubricant is, for example, a good abrasion resistance when added to an engine lubricating oil.
  • a 5G magnetic polyamide-amine compound is dissolved in a 100N base oil, and its antiwear property is tested by a multifunctional friction and wear tester (SRV). As the load increases, the friction coefficient decreases slightly, and the friction coefficient tends to be stable around 0.119. This is because the oil film on the surface of the friction pair is gradually formed and stable, indicating that the 5G magnetic polyamide-amine compound has good abrasion resistance.
  • the nano-scale magnetic dendrimer compound can form an oil film on the surface of the object, and since the magnetic dendrimer compound is a nano-sized particle, it can also be filled into pits or scratches on the surface of the object to fill the pit or the scratch. Traces that can act to repair the surface of an object.
  • the lubricant containing the magnetic dendrimer compound of the present invention has a function of cooling the surface of the object as well as sealing while having excellent extreme pressure properties.
  • the magnetic dendrimer compound of the present invention obviously does not contain harmful elements such as S, P, Cl, Pb, and the like, and therefore, it is added to various lubricants as an additive such as an anti-wear agent, and does not cause any damage to the environment.
  • VSM vibrating sample magnetometer
  • 5G magnetic properties are observed.
  • the specific saturation magnetization of the polyamide-amine compound was 58.5 emu/g, and the specific saturation magnetization was not significantly lower than that of the pure Fe 3 O 4 inner particle. From this, it can be seen that the prepared magnetic polyamide-amine compound has strong magnetic properties.
  • the particle size analysis of the 5G magnetic polyamide-amine compound was carried out by transmission electron microscopy. As can be seen from Fig. 3, the particle size of the 5G magnetic polyamide-amine compound was about 30 nm.
  • the present invention uses a multifunctional friction and wear tester (SRV) to test the lubricating oil containing the nano-sized polyamide-amine compound of the present invention.
  • Test conditions friction pair mode: ball and disc, test conditions: 50hz, 50 ° C, gradient pressurization, initial 50N, pressure after 100 minutes, 100N, pressurization in sequence, until 2000N (or friction coefficient greater than 0.3) termination.
  • the measurement of the content of Fe and/or Ni and the content of Si in the lubricant is carried out in accordance with the method specified in the standard of ASTM D5185.
  • the distribution coefficient is a parameter attached by gel chromatography. The closer the parameter is to 1, the more uniform the molecular distribution.
  • the molecular formula of 0G PAMAM magnetic nano anti-wear agent is (Fe 3 O 4 &SiO 2 )Si(OCH 3 ) 3 (CH 2 ) 3 N[(CH 2 ) 2 CONH(CH 2 ) 2 NH] 2 ( C 12 H 25 ) 2 , molecular weight 989.
  • the 1 to 10 generation PAMAM magnetic nano anti-wear agents were analyzed by gel permeation chromatography.
  • the molecular formula of 0G PAMAM magnetic nano anti-wear agent is (Ni&SiO 2 )Si(OCH 3 ) 3 (CH 2 ) 3 N[(CH 2 ) 2 CONH(CH 2 ) 2 NH] 2 (C 18 H 37 2 )
  • the molecular weight is 983.
  • the 1 to 10 generation PAMAM magnetic nano anti-wear agents were analyzed by gel permeation chromatography.
  • 4G magnetic polymerization is used respectively.
  • A* contains anti-wear additives, and anti-wear additives refer to zinc dialkyl dithiophosphate (ZnDDP).
  • M* friction pair mode ball and disc, test conditions: 50hz, 200g, 80 °C.
  • M* friction pair mode ball and disc, test conditions: 50hz, 200g, 80 °C.
  • the anti-wear performance test of Formula I was carried out using SRV.
  • the test results show that the friction coefficient curve is unstable.
  • M* friction pair mode ball and disc, test conditions: 50hz, 200g, 80 °C.
  • the anti-wear performance test of Formula I was carried out using SRV.
  • the test results show that the friction coefficient curve is unstable.
  • D* does not contain anti-wear additives.
  • M* friction pair mode ball and disc, test conditions: 50hz, 200g, 80 °C.
  • the anti-wear performance test of Formula I was carried out using SRV.
  • the test results show that the friction coefficient curve is unstable.
  • E* does not contain anti-wear additives.
  • M* friction pair mode ball and disc, test conditions: 50hz, 200g, 80 °C.
  • the anti-wear performance test of Formula I was carried out using SRV.
  • the test results show that the friction coefficient curve is unstable.
  • F* does not contain anti-wear additives.
  • M* friction pair mode ball and disc, test conditions: 50hz, 200g, 80 °C.
  • the anti-wear performance test of Formula I was carried out using SRV.
  • the test results show that the friction coefficient curve is unstable.
  • M* does not contain anti-wear additives.
  • M* friction pair mode ball and disc, test conditions: 50hz, 200g, 80 °C.
  • the anti-wear performance test of Formula I was carried out using SRV.
  • the test results show that the friction coefficient curve is unstable.
  • N* does not contain anti-wear additives.
  • M* friction pair mode ball and disc, test conditions: 50hz, 200g, 80 °C.
  • the anti-wear performance test of Formula I was carried out using SRV.
  • the test results show that the friction coefficient curve is unstable.
  • Salt anti-wear agent (such as molybdenum dialkyl dithiophosphate), formulated with SN/GF-5 0W-20 gasoline engine oil.
  • P* contains anti-wear additives, and anti-wear additives refer to zinc dialkyl dithiophosphate (ZDDP).
  • M* friction pair mode ball and disc, test conditions: 50hz, 200g, 80 °C.
  • the coefficient of friction of the SN/GF-50W-20 oil formulated using the 7G magnetic nano antiwear agent K of the present example was 0.07, and the molybdenum dialkyldithiophosphate was used as an anti- Grinding agent formulated SN/GF-5 0W-20
  • Molybdenum salt anti-wear agent such as molybdenum dialkyl dithiophosphate
  • anti-wear additives refer to zinc dialkyl dithiophosphate (ZDDP).
  • M* friction pair mode ball and disc, test conditions: 50hz, 200g, 80 °C.
  • the coefficient of friction of the SN/GF-50W-30 oil formulated using the 8G magnetic nano antiwear agent L of the present embodiment was 0.08, and the molybdenum dialkyl dithiophosphate was used as an anti-
  • Molybdenum salt anti-wear agent such as molybdenum dialkyl dithiophosphate
  • CI-4 10W-30 diesel engine oil was used as the magnetic nano anti-wear agent M (Ni: 6.4 ppm, Si: 1.2 ppm) and the organic common in the market.
  • Molybdenum salt anti-wear agent such as molybdenum dialkyl dithiophosphate
  • W* contains anti-wear additives, and anti-wear additives refer to zinc dialkyl dithiophosphate (ZDDP).
  • M* friction pair mode ball and disc, test conditions: 50hz, 200g, 80 °C.
  • the coefficient of friction of the CI-410W-30 oil formulated using the 9G magnetic nano anti-wear agent of the present embodiment is 0.06, and the molybdenum dialkyl dithiophosphate is formulated as an antiwear agent.
  • Salt anti-wear agent such as molybdenum dialkyl dithiophosphate
  • CF-4 15W-40 diesel engine oil was used as magnetic nano antiwear agent N (Fe: 7ppm, Si: 0.17ppm) and organic molybdenum which is common in the market.
  • Salt anti-wear agent such as molybdenum dialkyl dithiophosphate
  • Y* contains anti-wear additives, and anti-wear additives refer to zinc dialkyl dithiophosphate (ZDDP).
  • M* friction pair mode ball and disc, test conditions: 50hz, 200g, 80 °C.
  • the friction coefficient of the CF-415W-40 diesel engine lubricating oil formulated using the 10G magnetic nano antiwear agent N of the present embodiment is 0.09, and the molybdenum dialkyldithiophosphate is used as an anti-
  • Molybdenum salt anti-wear agent (such as molybdenum dialkyl dithiophosphate), blended with SM 0W-30 gasoline engine oil.
  • Z* contains anti-wear additives, and anti-wear additives refer to zinc dialkyl dithiophosphate (ZnDDP).
  • M* friction pair mode ball and disc, test conditions: 50hz, 200g, 80 °C.
  • Molybdenum salt anti-wear agent (such as molybdenum dialkyl dithiophosphate), formulated with SN 5W-30 gasoline engine oil.
  • R* contains anti-wear additives, and anti-wear additives refer to zinc dialkyl dithiophosphate (ZnDDP).
  • M* friction pair mode ball and disc, test conditions: 50hz, 200g, 80 °C.
  • the friction coefficient of the SN 5W-30 oil formulated with the 3G magnetic nano antiwear agent Q of the present embodiment is 0.08, and the molybdenum dialkyl dithiophosphate is formulated as an antiwear agent.
  • 1G magnetic polyamide-amine compound with Fe 3 O 4 &SiO 2 as core as magnetic nano anti-wear agent for gasoline engine lubricating oil.
  • 1G magnetic polyamide-amine compound (as 1G magnetic) Nano anti-wear agent O (Fe: 10ppm, Si: 0.2ppm)
  • Organic molybdenum salt anti-wear agent (such as molybdenum dialkyl dithiophosphate), which is commonly used in the market, is formulated with SM 5W-30 gasoline engine lubricating oil.
  • O* contains anti-wear additives, and anti-wear additives refer to zinc dialkyl dithiophosphate (ZnDDP).
  • M* friction pair mode ball and disc, test conditions: 50hz, 200g, 80 °C.
  • the friction coefficient of the SM5W-20 oil formulated with the 1G magnetic nano antiwear agent O of the present embodiment is 0.08, and the molybdenum dialkyl dithiophosphate is formulated as an antiwear agent.
  • the SM 5W-20 oil has a coefficient of friction of 0.11, which indicates that the 1G magnetic polyamide-amine compound is an excellent magnetic nano antiwear agent.
  • a 5G magnetic polyamide-amine compound having ⁇ -Fe 2 O 3 &SiO 2 as a core was dissolved in a 100 N base oil, and subjected to abrasion resistance test using SRV. The result is shown in Figure 4. It can be seen from Fig. 4 that as the load increases, the friction coefficient decreases slightly, and the friction coefficient tends to be stable around 0.119. This is because the frictional surface oil film is gradually formed and stable, indicating that the 5G magnetic polyamide-amine compound has good antiwear properties. When the load is applied to 1100 N, the friction coefficient suddenly rises because the oil film on the friction surface is broken and the lubrication is lost.

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Abstract

本发明公开了一种磁性树枝分子化合物及其制备方法，其分子式如式I所示：Γ(CH2)3N(2 n+1 -1)R1 (2 n+2 -2)R2 (2 n+1 )I其中，Γ表示表面包覆了SiO2的磁性颗粒，且所述磁性颗粒经硅烷偶联剂进行了表面修饰，所述(CH2)3N(2 n+1 -1)R1为具有树枝状结构的基团，所述R2为亲油性基团，0≤n≤100。本发明还公开了一种含有所述磁性树枝分子化合物的润滑剂。

Description

一种磁性树脂化合物及其制备方法及应用 技术领域
本发明涉及一种磁性树脂化合物，具体地说，涉及可用于润滑剂的磁性纳米抗磨添加剂的磁性树脂化合物及制备方法，尤其涉及一种磁性聚酰胺-胺类化合物及制备方法。
背景技术
近年来，随着工业产品尤其是汽车工业产品的全面升级，使得对润滑油性能的要求越来越高。新的环保法规的出台，对含硫、磷、氯润滑油添加剂的使用量提出了严格的限制。目前传统的润滑油抗磨剂有硫类抗磨剂(如硫化烯烃、硫化酯、硫化油等)、磷类抗磨剂(如磷酸酯、亚磷酸酯、烷基膦酸酯等)、卤类抗磨剂(如氯化石蜡、氯代烃、氯代脂肪酸等)、有机金属类(如环烷酸铅、二烷基二硫代磷酸盐(ZnDDP)等)等。
但随着现代工业的快速发展及人类对自生环境的要求和健康意识的不断提高，这些传统的抗磨剂已经越来越难满足苛刻工况及时代发展对它们的要求。如氯类抗磨剂对因其毒性问题已被有的国家如美国和西欧禁用；环烷酸铅也因生态和毒性问题逐渐被淘汰；硫类、磷类抗磨剂及ZnDDP因其含有的P和S会使尾气转化器中的三效催化剂中毒、影响氧气传感器测量准确性及对生态环境的毒性，已被国际规定限量使用。
正是传统润滑油抗磨剂所面临的巨大挑战，纳米材料成为润滑油抗磨剂成为研究的热点。纳米材料是20世纪80年代中期发展起来的新型材料，具有不同于微观原子、分子，也不同于宏观物质的超常特性，以纳米材料为基础制备的新型润滑材料作为润滑油添加剂，其对摩擦学性能的贡献并不像传统润滑油添加剂利用其结构上的特点来实现其抗磨减膜作用的，而是通过利用纳米颗粒本身特性来实现的。纳米粒子因粒度小而更容易进入摩擦表面，可能形成更厚的表面膜，使摩擦副表面能很好地分离，提高抗磨减摩效果。
树枝状分子是具有高支度化的三维大分子，具有非常规整及可控制的结构，并且有大量功能性端基。自1978年Vogtle等首次报道了逐步重复以合成树枝状分子的概念，并随后由Tomalia小组合成了真正的树枝状大分子以来，逐步成为科学家们关注的热点。由于分子本身具有纳米尺寸，并且分子量分布可达单分散性，同时树枝状大分子表面具有以几何倍数增加的极易修饰的氨基官能团。这些结构特点使树枝大分子在润滑油中具有良好分散性成为可能，满足了润滑油纳米添加剂的最基本要求。但目前，树枝大分子作为润滑油 抗磨添加剂尚未见报道。
发明内容
本发明的目的是提供一种新型磁性树枝状分子化合物。
本发明的另一目的是提供该新型磁性树枝状分子化合物的制备方法。
本发明的再一目的是提供该新型磁性树枝状分子化合物作为润滑油用磁性抗磨添加剂中的应用。
为了实现本发明目的，本发明提供了以下技术方案：
1)一种磁性树枝分子化合物，其分子式如式I所示：
Γ(CH2)3N(2 n+1 -1)R1 (2 n+2 -2)R2 (2 n+1 )I
其中，Γ表示表面包覆了SiO2的磁性颗粒，且所述磁性颗粒经硅烷偶联剂进行了表面修饰，所述(CH2)3N(2 n+1 -1)R1 (2 n+2 -2)为具有树枝状结构的基团，所述R2 (2 n+1 )为亲油性基团，0≤n≤100。
2)在本发明的第1)项所述的磁性树枝分子化合物的一个实施方式中，所述磁性颗粒为磁性纳米颗粒。
3)在本发明的第1)或2)项所述的磁性树枝分子化合物的一个实施方式中，其中，0≤n≤10。
4)在本发明的第1)-第3)项中任一项所述的磁性树枝分子化合物的一个实施方式中，所述磁性颗粒含有Fe3O4、Ni或γ-Fe2O3中的至少一种。
5)在本发明的第1)-第4)项中任一项所述的磁性树枝分子化合物的一个实施方式中，所述磁性颗粒选自外层包覆有SiO2的核壳式的Fe3O4&SiO2磁性纳米粒子，且所述磁性颗粒经硅烷偶联剂进行了表面修饰。
6)在本发明的第1)-第5)项中任一项所述的磁性树枝分子化合物的一个实施方式中，所述硅烷偶联剂为3-氨基丙基三乙氧基硅烷、3-缩水甘油醚氧基丙基三甲氧基硅烷或3-氨基丙基三甲氧基硅烷。
7)在本发明的第1)-第6)项中任一项所述的磁性树枝分子化合物的一个实施方式中，所述R1选自具有以式II的所示重复单元结构的聚酰胺-胺型树枝状高分子；
-(CH2)2CONH(CH2)2NH-II。
8)在本发明的第1)-第7)项中任一项所述的磁性树枝分子化合物的一个实施方式中，所述R2选自C1～18的支链或直链的烷基。
在本发明的磁性树枝分子化合物中，优选为具有式III所示的分子式的磁性聚酰胺- 胺类化合物，即所述树枝分子为聚酰胺-胺型树枝状高分子化合物(PAMAM)；
Γ(CH2)3N(2 n+1 -1)[(CH2)2CONH(CH2)2NH](2 n+2 -2)(CmH2m+1)2 n+1  III
其中，Γ为磁性纳米颗粒(粒径为1～100nm)，0≤n≤10，1≤m≤18。优选地，所述磁性纳米颗粒Γ含有Fe3O4、Ni或γ-Fe2O3中的至少一种，且所述磁性纳米颗粒Γ外壳层具包覆有SiO2，由此构成核壳式的Fe3O4&SiO2磁性纳米粒子。最优选的，所述核壳式的Fe3O4&SiO2磁性纳米粒子还可经过硅烷偶联剂进行表面修饰的磁性纳米颗粒，硅烷偶联剂选自如3-氨基丙基三乙氧基硅烷、3-缩水甘油醚氧基丙基三甲氧基硅烷或3-氨基丙基三甲氧基硅烷等类似化合物。
具体地说，所述磁性树枝分子化合物优选为：0代聚磁性树枝分子化合物(0G，n＝0，1≤m≤18)、1代磁性树枝分子化合物(1G，n＝1，1≤m≤18)、2代磁性树枝分子化合物(2G，n＝2，1≤m≤18)、3代磁性树枝分子化合物(3G，n＝3，1≤m≤18)、4代磁性树枝分子化合物(4G，n＝4，1≤m≤18)、5代磁性树枝分子化合物(5G，n＝5，1≤m≤18)、6代磁性树枝分子化合物(6G，n＝6，1≤m≤18)、7代磁性树枝分子化合物(7G，n＝7，1≤m≤18)、8代磁性树枝分子化合物(8G，n＝8，1≤m≤18)、9代磁性树枝分子化合物(9G，n＝9，1≤m≤18)和10代磁性树枝分子化合物(10G，n＝10，1≤m≤18)。
9)一种本发明第1)-第8)项中任一项所述的磁性树枝分子化合物的制备方法，其特征在于，包括如下步骤：
i)提供包覆了SiO2的磁性颗粒；
ii)使用硅烷偶联剂对所述磁性颗粒的表面进行修饰，然后将修饰后的产物与所述树枝状分子反应，使得所述树枝状分子键合于所述磁性颗粒；
iii)将步骤ii)得到的树枝分子键合磁性颗粒产物与带有亲油基团的化合物反应，得到所述磁性树枝分子化合物。
10)在本发明的第9)项所述的制备方法的一个实施方式中，所述带有亲油基团的化合物为卤代烃，优选一卤代烷烃，更优选为一碘代烷烃。
11)一种含有本发明第1)-第8)项中任一项所述的磁性树枝分子化合物在制备润滑剂用抗磨添加剂中的应用。
12)一种含有本发明第1)-第8)项中任一项所述的磁性树枝分子化合物的润滑剂。
13)在本发明的第12)项所述的润滑剂的一个实施方式中，所磁性树枝分子化合物在润滑剂中的质量含量为100ppm～5％。
14)在本发明的第12)或第13)项所述的润滑剂的一个实施方式中，Fe和/或Ni的重量含量为0.01ppm～0.20％，优选0.01ppm～429ppm。
15)在本发明的第12)-第14)中任一项所述的润滑剂的一个实施方式中，所述润滑剂中的Si的重量含量为0.01～20.1ppm。
16)在本发明的第12)-第15)中任一项所述的润滑剂的一个实施方式中，所述磁性树枝分子化合物选自式III所示的磁性聚酰胺-胺类化合物，
Γ(CH2)3N(2 n+1 -1)[(CH2)2CONH(CH2)2NH](2 n+2 -2)(CmH2m+1)2 n+1  III
其中，Γ表示表面包覆了SiO2的磁性颗粒，且所述磁性颗粒经硅烷偶联剂进行了表面修饰，所述(CH2)3N(2 n+1 -1)R1 (2 n+2 -2)为具有树枝状结构的基团，所述(CmH2m+1)2 n+1为亲油性基团，0≤n≤10，1≤m≤18。
17)在本发明的第16)项所述的润滑剂的一个实施方式中，所述磁性聚酰胺-胺类化合物中n选自5～9中的整数，m选自9～13中的整数。
在本发明的润滑剂中，所述磁性聚酰胺-胺类化合物优选以下化合物中的至少一种：5代磁性树枝分子化合物(5G，n＝5，m＝12)、6代磁性树枝分子化合物(6G，n＝6，m＝12)、7代磁性树枝分子化合物(7G，n＝7，m＝12)、8代磁性树枝分子化合物(8G，n＝8，m＝12)、9代磁性树枝分子化合物(9G，n＝9，m＝12)和10代磁性树枝分子化合物(10G，n＝10，m＝12)。
本发明磁性树枝分子化合物具有如下优点：
1.靶向作用
磁性树枝分子化合物不因增加了树枝分子化合物而使得磁性减弱，采用振动样品磁性计(VSM)对所述Fe3O4磁性纳米颗粒，和Fe3O4磁性纳米所述级树枝分子化合物进行磁滞回归线分析，两者饱和磁化强度并无明显降低。由此可以看出，制备的磁性树枝分子化合物具有较强的磁性。含有本发明磁性树枝分子化合物的油品，可以准确并迅速到达摩擦磨损部位，在摩擦副表面形成特殊的保护油膜。因此，磁性树枝分子化合物具有磨损靶向作用。
2.纳米修复作用
通过对核壳式的Fe3O4&SiO2磁性纳米粒子进行表面修饰，制备磁性树枝分子化合物。由于核(Fe3O4&SiO2)和表面修饰物(树枝分子化合物)都具有纳米尺寸(1～100nm)，因此制备的磁性颗粒树枝分子化合物也应是纳米级的。采用透射电镜对5G磁性树枝分子化合物进行粒径分析，所述纳米级树枝分子化合物化合物的粒径优选约30nm。含有本发明的纳米树枝分子化合物的油品，对有磨损的摩擦副表面具有修复作用。
3.良好的油溶性
本发明所述磁性树枝分子化合物在基础油中的溶解性很好，可以溶解I、II、III和IV 基础油或合成油中。这是由于所述本发明的树枝分子化合物的最末端设置有如长链烷基等亲油性基团。
4.具有良好的抗磨性能、优异的极压性能
将本发明的磁性树枝分子化合物作为抗磨剂添加到润滑剂中是，例如添加到发动机润滑油中时，能起到良好的耐磨效果。例如将5G磁性聚酰胺-胺类化合物溶解到100N的基础油中，采用多功能摩擦磨损试验仪(SRV)对其进行抗磨性能测试。随着负载增加，摩擦系数略有降低，摩擦系数在0.119左右趋于稳定。这是由于摩擦副表面油膜逐渐形成，并且稳定，说明5G磁性聚酰胺-胺类化合物具有良好的抗磨性能。另外，纳米级磁性树枝分子化合物除了能在物体表面形成油膜，由于磁性树枝分子化合物为纳米级颗粒，其还能填充到所述物体表面的凹坑或划痕中，填补所述凹坑或划痕，从而可以起到修复物体表面的作用。同时，含有本发明的磁性树枝分子化合物的润滑剂还具有冷却物体表面以及密封作用同时具有优异的极压性能。
5.绿色、环保
本发明的磁性树枝分子化合物明显不含有S、P、Cl、Pb等有害元素，因此使用其作为抗磨剂等添加剂加入各种润滑剂中是，对环境不会造成任何损害。
附图说明
图1为本发明所述的以Fe3O4&SiO2为核心纳米级磁性颗粒的树枝分子化合物，纳米级聚酰胺-胺类树枝化合物(0G、1G，m＝12)反应过程。
图2为本发明所述Fe3O4纳米粒子和Fe3O4磁性颗粒纳米级聚酰胺-胺类化合物(5G，m＝12)磁滞回归线。
图3为本发明所述5G磁性聚酰胺-胺类化合物(m＝12)透射电镜图片。
图4为本发明所述以Fe3O4&SiO2为核心5G磁性聚酰胺-胺类化合物(m＝12)多功能摩擦磨损试验图。
图5为本发明所述以Fe3O4&SiO2为核心5G聚酰胺-胺类抗磨剂(m＝12)与二烷基二硫代磷酸钼极压性能对比图。
具体实施方式
以下结合实施例和附图并对本发明进行详细说明，但本发明的范围并不限于以下实施例。
在本发明中，采用振动样品磁性计(VSM)对Fe3O4纳米粒子和磁性聚酰胺-胺类化合 物(5G，m＝12)进行磁滞回归线分析，从图2可以看出，5G磁性聚酰胺-胺类化合物的比饱和磁化强度为58.5emu/g，与纯Fe3O4内米粒子相比，其比饱和磁化强度并无明显降低。由此可以看出，制备的磁性聚酰胺-胺类化合物具有较强的磁性。
采用透射电镜对5G磁性聚酰胺-胺类化合物进行粒径分析，从图3可以看出，5G磁性聚酰胺-胺类化合物的粒径大约为30nm。
本发明使用采用多功能摩擦磨损试验仪(SRV)对所述含有本发明的纳米级聚酰胺-胺类化合物的润滑油的进行测试。试验条件：摩擦副模式：球与盘，试验条件：50hz，50℃，梯度加压，初始50N，2分钟后压力为100N，依次加压，直至2000N(或摩擦系数大于0.3)终止。
在本发明中，所述润滑剂中的Fe和/或Ni的含量以及Si的含量的测量按照ASTM D5185的标准中规定的方法来进行。
分布系数为采用凝胶色谱测定所附带的参数，该参数越接近1，表示该分子分布越均匀。
实施例1
以Fe3O4&SiO2为核心的磁性聚酰胺-胺类化合物(n＝0，m＝12)的制备。
(1)将0.1mol/L的FeCl2·4H2O溶液、0.2mol/L的FeCl3·6H2O溶液按(体积比2∶1)加到第一容器中，放置于(30±1)℃超声反应器，超声同时滴加0.1mol/L的NaOH溶液，直至溶液pH＝12，利用磁场分离出磁性颗粒。用去离子水洗涤磁性颗粒，至洗涤液的pH＝7，即可得到黑色的Fe3O4内米粒子。
(2)称取18.4g的Fe3O4内米粒子分散于无水乙醇(100mL)中，加入几滴油酸，然后超声分散10分钟；将分散后的溶液转入第二容器中，加入20.8g正硅酸乙酯(TEOS)和7g NH3·H2O，搅拌3小时；反应完成后，在磁场吸引的条件下，将溶液用蒸馏水反复洗涤，直至清洗后的溶液不再变浑浊；把得到的沉淀进行80℃真空干燥，最后研细得到最终的核壳式的Fe3O4&SiO2磁性纳米粒子。
(3)称取5g所述核壳式的Fe3O4&SiO2磁性纳米粒子置于烧瓶中，滴加20mL体积浓度为10％的硅烷偶联剂(KH5503-氨基丙基三乙氧基硅烷)甲苯溶液，在温度50℃条件下，反应60min，待降至室温后减压抽滤，并用甲醇洗涤，然后于70℃真空干燥箱干燥12h。
(4)将5克硅烷化(表面修饰)之后得到的产物置于烧瓶中，缓慢滴加30％(体积百分数)的丙烯酸甲酯的甲醇溶液20mL，在温度为60℃的条件下搅拌90min后，待降至室温后减压抽滤，用甲醇洗涤，烘干。取5.8克置于烧瓶中，加入20mL 30％(体积百分数)的乙二胺的甲醇溶液，在温度为60℃的条件下搅拌180min后，待降至室温后减压抽滤，用甲醇洗涤，烘干，得到0代PAMAM树枝分子修饰的磁性纳米颗粒。
(5)将得到的1.8克0代PAMAM树枝分子加入0.5g C12H25I，室温搅拌10min后，将样品放入微波萃取罐中，在微波功率200W、温度为50℃的条件下反应30min，待降至室温后减压抽滤，用甲醇洗涤，烘干，即得到2.1克0G磁性聚酰胺-胺类化合物，即PAMAM磁性纳米抗磨剂(0G，n＝0，m＝12)。
经检测分析，0G PAMAM磁性纳米抗磨剂的分子式为(Fe3O4&SiO2)Si(OCH3)3(CH2)3N[(CH2)2CONH(CH2)2NH]2(C12H25)2，分子量为989。
13CNMR，6(ppm)，170-180(双峰，C＝O)，52-60(五峰，C-Si)，45-51(双峰，CH3)，31-40(双峰，C-N)，10-20(四峰，CH2)。FTIR(KBr)υ(cm-1)：2980(υCH3)，2940、2870、1467(υCH2)，1644(υC＝O)，1560(υ-N-H)，1350(υC-N)，1275(υsi-C)，
Figure PCTCN2014088492-appb-000001
1080(υsi-O)，1401.8(υsi-O-Fe)，579((υFe-O-si)。
重复步骤4和步骤5将依次得到1～10代PAMAM树枝分子修饰的硅胶包覆Fe3O4&SiO2磁性纳米粒子(m＝12)，如此得到1～10代磁性聚酰胺-胺类化合物(1～10G，n＝1-10，m＝12)。
采用凝胶渗透色谱对1～10代PAMAM磁性纳米抗磨剂进行分析，其中1G PAMAM磁性纳米抗磨剂(m＝12)的分子式为：
(Fe3O4&SiO2)Si(OCH3)3(CH2)3N3[(CH2)2CONH(CH2)2NH]6(C12H25)4，数均分子量实测为1721，分布系数为1.05。
2G磁性纳米级聚酰胺-胺类化合物(m＝12)的分子式为：
(Fe3O4&SiO2)Si(OCH3)3(CH2)3N7[(CH2)2CONH(CH2)2NH]14(C12H25)8，数均分子量实测为3332，分布系数为1.09。
3G磁性纳米级聚酰胺-胺类化合物(m＝12)的分子式为：
(Fe3O4&SiO2)Si(OCH3)3(CH2)3N15[(CH2)2CONH(CH2)2NH]30(C12H25)16，数均分子量实测 为6241，分布系数为1.15。
4G磁性纳米级聚酰胺-胺类化合物(m＝12)的分子式为：
(Fe3O4&SiO2)Si(OCH3)3(CH2)3N31[(CH2)2CONH(CH2)2NH]62(C12H25)32，数均分子量实测为13051，分布系数为1.18。
5G磁性聚酰胺-胺类化合物(m＝12)的分子式为：
(Fe3O4&SiO2)Si(OCH3)3(CH2)3N63[(CH2)2CONH(CH2)2NH]126(C12H25)64，数均分子量实测为24752，分布系数为1.23。
6G磁性聚酰胺-胺类化合物(m＝12)的分子式为：
(Fe3O4&SiO2)Si(OCH3)3(CH2)3N127[(CH2)2CONH(CH2)2NH]254(C12H25)128，数均分子量实测为46012，分布系数为1.29。
7G磁性聚酰胺-胺类化合物(m＝12)的分子式为：
(Fe3O4&SiO2)Si(OCH3)3(CH2)3N255[(CH2)2CONH(CH2)2NH]510(C12H25)256，数均分子量实测为93245，分布系数为1.34。
8G磁性聚酰胺-胺类化合物(m＝12)的分子式为：
(Fe3O4&SiO2)Si(OCH3)3(CH2)3N511[(CH2)2CONH(CH2)2NH]1022(C12H25)512，数均分子量实测为184059，分布系数为1.38。
9G磁性聚酰胺-胺类化合物(m＝12)的分子式为：
(Fe3O4&SiO2)Si(OCH3)3(CH2)3N1023[(CH2)2CONH(CH2)2NH]204(C12H25)1024，数均分子量实测为370372，分布系数为1.41。
10G磁性聚酰胺-胺类化合物(m＝12)的分子式为：
(Fe3O4&SiO2)Si(OCH3)3(CH2)3N2047[(CH2)2CONH(CH2)2NH]409(C12H25)2048，数均分子量实测为728913，分布系数为1.49。
实施例2
以Ni&SiO2为核心0G PAMAM磁性聚酰胺-胺类化合物(m＝18)的制备。
(1)称取10g的Ni纳米粒子分散于无水乙醇(100mL)中，加入油酸，然后超声分散10分钟；将分散后的溶液转入250mL的第一容器中，加入15g TEOS和5gNH3·H2O，搅拌3小时；反应完成后，在磁场吸引的条件下，将溶液用蒸馏水反复洗涤，直至清洗后的溶液 不再变浑浊；把得到的沉淀进行80℃真空干燥，最后研细得到最终的核壳式的Ni&SiO2磁性纳米粒子。
(2)称取5g核壳式的Ni&SiO2磁性纳米粒子置于烧瓶中，滴加20mL体积浓度为10％的硅烷偶联剂(KH5503-氨基丙基三乙氧基硅烷)甲苯溶液，在温度50℃条件下，反应60min，待降至室温后减压抽滤，并用甲醇洗涤，然后于70℃真空干燥箱干燥12h。
(3)将5克硅烷化之后得到的产物置于第二容器中，缓慢滴加30％(体积百分数)的丙烯酸甲酯的甲醇溶液20mL，在温度为60℃的条件下搅拌90min后，待降至室温后减压抽滤，用甲醇洗涤，烘干。取5.8克置于烧瓶中，加入20mL 30％(体积百分数)的乙二胺的甲醇溶液，在温度为60℃的条件下搅拌180min后，待降至室温后减压抽滤，用甲醇洗涤，烘干，得到0代PAMAM树枝分子修饰的磁性纳米颗粒。
(4)将得到的1.8克0代PAMAM树枝分子加入0.5g C18H37I，室温搅拌10min后，将样品放入微波萃取罐中，在微波功率200W、温度为50℃的条件下反应30min，待降至室温后减压抽滤，用甲醇洗涤，烘干，即得到2.1克0G磁性聚酰胺-胺类化合物，即以Ni&SiO2为核心PAMAM磁性纳米抗磨剂(0G，n＝0，m＝18)。
经检测分析，0G PAMAM磁性纳米抗磨剂的分子式为(Ni&SiO2)Si(OCH3)3(CH2)3N[(CH2)2CONH(CH2)2NH]2(C18H37)2，分子量为983。
13CNMR，6(ppm)，170-180(双峰，C＝O)，52-60(五峰，C-Si)，45-51(双峰，CH3)，31-40(双峰，C-N)，10-20(四峰，CH2)。FTIR(KBr)υ(cm-1)：2980(υCH3)，2940、2870、1467(υCH2)，1644(υC＝O)，1560(υ-N-H)，1350(υC-N)，1275(υsi-C)，
Figure PCTCN2014088492-appb-000002
1080(υsi-O)，403(υNi-O)
重复步骤3和步骤4，将依次得到1～10代磁性聚酰胺-胺类化合物(1～10G，n＝1-10，m＝18)。
采用凝胶渗透色谱对1～10代PAMAM磁性纳米抗磨剂进行分析，其中1G PAMAM磁性纳米抗磨剂(m＝18)的分子式为：
(Fe3O4&SiO2)Si(OCH3)3(CH2)3N3[(CH2)2CONH(CH2)2NH]6(C18H37)4，数均分子量实测为1883，分布系数为1.02。
2G磁性聚酰胺-胺类化合物(m＝18)的分子式为：
(Ni&SiO2)Si(OCH3)3(CH2)3N7[(CH2)2CONH(CH2)2NH]14(C18H37)8，数均分子量实测为3830，分布系数为1.05。
3G磁性聚酰胺-胺类化合物(m＝18)的分子式为：
(Ni&SiO2)Si(OCH3)3(CH2)3N15[(CH2)2CONH(CH2)2NH]30(C18H37)16，数均分子量实测为7411，分布系数为1.09。
4G磁性聚酰胺-胺类化合物(m＝18)的分子式为：
(Ni&SiO2)Si(OCH3)3(CH2)3N31[(CH2)2CONH(CH2)2NH]62(C18H37)32，数均分子量实测为15565，分布系数为1.15。
5G磁性聚酰胺-胺类化合物(m＝18)的分子式为：
(Ni&SiO2)Si(OCH3)3(CH2)3N63[(CH2)2CONH(CH2)2NH]126(C18H37)64，数均分子量实测为27266，分布系数为1.19。
6G磁性聚酰胺-胺类化合物(m＝18)的分子式为：
(Ni&SiO2)Si(OCH3)3(CH2)3N127[(CH2)2CONH(CH2)2NH]254(C18H37)128，数均分子量实测为56590，分布系数为1.22。
7G磁性聚酰胺-胺类化合物(m＝18)的分子式为：
(Ni&SiO2)Si(OCH3)3(CH2)3N255[(CH2)2CONH(CH2)2NH]510(C18H37)256，数均分子量实测为114575，分布系数为1.29。
8G磁性聚酰胺-胺类化合物(m＝18)的分子式为：
(Ni&SiO2)Si(OCH3)3(CH2)3N511[(CH2)2CONH(CH2)2NH]1022(C18H37)512，数均分子量实测为226895，分布系数为1.33。
9G磁性聚酰胺-胺类化合物(m＝18)的分子式为：
(Ni&SiO2)Si(OCH3)3(CH2)3N1023[(CH2)2CONH(CH2)2NH]2046(C18H37)1024，数均分子量实测为456214，分布系数为1.39。
10G磁性聚酰胺-胺类化合物(m＝18)的分子式为：
(Ni&SiO2)Si(OCH3)3(CH2)3N2047[(CH2)2CONH(CH2)2NH]4094(C18H37)2048，数均分子量实测为900771，分布系数为1.45。
实施例3
以Fe3O4&SiO2为核心的4G磁性聚酰胺-胺类化合物(n＝4，m＝15)作为磁性纳米抗磨剂用于汽油发动机润滑油按照表1的配方，分别采用4G磁性聚酰胺-胺类化合物(n＝4，m＝15)作为4G磁性纳米抗磨剂A(Fe：2.58ppm、Si：0.05ppm)、目前市场中常见的有机钼盐抗磨剂(如二烷基二硫代磷酸钼)，调配SM 5W-30汽油发动机润滑油。
表1 SM 5W-30汽油发动机润滑油
Figure PCTCN2014088492-appb-000003
注：A*里面含有抗磨添加剂，抗磨添加剂指的是二烷基二硫代磷酸锌(ZnDDP)。
SM 5W-30汽油发动机润滑油的分析结果如下：
表2 SM 5W-30汽油发动机润滑油分析结果
Figure PCTCN2014088492-appb-000004
注：M*摩擦副模式：球与盘，试验条件：50hz，200g，80℃。
从表2的分析数据可以看出，使用本实施例的用4G磁性纳米抗磨剂A调配的SM 5W-30 油品的摩擦系数为0.07，而二烷基二硫代磷酸钼作为抗磨剂调配的SM 5W-30油品的摩擦系数为0.11，由此说明4G磁性聚酰胺-胺类化合物(n＝4，m＝15)是非常优秀的磁性纳米抗磨剂。
实施例4
以γ-Fe2O3&SiO2为核心4G磁性聚酰胺-胺类化合物(n＝4，m＝18)作为磁性纳米抗磨剂用于柴油发动机润滑油中。
按照表3的配方，用4G磁性聚酰胺-胺类化合物(n＝4，m＝18)作为4G磁性纳米抗磨剂B(Fe：429ppm、Si：9.1ppm)调配CJ-4 5W-40柴油发动机润滑油。
表3 CJ-4 5W-40柴油发动机润滑油配方
Figure PCTCN2014088492-appb-000005
注：B*里面不含有抗磨添加剂。
CJ-4 5W-40柴油油机油的分析结果如下：
表4 CJ-4 5W-40柴油发动机润滑油分析结果
Figure PCTCN2014088492-appb-000006
Figure PCTCN2014088492-appb-000007
注：M*摩擦副模式：球与盘，试验条件：50hz，200g，80℃。
从上表可以看出，采用SRV对配方I进行抗磨性能测试，试验结果表明，摩擦系数曲线不稳定。而加入本实施例的4G磁性纳米抗磨剂B后，CJ-4 5W-40柴油发动机润滑油的摩擦系数稳定，仅为0.09，由此说明4G磁性聚酰胺-胺类化合物(n＝4，m＝18)具有良好的抗磨性能，是非常优秀的抗磨添加剂。
实施例5
以γ-Fe3O4&SiO2为核心4G磁性聚酰胺-胺类化合物(n＝4，m＝18)作为磁性纳米抗磨剂用于柴油发动机润滑油中。
按照表5的配方，用4G磁性聚酰胺-胺类化合物(n＝4，m＝18)作为4G磁性纳米抗磨剂C(Fe：259ppm、Si：5.41ppm)调配CJ-4 5W-40柴油发动机润滑油。
表5 CJ-4 5W-40柴油发动机润滑油配方
Figure PCTCN2014088492-appb-000008
注：C*里面不含有抗磨添加剂。
CJ-4 5W-40柴油油机油的分析结果如下：
表6 CJ-4 5W-40柴油发动机润滑油分析结果
Figure PCTCN2014088492-appb-000009
Figure PCTCN2014088492-appb-000010
注：M*摩擦副模式：球与盘，试验条件：50hz，200g，80℃。
从上表可以看出，采用SRV对配方I进行抗磨性能测试，试验结果表明，摩擦系数曲线不稳定。而加入本实施例的4G磁性纳米抗磨剂C后，CJ-4 5W-40柴油发动机润滑油的摩擦系数稳定，仅为0.09，由此说明4G磁性聚酰胺-胺类化合物(n＝4，m＝18)具有良好的抗磨性能，是非常优秀的抗磨添加剂。
实施例6
以Ni&SiO2为核心5G磁性聚酰胺-胺类化合物(n＝5，m＝12)作为磁性纳米抗磨剂用于柴油发动机润滑油中。
按照表7的配方，用5G磁性聚酰胺-胺类化合物(n＝5，m＝12)作为磁性纳米抗磨剂D(Ni：108ppm、Si：20.1ppm)调配CF-4 5W-30柴油发动机润滑油。
表7 CF-4 5W-30柴油发动机润滑油配方
Figure PCTCN2014088492-appb-000011
注：D*里面不含有抗磨添加剂。
CF-4 5W-30柴油油机油的分析结果如下：
表8 CF-4 5W-30柴油发动机润滑油分析结果
Figure PCTCN2014088492-appb-000012
Figure PCTCN2014088492-appb-000013
注：M*摩擦副模式：球与盘，试验条件：50hz，200g，80℃。
从上表可以看出，采用SRV对配方I进行抗磨性能测试，试验结果表明，摩擦系数曲线不稳定。而加入本实施例的5G磁性纳米抗磨剂D后，CF-4 5W-30柴油发动机润滑油的摩擦系数稳定，仅为0.08，由此说明5G磁性聚酰胺-胺类化合物(n＝5，m＝12)具有良好的抗磨性能，是非常优秀的抗磨添加剂。
实施例7
以Fe3O4&SiO2为核心5G磁性聚酰胺-胺类化合物(n＝5，m＝5)作为磁性纳米抗磨剂用于柴油发动机润滑油中。
按照表9的配方，用5G磁性聚酰胺-胺类化合物(n＝5，m＝5)作为磁性纳米抗磨剂E(Fe：68ppm、Si：1.45ppm)调配CF-4 5W-30柴油发动机润滑油。
表9 CF-4 5W-30柴油发动机润滑油配方
Figure PCTCN2014088492-appb-000014
注：E*里面不含有抗磨添加剂。
CF-4 5W-30柴油油机油的分析结果如下：
表10 CF-4 5W-30柴油发动机润滑油分析结果
Figure PCTCN2014088492-appb-000015
注：M*摩擦副模式：球与盘，试验条件：50hz，200g，80℃。
从上表可以看出，采用SRV对配方I进行抗磨性能测试，试验结果表明，摩擦系数曲线不稳定。而加入本实施例的5G磁性纳米抗磨剂E后，CF-4 5W-30柴油发动机润滑油的摩擦系数稳定，仅为0.08，由此说明5G磁性聚酰胺-胺类化合物(n＝5，m＝5)具有良好的抗磨性能，是非常优秀的抗磨添加剂。
实施例8
以Fe3O4&SiO2为核心6G磁性聚酰胺-胺类化合物(n＝6，m＝12)作为磁性纳米抗磨剂用于柴油发动机润滑油中。
按照表9的配方，用6G磁性聚酰胺-胺类化合物(n＝6，m＝12)作为磁性纳米抗磨剂F(Fe：73ppm、Si：1.52ppm)调配CF-4 5W-30柴油发动机润滑油。
表11 CF-4 5W-30柴油发动机润滑油配方
Figure PCTCN2014088492-appb-000016
Figure PCTCN2014088492-appb-000017
注：F*里面不含有抗磨添加剂。
CF-4 5W-30柴油油机油的分析结果如下：
表12 CF-4 5W-30柴油发动机润滑油分析结果
Figure PCTCN2014088492-appb-000018
注：M*摩擦副模式：球与盘，试验条件：50hz，200g，80℃。
从上表可以看出，采用SRV对配方I进行抗磨性能测试，试验结果表明，摩擦系数曲线不稳定。而加入本实施例的6G磁性纳米抗磨剂F后，CF-4 5W-30柴油发动机润滑油的摩擦系数稳定，仅为0.07，由此说明6G磁性聚酰胺-胺类化合物(n＝6，m＝12)具有良好的抗磨性能，是非常优秀的抗磨添加剂。
实施例9
以γ-Fe2O3&SiO2为核心6G磁性聚酰胺-胺类化合物(n＝6，m＝3)作为磁性纳米抗磨剂用于柴油发动机润滑油中。
按照表13的配方，用6G磁性聚酰胺-胺类化合物(n＝6，m＝3)作为磁性纳米抗磨剂H(Fe：49ppm、Si：1.08ppm)调配CF-4 5W-30柴油发动机润滑油。
表13 CF-4 5W-30柴油发动机润滑油配方
Figure PCTCN2014088492-appb-000019
Figure PCTCN2014088492-appb-000020
注：M*里面不含有抗磨添加剂。
CF-4 5W-30柴油油机油的分析结果如下：
表14 CF-4 5W-30柴油发动机润滑油分析结果
Figure PCTCN2014088492-appb-000021
注：M*摩擦副模式：球与盘，试验条件：50hz，200g，80℃。
从上表可以看出，采用SRV对配方I进行抗磨性能测试，试验结果表明，摩擦系数曲线不稳定。而加入本实施例的6G磁性纳米抗磨剂H后，CF-4 5W-30柴油发动机润滑油的摩擦系数稳定，仅为0.08，由此说明6G磁性聚酰胺-胺类化合物(n＝6，m＝3)具有良好的抗磨性能，是非常优秀的抗磨添加剂。
实施例10
以Fe2O3&SiO2为核心7G磁性聚酰胺-胺类化合物(n＝7，m＝1)作为磁性纳米抗磨剂用于柴油发动机润滑油
按照表15的配方，用7G磁性聚酰胺-胺类化合物(n＝7，m＝1)作为磁性纳米抗磨剂J(Fe：50ppm、Si：1.0ppm)调配CF-4 5W-40柴油发动机润滑油。
表15 CF-4 5W-40柴油发动机润滑油配方
Figure PCTCN2014088492-appb-000022
注：N*里面不含有抗磨添加剂。
CF-4 5W-40柴油发动机润滑油的分析结果如下：
表16 CF-4 5W-40柴油发动机润滑油分析结果
Figure PCTCN2014088492-appb-000023
注：M*摩擦副模式：球与盘，试验条件：50hz，200g，80℃。
从上表可以看出，采用SRV对配方I进行抗磨性能测试，试验结果表明，摩擦系数曲线不稳定。而加入本实施例的7G磁性纳米抗磨剂J后，CF-4 5W-40柴油发动机润滑油的摩擦系数稳定，仅为0.06，由此说明7G磁性聚酰胺-胺类化合物(n＝7，m＝1)具有良好的抗磨性能，是非常优秀的抗磨添加剂。
实施例11
以Fe3O4&SiO2为核心7G磁性聚酰胺-胺类化合物(n＝7，m＝12)作为磁性纳米抗磨剂 用于汽油发动机润滑油中。
按照表17的配方，分别采用7G磁性聚酰胺-胺类化合物(n＝7，m＝12)作为磁性纳米抗磨剂K(Fe：28ppm、Si：0.61ppm)和目前市场中常见的有机钼盐抗磨剂(如二烷基二硫代磷酸钼)，调配SN/GF-5 0W-20汽油发动机润滑油。
表17 SN/GF-5 0W-20汽油发动机润滑油
Figure PCTCN2014088492-appb-000024
注：P*里面含有抗磨添加剂，抗磨添加剂指的是二烷基二硫代磷酸锌(ZDDP)。
SN/GF-5 0W-20汽油发动机润滑油的分析结果如下：
表18 SN/GF-5 0W-20汽油发动机润滑油分析结果
Figure PCTCN2014088492-appb-000025
注：M*摩擦副模式：球与盘，试验条件：50hz，200g，80℃。
从表18的分析数据可以看出，使用本实施例的7G磁性纳米抗磨剂K调配的SN/GF-50W-20油品的摩擦系数为0.07，而二烷基二硫代磷酸钼作为抗磨剂调配的SN/GF-5 0W-20 油品的摩擦系数为0.10，由此说明7G磁性聚酰胺-胺类化合物(n＝7，m＝12)是非常优秀的磁性纳米抗磨剂。
实施例12
以Ni&SiO2为核心8G磁性聚酰胺-胺类化合物(n＝8，m＝8)作为磁性纳米抗磨剂用于汽油发动机润滑油中。
按照表19的配方，分别采用8G磁性聚酰胺-胺类化合物(n＝8，m＝8)作为磁性纳米抗磨剂L(Ni：0.31ppm、Si：0.06ppm)和目前市场中常见的有机钼盐抗磨剂(如二烷基二硫代磷酸钼)，调配SN/GF-5 0W-30汽油发动机润滑油。
表19 SN/GF-5 0W-20汽油发动机润滑油
Figure PCTCN2014088492-appb-000026
注：Q里面含有抗磨添加剂，抗磨添加剂指的是二烷基二硫代磷酸锌(ZDDP)。
SN/GF-5 0W-30汽油发动机润滑油的分析结果如下：
表20 SN/GF-5 0W-30汽油发动机润滑油分析结果
Figure PCTCN2014088492-appb-000027
Figure PCTCN2014088492-appb-000028
注：M*摩擦副模式：球与盘，试验条件：50hz，200g，80℃。
从表20的分析数据可以看出，使用本实施例的8G磁性纳米抗磨剂L调配的SN/GF-50W-30油品的摩擦系数为0.08，而二烷基二硫代磷酸钼作为抗磨剂调配的SN/GF-5 0W-20油品的摩擦系数为0.11，由此说明8G磁性聚酰胺-胺类化合物(n＝8，m＝8)是非常优秀的磁性纳米抗磨剂。
实施例13
以Ni&SiO2为核心9G磁性聚酰胺-胺类化合物(n＝9，m＝5)作为磁性纳米抗磨剂用于柴油发动机润滑油中。
按照表21的配方，分别采用9G磁性聚酰胺-胺类化合物(n＝9，m＝5)作为磁性纳米抗磨剂M(Ni：6.4ppm、Si：1.2ppm)和目前市场中常见的有机钼盐抗磨剂(如二烷基二硫代磷酸钼)，调配CI-4 10W-30柴油发动机润滑油。
表21 CI-4 10W-30柴油发动机润滑油
Figure PCTCN2014088492-appb-000029
注：W*里面含有抗磨添加剂，抗磨添加剂指的是二烷基二硫代磷酸锌(ZDDP)。
CI-410W-30柴油发动机润滑油的分析结果如下：
表22 CI-4 10W-30柴油发动机润滑油分析结果
Figure PCTCN2014088492-appb-000030
Figure PCTCN2014088492-appb-000031
注：M*摩擦副模式：球与盘，试验条件：50hz，200g，80℃。
从表22的分析数据可以看出，使用本实施例的9G磁性纳米抗磨剂调配的CI-410W-30油品的摩擦系数为0.06，而二烷基二硫代磷酸钼作为抗磨剂调配的CI-410W-30油品的摩擦系数为0.13，由此说明9G磁性聚酰胺-胺类化合物(n＝9，m＝5)是非常优秀的磁性纳米抗磨剂。
实施例14
以γ-Fe2O3&SiO2为核心10G磁性聚酰胺-胺类化合物(n＝10，m＝4)作为磁性纳米抗磨剂用于柴油发动机润滑油
按照表23的配方，分别采用10G磁性聚酰胺-胺类化合物(n＝10，m＝4)作为磁性纳米抗磨剂N(Fe：7ppm、Si：0.17ppm)和目前市场中常见的有机钼盐抗磨剂(如二烷基二硫代磷酸钼)，调配CF-4 15W-40柴油发动机润滑油。
表23 CF-4 15W-40汽油发动机润滑油
Figure PCTCN2014088492-appb-000032
注：Y*里面含有抗磨添加剂，抗磨添加剂指的是二烷基二硫代磷酸锌(ZDDP)。
CF-415W-40柴油发动机润滑油的分析结果如下：
表24 CF-4 15W-40柴油发动机润滑油分析结果
Figure PCTCN2014088492-appb-000033
Figure PCTCN2014088492-appb-000034
注：M*摩擦副模式：球与盘，试验条件：50hz，200g，80℃。
从表24的分析数据可以看出，使用本实施例的10G磁性纳米抗磨剂N调配的CF-415W-40柴油发动机润滑油的摩擦系数为0.09，而二烷基二硫代磷酸钼作为抗磨剂调配的CF-415W-40柴油发动机润滑油的摩擦系数为0.13，由此说明10G磁性聚酰胺-胺类化合物(n＝10，m＝4)是非常优秀的磁性纳米抗磨剂。
实施例15
以Fe3O4&SiO2为核心6G磁性聚酰胺-胺类化合物(n＝6，m＝12)作为磁性纳米抗磨剂用于汽油发动机润滑油中。
按照表25的配方，分别采用6G磁性聚酰胺-胺类化合物(n＝6，m＝12)作为磁性纳米抗磨剂P(Fe：0.3ppm、Si：0.01ppm)和目前市场中常见的有机钼盐抗磨剂(如二烷基二硫代磷酸钼)，调配SM 0W-30汽油发动机润滑油。
表25 SM 0W-30汽油发动机润滑油
Figure PCTCN2014088492-appb-000035
注：Z*里面含有抗磨添加剂，抗磨添加剂指的是二烷基二硫代磷酸锌(ZnDDP)。
SM 0W-30汽油发动机润滑油的分析结果如下：
表26 SM 0W-30汽油发动机润滑油分析结果
Figure PCTCN2014088492-appb-000036
注：M*摩擦副模式：球与盘，试验条件：50hz，200g，80℃。
从表26的分析数据可以看出，使用6G磁性纳米抗磨剂P调配的SM 0W-30油品的摩擦系数为0.06，而二烷基二硫代磷酸钼作为抗磨剂调配的SM 0W-30油品的摩擦系数为0.12，由此说明6G磁性聚酰胺-胺类化合物(n＝6，m＝12)是非常优秀的磁性纳米抗磨剂。
实施例16
以γ-Fe2O3&SiO2为核心3G磁性聚酰胺-胺类化合物(n＝3，m＝17)作为磁性纳米抗磨剂用于汽油发动机润滑油中。
按照表27的配方，分别采用3G磁性聚酰胺-胺类化合物(n＝3，m＝17)作为磁性纳米抗磨剂Q(Fe：2.3ppm、Si：0.05ppm)和目前市场中常见的有机钼盐抗磨剂(如二烷基二硫代磷酸钼)，调配SN 5W-30汽油发动机润滑油。
表27 SN 5W-30汽油发动机机润滑油
Figure PCTCN2014088492-appb-000037
Figure PCTCN2014088492-appb-000038
注：R*里面含有抗磨添加剂，抗磨添加剂指的是二烷基二硫代磷酸锌(ZnDDP)。
SN 5W-30汽油发动机润滑油的分析结果如下：
表28 SN 5W-30汽油发动机润滑油分析结果
Figure PCTCN2014088492-appb-000039
注：M*摩擦副模式：球与盘，试验条件：50hz，200g，80℃。
从表28的分析数据可以看出，使用本实施例用3G磁性纳米抗磨剂Q调配的SN 5W-30油品的摩擦系数为0.08，而二烷基二硫代磷酸钼作为抗磨剂调配的SN 5W-30油品的摩擦系数为0.12，由此说明磁性聚酰胺-胺类化合物(n＝3，m＝17)是非常优秀的磁性纳米抗磨剂。
实施例17
以Fe3O4&SiO2为核心的1G磁性聚酰胺-胺类化合物作为磁性纳米抗磨剂用于汽油发动机润滑油按照表29的配方，分别采用1G磁性聚酰胺-胺类化合物(作为1G磁性纳米抗磨剂O(Fe：10ppm、Si：0.2ppm)目前市场中常见的有机钼盐抗磨剂(如二烷基二硫代磷酸钼)，调配SM 5W-30汽油发动机润滑油。
表29 SM 5W-20汽油发动机润滑油
Figure PCTCN2014088492-appb-000040
Figure PCTCN2014088492-appb-000041
注：O*里面含有抗磨添加剂，抗磨添加剂指的是二烷基二硫代磷酸锌(ZnDDP)。
SM 5W-20汽油发动机润滑油的分析结果如下：
表30 SM 5W-20汽油发动机润滑油分析结果
Figure PCTCN2014088492-appb-000042
注：M*摩擦副模式：球与盘，试验条件：50hz，200g，80℃。
从表30的分析数据可以看出，使用本实施例的用1G磁性纳米抗磨剂O调配的SM5W-20油品的摩擦系数为0.08，而二烷基二硫代磷酸钼作为抗磨剂调配的SM 5W-20油品的摩擦系数为0.11，由此说明1G磁性聚酰胺-胺类化合物是非常优秀的磁性纳米抗磨剂。
实施例18
将γ-Fe2O3&SiO2为核心的5G磁性聚酰胺-胺类化合物溶解到100N的基础油中，使用SRV对其进行抗磨性能测试。其结果如图4所示。从图4可以看出，随着负载增加，摩擦系数略有降低，摩擦系数在0.119左右趋于稳定。这是由于摩擦付表面油膜逐渐形成，并且稳定，说明5G磁性聚酰胺-胺类化合物具有良好的抗磨性能。而当负载加到1100N时，摩 擦系数突然升高，这是由于摩擦付表面的油膜破裂，失去润滑作用。而常用的有机钼盐(如二烷基二硫代磷酸钼)在相同条件下，当负载加到800N时，摩擦付表面的油膜破裂(如图5)，由此说明，5G磁性聚酰胺-胺类化合物具有优异的极压性能。
虽然，上文中已经用一般性说明及具体实施方案对本发明作了详尽的描述，但在本发明基础上，可以对之作一些修改或改进，这对本领域技术人员而言是显而易见的。因此，在不偏离本发明精神的基础上所做的这些修改或改进，均属于本发明要求保护的范围。

Claims (17)

  1. 一种磁性树枝分子化合物，其分子式如式I所示：
    Figure PCTCN2014088492-appb-100001
    其中，Г表示表面包覆了SiO2的磁性颗粒，且所述磁性颗粒经硅烷偶联剂进行了表面修饰，所述
    Figure PCTCN2014088492-appb-100002
    为具有树枝状结构的基团，所述
    Figure PCTCN2014088492-appb-100003
    为亲油性基团，0≤n≤100。
  2. 根据权利要求1所述的磁性树枝分子化合物，其特征在于，所述磁性颗粒为磁性纳米颗粒。
  3. 根据权利要求1或2所述的磁性树枝分子化合物，其特征在于，0≤n≤10。
  4. 根据权利要求1-3中任一项所述的磁性树枝分子化合物，其特征在于，所述磁性颗粒含有Fe3O4、Ni或γ-Fe2O3中的至少一种。
  5. 根据权利要求1-4中任一项所述的磁性树枝分子化合物，其特征在于，所述磁性颗粒选自外层包覆有SiO2的核壳式的Fe3O4&SiO2磁性纳米粒子，且所述磁性颗粒经硅烷偶联剂进行了表面修饰。
  6. 根据权利要求1-5中任一项所述的磁性树枝分子化合物，其特征在于，所述硅烷偶联剂为3-氨基丙基三乙氧基硅烷、3-缩水甘油醚氧基丙基三甲氧基硅烷或3-氨基丙基三甲氧基硅烷。
  7. 根据权利要求1-6中任一项所述的磁性树枝分子化合物，所述R1选自具有以式II的所示重复单元结构的聚酰胺-胺型树枝状高分子；
    -(CH2)2CONH(CH2)2NH-    II。
  8. 根据权利要求1-7中任一项所述的磁性树枝分子化合物，所述R2选自C1-18的支链或直链的烷基。
  9. 一种根据权利要求1-8中任一项所述的磁性树枝分子化合物的制备方法，其特征在于，包括如下步骤：
    i)提供包覆了SiO2的磁性颗粒；
    ii)使用硅烷偶联剂对所述磁性颗粒的表面进行修饰，然后将修饰后的产物与所述树枝状分子反应，使得所述树枝状分子键合于所述磁性纳米颗粒；
    iii)将步骤ii)得到的树枝分子键合磁性颗粒产物与带有亲油基团的化合物反应，得到所述磁性树枝分子化合物。
  10. 根据权利要求9所述的方法，其特征在于，所述带有亲油基团的化合物为卤代烃，优选一卤代烷烃，更优选为一碘代烷烃。
  11. 权利要求1-8中任一项所述的磁性树枝分子化合物在制备润滑油用抗磨添加剂中的应用。
  12. 一种含有根据权利要求1-8中任一项所述的磁性树枝分子化合物的润滑剂。
  13. 根据权利要求12所述的润滑剂，其特征在于，所磁性树枝分子化合物在所述润滑剂中的质量含量为100ppm～5％。
  14. 根据权利要求12或13所述的润滑剂，其特征在于，Fe和/或Ni的重量含量为0.01ppm～0.20％，优选0.01ppm～429ppm。
  15. 根据权利要求12-14中任一项所述的润滑剂，其特征在于，所述润滑剂中的Si的重量含量为0.01～0.20％，优选0.01～20.1ppm。
  16. 根据权利要求12-15中任一项所述的润滑剂，其特征在于，所述磁性树枝分子化合物选自式III所示的磁性聚酰胺-胺类化合物，
    Figure PCTCN2014088492-appb-100004
    其中，Г表示表面包覆了SiO2的磁性颗粒，且所述磁性颗粒经硅烷偶联剂进行了表面修饰，所述
    Figure PCTCN2014088492-appb-100005
    为具有树枝状结构的基团，所述
    Figure PCTCN2014088492-appb-100006
    为亲油性基团，0≤n≤10，1≤m≤18。
  17. 根据权利要求16所述的润滑剂，其特征在于，所述磁性聚酰胺-胺类化合物中n选自5～9中的整数，m选自9～13中的整数。
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